Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence.

PubMed

Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K L; Sum, Tze Chien; Huang, Wei

2017-02-27

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 10 15  cm -3 , defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence.

Magnetic field enhancement of organic photovoltaic cells performance.

PubMed

Oviedo-Casado, S; Urbina, A; Prior, J

2017-06-27

Charge separation is a critical process for achieving high efficiencies in organic photovoltaic cells. The initial tightly bound excitonic electron-hole pair has to dissociate fast enough in order to avoid photocurrent generation and thus power conversion efficiency loss via geminate recombination. Such process takes place assisted by transitional states that lie between the initial exciton and the free charge state. Due to spin conservation rules these intermediate charge transfer states typically have singlet character. Here we propose a donor-acceptor model for a generic organic photovoltaic cell in which the process of charge separation is modulated by a magnetic field which tunes the energy levels. The impact of a magnetic field is to intensify the generation of charge transfer states with triplet character via inter-system crossing. As the ground state of the system has singlet character, triplet states are recombination-protected, thus leading to a higher probability of successful charge separation. Using the open quantum systems formalism we demonstrate that the population of triplet charge transfer states grows in the presence of a magnetic field, and discuss the impact on carrier population and hence photocurrent, highlighting its potential as a tool for research on charge transfer kinetics in this complex systems.

Effects of the impurity-host interactions on the nonradiative processes in ZnS:Cr

NASA Astrophysics Data System (ADS)

Tablero, C.

2010-11-01

There is a great deal of controversy about whether the behavior of an intermediate band in the gap of semiconductors is similar or not to the deep-gap levels. It can have significant consequences, for example, on the nonradiative recombination. In order to analyze the behavior of an intermediate band, we have considered the effect of the inward and outward displacements corresponding to breathing and longitudinal modes of Cr-doped ZnS and on the charge density for different processes involved in the nonradiative recombination using first-principles. This metal-doped zinc chalcogenide has a partially filled band within the host semiconductor gap. In contrast to the properties exhibited by deep-gap levels in other systems, we find small variations in the equilibrium configurations, forces, and electronic density around the Cr when the nonradiative recombination mechanisms modify the intermediate band charge. The charge density around the impurity is equilibrated in response to the perturbations in the equilibrium nuclear configuration and the charge of the intermediate band. The equilibration follows a Le Chatelier principle through the modification of the contribution from the impurity to the intermediate band and to the valence band. The intermediate band introduced by Cr in ZnS for the concentrations analyzed makes the electronic capture difficult and later multiphonon emission in the charge-transfer processes, in accordance with experimental results.

Impact of Electrodes on Recombination in Bulk Heterojunction Organic Solar Cells

PubMed Central

2018-01-01

In recent years, the efficiency of organic solar cells (OSCs) has increased to more than 13%, although different barriers are on the way for reaching higher efficiencies. One crucial barrier is the recombination of charge carriers, which can either occur as the bulk recombination of photogenerated charges or the recombination of photogenerated charges and electrodic induced charges (EICs). This work studies the impact of EICs on the recombination lifetime in OSCs. To this end, the net recombination lifetime of photogenerated charge carriers in the presence of EICs is measured by means of conventional and newly developed transient photovoltage techniques. Moreover, a new approach has been introduced to exclusively measure the bulk recombination lifetime, i.e., in the absence of EICs; this approach was conducted by depositing transparent insulating layers on both sides of the OSC active layer. An examination of these approaches on OSCs with different active layer materials, thicknesses, and varying light intensities determined that the EICs can only reduce the recombination lifetime of the photogenerated charges in OSCs with very weak recombination strength. This work supports that for OSCs with highly reduced recombination strength, eliminating the recombination of photogenerated charges and EICs is critical for achieving better performance. Therefore, the use of a proper blocking layer suppresses EIC recombination in systems with very weak recombination. PMID:29546982

Reduced Carrier Recombination in PbS - CuInS2 Quantum Dot Solar Cells

PubMed Central

Sun, Zhenhua; Sitbon, Gary; Pons, Thomas; Bakulin, Artem A.; Chen, Zhuoying

2015-01-01

Energy loss due to carrier recombination is among the major factors limiting the performance of TiO2/PbS colloidal quantum dot (QD) heterojunction solar cells. In this work, enhanced photocurrent is achieved by incorporating another type of hole-transporting QDs, Zn-doped CuInS2 (Zn-CIS) QDs into the PbS QD matrix. Binary QD solar cells exhibit a reduced charge recombination associated with the spatial charge separation between these two types of QDs. A ~30% increase in short-circuit current density and a ~20% increase in power conversion efficiency are observed in binary QD solar cells compared to cells built from PbS QDs only. In agreement with the charge transfer process identified through ultrafast pump/probe spectroscopy between these two QD components, transient photovoltage characteristics of single-component and binary QDs solar cells reveal longer carrier recombination time constants associated with the incorporation of Zn-CIS QDs. This work presents a straightforward, solution-processed method based on the incorporation of another QDs in the PbS QD matrix to control the carrier dynamics in colloidal QD materials and enhance solar cell performance. PMID:26024021

Spectral Diagnostics of Galactic and Stellar X-Ray Emission from Charge Exchange Recombination

NASA Technical Reports Server (NTRS)

Wargelin, B.

2002-01-01

The proposed research uses the electron beam ion trap at the Lawrence Livermore National Laboratory (LLNL) to study X-ray emission from charge-exchange recombination of highly charged ions with neutral gases. The resulting data fill a void in existing experimental and theoretical understanding of this atomic physics process, and are needed to explain all or part of the observed X-ray emission from the soft X-ray background, stellar winds, the Galactic Center, supernova ejecta, and photoionized nebulae. Progress made during the first year of the grant is described, as is work planned for the second year.

The effect of solvent relaxation time constants on free energy gap law for ultrafast charge recombination following photoinduced charge separation.

PubMed

Mikhailova, Valentina A; Malykhin, Roman E; Ivanov, Anatoly I

2018-05-16

To elucidate the regularities inherent in the kinetics of ultrafast charge recombination following photoinduced charge separation in donor-acceptor dyads in solutions, the simulations of the kinetics have been performed within the stochastic multichannel point-transition model. Increasing the solvent relaxation time scales has been shown to strongly vary the dependence of the charge recombination rate constant on the free energy gap. In slow relaxing solvents the non-equilibrium charge recombination occurring in parallel with solvent relaxation is very effective so that the charge recombination terminates at the non-equilibrium stage. This results in a crucial difference between the free energy gap laws for the ultrafast charge recombination and the thermal charge transfer. For the thermal reactions the well-known Marcus bell-shaped dependence of the rate constant on the free energy gap is realized while for the ultrafast charge recombination only a descending branch is predicted in the whole area of the free energy gap exceeding 0.2 eV. From the available experimental data on the population kinetics of the second and first excited states for a series of Zn-porphyrin-imide dyads in toluene and tetrahydrofuran solutions, an effective rate constant of the charge recombination into the first excited state has been calculated. The obtained rate constant being very high is nearly invariable in the area of the charge recombination free energy gap from 0.2 to 0.6 eV that supports the theoretical prediction.

"Fuel Gage" for Electric Vehicles

NASA Technical Reports Server (NTRS)

Rowlette, J. J.

1984-01-01

Gas-emmission and time-integrated-current measurements indicate battery charge state. Tests indicate possibility of monitoring state of charge of lead/acid batteries at any stage in charging cycle by measuring charging current and either gas evolution or electrode potential. Data then processed by microcomputer. Uses include cell voltage, cell pressure, cell temperature and rate of gas recombination on catalyst.

The rates of charge separation and energy destructive charge recombination processes within an organic dyad in presence of metal-semiconductor core shell nanocomposites.

PubMed

Mandal, Gopa; Bhattacharya, Sudeshna; Das, Subrata; Ganguly, Tapan

2012-01-01

Steady state and time resolved spectroscopic measurements were made at the ambient temperature on an organic dyad, 1-(4-Chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA), where the donor 1-methoxynaphthalene (1 MNT) is connected with the acceptor p-chloroacetophenone (PCA) by an unsaturated olefinic bond, in presence of Ag@TiO2 nanoparticles. Time resolved fluorescence and absorption measurements reveal that the rate parameters associated with charge separation, k(CS), within the dyad increases whereas charge recombination rate k(CR) reduces significantly when the surrounding medium is changed from only chloroform to mixture of chloroform and Ag@TiO2 (noble metal-semiconductor) nanocomposites. The observed results indicate that the dyad being combined with core-shell nanocomposites may form organic-inorganic nanocomposite system useful for developing light energy conversion devices. Use of metal-semiconductor nanoparticles may provide thus new ways to modulate charge recombination processes in light energy conversion devices. From comparison with the results obtained in our earlier investigations with only TiO2 nanoparticles, it is inferred that much improved version of light energy conversion device, where charge-separated species could be protected for longer period of time of the order of millisecond, could be designed by using metal-semiconductor core-shell nanocomposites rather than semiconductor nanoparticles only.

Influence of the electron-cation interaction on electron mobility in dye-sensitized ZnO and TiO2 nanocrystals: a study using ultrafast terahertz spectroscopy.

PubMed

Nemec, H; Rochford, J; Taratula, O; Galoppini, E; Kuzel, P; Polívka, T; Yartsev, A; Sundström, V

2010-05-14

Charge transport and recombination in nanostructured semiconductors are poorly understood key processes in dye-sensitized solar cells. We have employed time-resolved spectroscopies in the terahertz and visible spectral regions supplemented with Monte Carlo simulations to obtain unique information on these processes. Our results show that charge transport in the active solar cell material can be very different from that in nonsensitized semiconductors, due to strong electrostatic interaction between injected electrons and dye cations at the surface of the semiconductor nanoparticle. For ZnO, this leads to formation of an electron-cation complex which causes fast charge recombination and dramatically decreases the electron mobility even after the dissociation of the complex. Sensitized TiO2 does not suffer from this problem due to its high permittivity efficiently screening the charges.

Engineering charge transport by heterostructuring solution-processed semiconductors

NASA Astrophysics Data System (ADS)

Voznyy, Oleksandr; Sutherland, Brandon R.; Ip, Alexander H.; Zhitomirsky, David; Sargent, Edward H.

2017-06-01

Solution-processed semiconductor devices are increasingly exploiting heterostructuring — an approach in which two or more materials with different energy landscapes are integrated into a composite system. Heterostructured materials offer an additional degree of freedom to control charge transport and recombination for more efficient optoelectronic devices. By exploiting energetic asymmetry, rationally engineered heterostructured materials can overcome weaknesses, augment strengths and introduce emergent physical phenomena that are otherwise inaccessible to single-material systems. These systems see benefit and application in two distinct branches of charge-carrier manipulation. First, they influence the balance between excitons and free charges to enhance electron extraction in solar cells and photodetectors. Second, they promote radiative recombination by spatially confining electrons and holes, which increases the quantum efficiency of light-emitting diodes. In this Review, we discuss advances in the design and composition of heterostructured materials, consider their implementation in semiconductor devices and examine unexplored paths for future advancement in the field.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stolterfoht, Martin; Armin, Ardalan; Pandey, Ajay K.

Photovoltaic performance in relation to charge transport is studied in efficient (7.6%) organic solar cells (PTB7:PC{sub 71}BM). Both electron and hole mobilities are experimentally measured in efficient solar cells using the resistance dependent photovoltage technique, while the inapplicability of classical techniques, such as space charge limited current and photogenerated charge extraction by linearly increasing voltage is discussed. Limits in the short-circuit current originate from optical losses, while charge transport is shown not to be a limiting process. Efficient charge extraction without recombination can be achieved with a mobility of charge carriers much lower than previously expected. The presence of dispersivemore » transport with strongly distributed mobilities in high efficiency solar cells is demonstrated. Reduced non-Langevin recombination is shown to be beneficial for solar cells with imbalanced, low, and dispersive electron and hole mobilities.« less

Effective Charge Carrier Utilization in Photocatalytic Conversions.

PubMed

Zhang, Peng; Wang, Tuo; Chang, Xiaoxia; Gong, Jinlong

2016-05-17

Continuous efforts have been devoted to searching for sustainable energy resources to alleviate the upcoming energy crises. Among various types of new energy resources, solar energy has been considered as one of the most promising choices, since it is clean, sustainable, and safe. Moreover, solar energy is the most abundant renewable energy, with a total power of 173 000 terawatts striking Earth continuously. Conversion of solar energy into chemical energy, which could potentially provide continuous and flexible energy supplies, has been investigated extensively. However, the conversion efficiency is still relatively low since complicated physical, electrical, and chemical processes are involved. Therefore, carefully designed photocatalysts with a wide absorption range of solar illumination, a high conductivity for charge carriers, a small number of recombination centers, and fast surface reaction kinetics are required to achieve a high activity. This Account describes our recent efforts to enhance the utilization of charge carriers for semiconductor photocatalysts toward efficient solar-to-chemical energy conversion. During photocatalytic reactions, photogenerated electrons and holes are involved in complex processes to convert solar energy into chemical energy. The initial step is the generation of charge carriers in semiconductor photocatalysts, which could be enhanced by extending the light absorption range. Integration of plasmonic materials and introduction of self-dopants have been proved to be effective methods to improve the light absorption ability of photocatalysts to produce larger amounts of photogenerated charge carriers. Subsequently, the photogenerated electrons and holes migrate to the surface. Therefore, acceleration of the transport process can result in enhanced solar energy conversion efficiency. Different strategies such as morphology control and conductivity improvement have been demonstrated to achieve this goal. Fine-tuning of the morphology of nanostructured photocatalysts can reduce the migration distance of charge carriers. Improving the conductivity of photocatalysts by using graphitic materials can also improve the transport of charge carriers. Upon charge carrier migration, electrons and holes also tend to recombine. The suppression of recombination can be achieved by constructing heterojunctions that enhance charge separation in the photocatalysts. Surface states acting as recombination centers should also be removed to improve the photocatalytic efficiency. Moreover, surface reactions, which are the core chemical processes during the solar energy conversion, can be enhanced by applying cocatalysts as well as suppressing side reactions. All of these strategies have been proved to be essential for enhancing the activities of semiconductor photocatalysts. It is hoped that delicate manipulation of photogenerated charge carriers in semiconductor photocatalysts will hold the key to effective solar-to-chemical energy conversion.

Investigation of Exciton Recombination Zone in Quantum Dot Light-Emitting Diodes Using a Fluorescent Probe.

PubMed

Huang, Xiaoyu; Zhang, Heng; Xu, Dingxin; Wen, Feng; Chen, Shuming

2017-08-23

Exciton recombination zone, where the photons are generated, can greatly affect the performance, such as the efficiency and color purity, of the quantum dot (QD) light-emitting diodes (QLEDs). To probe the exciton recombination zone, 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) is doped into the charge transport layer as a fluorescent sensor; by monitoring the Förster resonant energy transfer (FRET) between QD and DCJTB, the location of the recombination zone can be determined. It is found that the electron transport layer (ETL) has a great impact on the recombination zone. For example, in QLEDs with ZnMgO ETL, the recombination zone is near the interface of the QD/hole transport layer (HTL) and is shifted to the interface of the QD/ETL as the driving voltage is increased, whereas in devices with 1,3,5-tris(2-N-phenylbenzimidazolyl) benzene (TPBi) ETL, the recombination zone is close to the interface of the QD/ETL and moved to the interface of the QD/HTL with the increase in the driving voltage. Our results can also clarify the light emission mechanism in QLEDs. In devices with ZnMgO ETL, the emission is dominated by the direct charge recombination, whereas in devices with TPBi ETL, the emission is contributed by both FRET and direct charge recombination. Our studies suggest that fluorescent probe can be a powerful tool for investigating the exciton recombination zone, light emission mechanism, and other fundamental processes in QLEDs.

Study of ND3-enhanced MAR processes in D2-N2 plasmas to induce plasma detachment

NASA Astrophysics Data System (ADS)

Abe, Shota; Chakraborty Thakur, Saikat; Doerner, Russ; Tynan, George

2017-10-01

The Molecular Assisted Recombination (MAR) process is thought to be a main channel of volumetric recombination to induce the plasma detachment operation. Authors have focused on a new plasma recombination process supported by ammonia molecules, which will be formed by impurity seeding of N2 for controlling divertor plasma temperature and heat loads in ITER. This ammonia-enhanced MAR process would occur throughout two steps. In this study, the first step of the new MAR process is investigated in low density plasmas (Ne 1016 m-3, Te 4 eV) fueled by D2 and N2. Ion and neutral densities are measured by a calibrated Electrostatic Quadrupole Plasma (EQP) analyzer, combination of an ion energy analyzer and mass spectrometer. The EQP shows formation of ND3 during discharges. Ion densities calculated by a rate equation model are compared with experimental results. We find that the model can reproduce the observed ion densities in the plasma. The model calculation shows that the dominant neutralization channel of Dx+(x =1-3) ions in the volume is the formation of NDy+(y =3 or 4) throughout charge/D+ exchange reactions with ND3. Furthermore, high density plasmas (Ne 1016 m-3) have been achieved to investigate electron-impact dissociative recombination processes of formed NDy+,which is the second step of this MAR process.

The flow of a dust particle by highly collisional drifting plasma

NASA Astrophysics Data System (ADS)

Grach, Veronika; Semenov, Vladimir; Trakhtengerts, Victor

We present the study of the flow of a dust particle by a weakly ionized highly collisional drifting plasma. The charging of a conductive sphere and wake formation downstream and upstream of it is analyzed in the case of a strong external field l0 = E0 /(4πen0 ) λD a (E0 is the magnitude of the external field, n0 is plasma density, λD is Debye length and a is a radius of the sphere). Under such conditions, the effects of the space charge field and ionization-recombination processes play crucial role. The sphere charge and the spatial distributions of plasma ions and electrons are calculated nu-merically; analytical expressions are obtained for some limiting cases. We obtain that the size of the wake is determined by the external field and the recombination rate. At low recombination rates (α/(4πµ+,- ) 1, where α is the recombination coefficient, µ+,- are mobilities of positive and negative plasma particles) the longitudinal scale of wake is about 20l0 , at high recombina-tion rates the longitudinal scale is about l0 . The transverse scale of the wake is determined by the ratio of the mobilities and can reach several dust particle radii. It was also shown that the absolute value of the dust particle charge decreases with increasing recombination rate. The total electric charge (the sphere charge plus the plasma space charge) is shown to be zero in accordance with predictions of the theory of static currents in a conducting medium. On the basis of the obtained spatial distributions of charged plasma particles, the electrostatic potential around the sphere is calculated numerically. The interaction potential between two systems "particle+wake" is analyzed for arbitrary locations of such systems. We obtain that the potential can be attractive at moderate and large distances, if the particles are not aligned in the direction perpendicular to the external electric field. The results can be important in understanding intergrain interactions in weakly ionized highly collisional anisotropic dusty plasmas.

Triphenylamine-Based Push–Pull Molecule for Photovoltaic Applications: From Synthesis to Ultrafast Device Photophysics

PubMed Central

2017-01-01

Small push–pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs. PMID:28413568

Role of Adsorbed Water on Charge Carrier Dynamics in Photoexcited TiO2

PubMed Central

2017-01-01

Overall photocatalytic water splitting is one of the most sought after processes for sustainable solar-to-chemical energy conversion. The efficiency of this process strongly depends on charge carrier recombination and interaction with surface adsorbates at different time scales. Here, we investigated how hydration of TiO2 P25 affects dynamics of photogenerated electrons at the millisecond to minute time scale characteristic for chemical reactions. We used rapid scan diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS). The decay of photogenerated electron absorption was substantially slower in the presence of associated water. For hydrated samples, the charge carrier recombination rates followed an Arrhenius-type behavior in the temperature range of 273–423 K; these became temperature-independent when the material was dehydrated at temperatures above 423 K or cooled below 273 K. A DFT+U analysis revealed that hydrogen bonding with adsorbed water stabilizes surface-trapped holes at anatase TiO2(101) facet and lowers the barriers for hole migration. Hence, hole mobility should be higher in the hydrated material than in the dehydrated system. This demonstrates that adsorbed associated water can efficiently stabilize photogenerated charge carriers in nanocrystalline TiO2 and suppress their recombination at the time scale up to minutes. PMID:28413570

High open-circuit voltage small-molecule p-DTS(FBTTh 2 ) 2.ICBA bulk heterojunction solar cells – morphology, excited-state dynamics, and photovoltaic performance

DOE PAGES

Ko Kyaw, Aung Ko; Gehrig, Dominik; Zhang, Jie; ...

2014-11-27

The photovoltaic performance of bulk heterojunction solar cells using the solution-processable small molecule donor 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole) (p-DTS(FBTTh 2) 2 in combination with indene-C60 bis-adduct (ICBA) as an acceptor is systematically optimized by altering the processing conditions. A high open-circuit voltage of 1 V, more than 0.2 V higher than that of a p-DTS(FBTTh 2) 2:PC 70BM blend, is achieved. However, the power conversion efficiency remains around 5% and thus is lower than ~8% previously reported for p-DTS(FBTTh 2) 2:PC 70BM. Transient absorption (TA) pump–probe spectroscopy over a wide spectral (Vis-NIR) and dynamic (fs to μs) range in combination with multivariate curvemore » resolution analysis of the TA data reveals that generation of free charges is more efficient in the blend with PC 70BM as an acceptor. In contrast, blends with ICBA create more coulombically bound interfacial charge transfer (CT) states, which recombine on the sub-nanosecond timescale by geminate recombination. Furthermore, the ns to μs charge carrier dynamics in p-DTS(FBTTh 2) 2:ICBA blends are only weakly intensity dependent implying a significant contribution of recombination from long-lived CT states and trapped charges, while those in p-DTS(FBTTh 2) 2:PC 70BM decay via an intensity-dependent recombination mechanism indicating that spatially separated (free) charge carriers are observed, which can be extracted as photocurrent from the device.« less

Experimental investigation of the excess charge and time constant of minority carriers in the thin diffused layer of 0.1 ohm-cm silicon solar cells

NASA Technical Reports Server (NTRS)

Godlewski, M. P.; Brandhorst, H. W., Jr.; Lindholm, F. A.; Sah, C. T.

1976-01-01

An experimental method is presented that can be used to interpret the relative roles of bandgap narrowing and recombination processes in the diffused layer. This method involves measuring the device time constant by open-circuit voltage decay and the base region diffusion length by X-ray excitation. A unique illuminated diode method is used to obtain the diode saturation current. These data are interpreted using a simple model to determine individually the minority carrier lifetime and the excess charge. These parameters are then used to infer the relative importance of bandgap narrowing and recombination processes in the diffused layer.

The influence of morphology on charge transport/recombination dynamics in planar perovskite solar cells

NASA Astrophysics Data System (ADS)

Yu, Man; Wang, Yi; Wang, Hao-Yi; Han, Jun; Qin, Yujun; Zhang, Jian-Ping; Ai, Xi-Cheng

2016-10-01

The photovoltaic performance of planar perovskite solar cell is significantly influenced by the morphology of perovskite film. In this work, five kinds of devices with different perovskite film morphologies were prepared by varying the concentration of CH3NH3Cl in precursor solutions. We found that best morphology of perovskite film results in the excellent photovoltaic performance with an average efficiency of 15.52% and a champion efficiency of 16.38%. Transient photovoltage and photocurrent measurements are performed to elucidate the mechanism of photoelectric conversion processes, which shows that the charge recombination is effectively suppressed and the charge transport is obviously promoted by optimized morphology.

An alternative approach to charge transport in semiconducting electrodes

NASA Technical Reports Server (NTRS)

Thomchick, J.; Buoncristiani, A. M.

1980-01-01

The excess-carrier charge transport through the space-charge region of a semiconducting electrode is analyzed by a technique known as the flux method. In this approach reflection and transmission coefficients appropriate for a sheet of uniform semiconducting material describe its transport properties. A review is presented of the flux method showing that the results for a semiconductor electrode reduce in a limiting case to those previously found by Gaertner if the depletion layer is treated as a perfectly transmitting medium in which scattering and recombination are ignored. Then, in the framework of the flux method the depletion layer is considered more realistically by explicitly taking into account scattering and recombination processes which occur in this region.

IONIZATION AND DUST CHARGING IN PROTOPLANETARY DISKS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivlev, A. V.; Caselli, P.; Akimkin, V. V., E-mail: ivlev@mpe.mpg.de

2016-12-10

Ionization–recombination balance in dense interstellar and circumstellar environments is a key factor for a variety of important physical processes, such as chemical reactions, dust charging and coagulation, coupling of the gas with magnetic field, and development of instabilities in protoplanetary disks. We determine a critical gas density above which the recombination of electrons and ions on the grain surface dominates over the gas-phase recombination. For this regime, we present a self-consistent analytical model, which allows us to calculate exactly the abundances of charged species in dusty gas, without making assumptions on the grain charge distribution. To demonstrate the importance ofmore » the proposed approach, we check whether the conventional approximation of low grain charges is valid for typical protoplanetary disks, and discuss the implications for dust coagulation and development of the “dead zone” in the disk. The presented model is applicable for arbitrary grain-size distributions and, for given dust properties and conditions of the disk, has only one free parameter—the effective mass of the ions, shown to have a small effect on the results. The model can be easily included in numerical simulations following the dust evolution in dense molecular clouds and protoplanetary disks.« less

Recombination-enhanced surface expansion of clusters in intense soft x-ray laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rupp, Daniela; Flückiger, Leonie; Adolph, Marcus

Here, we studied the nanoplasma formation and explosion dynamics of single large xenon clusters in ultrashort, intense x-ray free-electron laser pulses via ion spectroscopy. The simultaneous measurement of single-shot diffraction images enabled a single-cluster analysis that is free from any averaging over the cluster size and laser intensity distributions. The measured charge state-resolved ion energy spectra show narrow distributions with peak positions that scale linearly with final ion charge state. These two distinct signatures are attributed to highly efficient recombination that eventually leads to the dominant formation of neutral atoms in the cluster. The measured mean ion energies exceed themore » value expected without recombination by more than an order of magnitude, indicating that the energy release resulting from electron-ion recombination constitutes a previously unnoticed nanoplasma heating process. This conclusion is supported by results from semiclassical molecular dynamics simulations.« less

Recombination-enhanced surface expansion of clusters in intense soft x-ray laser pulses

DOE PAGES

Rupp, Daniela; Flückiger, Leonie; Adolph, Marcus; ...

2016-10-07

Here, we studied the nanoplasma formation and explosion dynamics of single large xenon clusters in ultrashort, intense x-ray free-electron laser pulses via ion spectroscopy. The simultaneous measurement of single-shot diffraction images enabled a single-cluster analysis that is free from any averaging over the cluster size and laser intensity distributions. The measured charge state-resolved ion energy spectra show narrow distributions with peak positions that scale linearly with final ion charge state. These two distinct signatures are attributed to highly efficient recombination that eventually leads to the dominant formation of neutral atoms in the cluster. The measured mean ion energies exceed themore » value expected without recombination by more than an order of magnitude, indicating that the energy release resulting from electron-ion recombination constitutes a previously unnoticed nanoplasma heating process. This conclusion is supported by results from semiclassical molecular dynamics simulations.« less

Chlorine Doping Reduces Electron–Hole Recombination in Lead Iodide Perovskites: Time-Domain Ab Initio Analysis

DOE PAGES

Liu, Jin; Prezhdo, Oleg V.

2015-10-27

Rapid development in lead halide perovskites has led to solution-processable thin film solar cells with power conversion efficiencies close to 20%. Nonradiative electron–hole recombination within perovskites has been identified as the main pathway of energy losses, competing with charge transport and limiting the efficiency. Using nonadiabatic (NA) molecular dynamics, combined with time-domain density functional theory, we show that nonradiative recombination happens faster than radiative recombination and long-range charge transfer to an acceptor material. Doping of lead iodide perovskites with chlorine atoms reduces charge recombination. On the one hand, chlorines decrease the NA coupling because they contribute little to the wavemore » functions of the valence and conduction band edges. On the other hand, chlorines shorten coherence time because they are lighter than iodines and introduce high-frequency modes. Both factors favor longer excited-state lifetimes. The simulation shows good agreement with the available experimental data and contributes to the comprehensive understanding of electronic and vibrational dynamics in perovskites. The generated insights into design of higher-efficiency solar cells range from fundamental scientific principles, such as the role of electron–vibrational coupling and quantum coherence, to practical guidelines, such as specific suggestions for chemical doping.« less

Discrimination between spin-dependent charge transport and spin-dependent recombination in π-conjugated polymers by correlated current and electroluminescence-detected magnetic resonance

NASA Astrophysics Data System (ADS)

Kavand, Marzieh; Baird, Douglas; van Schooten, Kipp; Malissa, Hans; Lupton, John M.; Boehme, Christoph

2016-08-01

Spin-dependent processes play a crucial role in organic electronic devices. Spin coherence can give rise to spin mixing due to a number of processes such as hyperfine coupling, and leads to a range of magnetic field effects. However, it is not straightforward to differentiate between pure single-carrier spin-dependent transport processes which control the current and therefore the electroluminescence, and spin-dependent electron-hole recombination which determines the electroluminescence yield and in turn modulates the current. We therefore investigate the correlation between the dynamics of spin-dependent electric current and spin-dependent electroluminescence in two derivatives of the conjugated polymer poly(phenylene-vinylene) using simultaneously measured pulsed electrically detected (pEDMR) and optically detected (pODMR) magnetic resonance spectroscopy. This experimental approach requires careful analysis of the transient response functions under optical and electrical detection. At room temperature and under bipolar charge-carrier injection conditions, a correlation of the pEDMR and the pODMR signals is observed, consistent with the hypothesis that the recombination currents involve spin-dependent electronic transitions. This observation is inconsistent with the hypothesis that these signals are caused by spin-dependent charge-carrier transport. These results therefore provide no evidence that supports earlier claims that spin-dependent transport plays a role for room-temperature magnetoresistance effects. At low temperatures, however, the correlation between pEDMR and pODMR is weakened, demonstrating that more than one spin-dependent process influences the optoelectronic materials' properties. This conclusion is consistent with prior studies of half-field resonances that were attributed to spin-dependent triplet exciton recombination, which becomes significant at low temperatures when the triplet lifetime increases.

HATCN-based charge recombination layers as effective interconnectors for tandem organic solar cells.

PubMed

Wang, Rong-Bin; Wang, Qian-Kun; Xie, Hao-Jun; Xu, Lu-Hai; Duhm, Steffen; Li, Yan-Qing; Tang, Jian-Xin

2014-09-10

A comprehensive understanding of the energy-level alignment at the organic heterojunction interfaces is of paramount importance to optimize the performance of organic solar cells (OSCs). Here, the detailed electronic structures of organic interconnectors, consisting of cesium fluoride-doped 4,7-diphenyl-1,10-phenanthroline and hexaazatriphenylene-hexacarbonitrile (HATCN), have been investigated via in situ photoemission spectroscopy, and their impact on the charge recombination process in tandem OSCs has been identified. The experimental determination shows that the HATCN interlayer plays a significant role in the interface energetics with a dramatic decrease in the reverse built-in potential for electrons and holes from stacked subcells, which is beneficial to the charge recombination between HATCN and the adjacent layer. In accordance with the energy-level alignments, the open-circuit voltage of tandem OSC incorporating a HATCN-based interconnector is almost 2 times that of a single-cell OSC, revealing the effectiveness of the HATCN-based interconnectors in tandem organic devices.

Control of Geminate Recombination by the Material Composition and Processing Conditions in Novel Polymer: Nonfullerene Acceptor Photovoltaic Devices.

PubMed

Zhang, Jiangbin; Gu, Qinying; Do, Thu Trang; Rundel, Kira; Sonar, Prashant; Friend, Richard H; McNeill, Christopher R; Bakulin, Artem A

2018-02-08

Herein, we report on the charge dynamics of photovoltaic devices based on two novel small-molecule nonfullerene acceptors featuring a central ketone unit. Using ultrafast near-infrared spectroscopy with optical and photocurrent detection methods, we identify one of the key loss channels in the devices as geminate recombination (GR) of interfacial charge transfer states (CTSs). We find that the magnitude of GR is highly sensitive to the choice of solvent and annealing conditions. Interestingly, regardless of these processing conditions, the same lifetime for GR (∼130 ps) is obtained by both detection methods upon decomposing the complex broadband transient optical spectra, suggesting this time scale is inherent and independent of morphology. These observations suggest that the CTSs in the studied material blends are mostly strongly bound, and that charge generation from these states is highly inefficient. We further rationalize our results by considering the impact of the processing on the morphology of the mixed donor and acceptor domains and discuss the potential consequences of the early charge dynamics on the performance of emerging nonfullerene photovoltaic devices. Our results demonstrate that careful choice of processing conditions enables enhanced exciton harvesting and suppression of GR by more than 3 orders of magnitude.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jin; Prezhdo, Oleg V.

Rapid development in lead halide perovskites has led to solution-processable thin film solar cells with power conversion efficiencies close to 20%. Nonradiative electron–hole recombination within perovskites has been identified as the main pathway of energy losses, competing with charge transport and limiting the efficiency. Using nonadiabatic (NA) molecular dynamics, combined with time-domain density functional theory, we show that nonradiative recombination happens faster than radiative recombination and long-range charge transfer to an acceptor material. Doping of lead iodide perovskites with chlorine atoms reduces charge recombination. On the one hand, chlorines decrease the NA coupling because they contribute little to the wavemore » functions of the valence and conduction band edges. On the other hand, chlorines shorten coherence time because they are lighter than iodines and introduce high-frequency modes. Both factors favor longer excited-state lifetimes. The simulation shows good agreement with the available experimental data and contributes to the comprehensive understanding of electronic and vibrational dynamics in perovskites. The generated insights into design of higher-efficiency solar cells range from fundamental scientific principles, such as the role of electron–vibrational coupling and quantum coherence, to practical guidelines, such as specific suggestions for chemical doping.« less

Evaluation of physics-based numerical modelling for diverse design architecture of perovskite solar cells

NASA Astrophysics Data System (ADS)

Mishra, A. K.; Catalan, Jorge; Camacho, Diana; Martinez, Miguel; Hodges, D.

2017-08-01

Solution processed organic-inorganic metal halide perovskite based solar cells are emerging as a new cost effective photovoltaic technology. In the context of increasing the power conversion efficiency (PCE) and sustainability of perovskite solar cells (PSC) devices, we comprehensively analyzed a physics-based numerical modelling for doped and un-doped PSC devices. Our analytics emphasized the role of different charge carrier layers from the view point of interfacial adhesion and its influence on charge extraction rate and charge recombination mechanism. Morphological and charge transport properties of perovskite thin film as a function of device architecture are also considered to investigate the photovoltaic properties of PSC. We observed that photocurrent is dominantly influenced by interfacial recombination process and photovoltage has functional relationship with defect density of perovskite absorption layer. A novel contour mapping method to understand the characteristics of current density-voltage (J-V) curves for each device as a function of perovskite layer thickness provide an important insight about the distribution spectrum of photovoltaic properties. Functional relationship of device efficiency and fill factor with absorption layer thickness are also discussed.

I-V-T analysis of radiation damage in high efficiency Si solar cells

NASA Technical Reports Server (NTRS)

Banerjee, S.; Anderson, W. A.; Rao, B. B.

1985-01-01

A detailed analysis of current-voltage characteristics of N(+)-P/P solar cells indicate that there is a combination of different mechanisms which results in an enhancement in the dark current and in turn deteriorates the photovoltaic performance of the solar cells after 1 MeV e(-) irradiation. The increase in the dark current is due to three effects, i.e., bulk recombination, space charge recombination by deep traps and space charge recombination through shallow traps. It is shown that the increase in bulk recombination current is about 2 to 3 orders of magnitude whereas space charge recombination current due to shallow traps increases only by an order or so and no space charge recombination through deep traps was observed after irradiation. Thus, in order to improve the radiation hardness of these devices, bulk properties should be preserved.

Ultrafast Recombination Dynamics in Dye-Sensitized SnO2/TiO2 Core/Shell Films.

PubMed

Gish, Melissa K; Lapides, Alexander M; Brennaman, M Kyle; Templeton, Joseph L; Meyer, Thomas J; Papanikolas, John M

2016-12-15

Interfacial dynamics are investigated in SnO 2 /TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([Ru II (bpy) 2 (4,4'-(PO 3 H 2 ) 2 bpy)] 2+ , RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived charge-separated states (CSS) depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of dye-sensitized photoelectrosynthesis cells (DSPECs).

High charge-carrier mobility enables exploitation of carrier multiplication in quantum-dot films

PubMed Central

Sandeep, C. S. Suchand; Cate, Sybren ten; Schins, Juleon M.; Savenije, Tom J.; Liu, Yao; Law, Matt; Kinge, Sachin; Houtepen, Arjan J.; Siebbeles, Laurens D. A.

2013-01-01

Carrier multiplication, the generation of multiple electron–hole pairs by a single photon, is of great interest for solar cells as it may enhance their photocurrent. This process has been shown to occur efficiently in colloidal quantum dots, however, harvesting of the generated multiple charges has proved difficult. Here we show that by tuning the charge-carrier mobility in quantum-dot films, carrier multiplication can be optimized and may show an efficiency as high as in colloidal dispersion. Our results are explained quantitatively by the competition between dissociation of multiple electron–hole pairs and Auger recombination. Above a mobility of ~1 cm2 V−1 s−1, all charges escape Auger recombination and are quantitatively converted to free charges, offering the prospect of cheap quantum-dot solar cells with efficiencies in excess of the Shockley–Queisser limit. In addition, we show that the threshold energy for carrier multiplication is reduced to twice the band gap of the quantum dots. PMID:23974282

Charge Dynamics in near-Surface, Variable-Density Ensembles of Nitrogen-Vacancy Centers in Diamond.

PubMed

Dhomkar, Siddharth; Jayakumar, Harishankar; Zangara, Pablo R; Meriles, Carlos A

2018-06-13

Although the spin properties of superficial shallow nitrogen-vacancy (NV) centers have been the subject of extensive scrutiny, considerably less attention has been devoted to studying the dynamics of NV charge conversion near the diamond surface. Using multicolor confocal microscopy, here we show that near-surface point defects arising from high-density ion implantation dramatically increase the ionization and recombination rates of shallow NVs compared to those in bulk diamond. Further, we find that these rates grow linearly, not quadratically, with laser intensity, indicative of single-photon processes enabled by NV state mixing with other defect states. Accompanying these findings, we observe NV ionization and recombination in the dark, likely the result of charge transfer to neighboring traps. Despite the altered charge dynamics, we show that one can imprint rewritable, long-lasting patterns of charged-initialized, near-surface NVs over large areas, an ability that could be exploited for electrochemical biosensing or to optically store digital data sets with subdiffraction resolution.

High-Performance Ultrathin Organic-Inorganic Hybrid Silicon Solar Cells via Solution-Processed Interface Modification.

PubMed

Zhang, Jie; Zhang, Yinan; Song, Tao; Shen, Xinlei; Yu, Xuegong; Lee, Shuit-Tong; Sun, Baoquan; Jia, Baohua

2017-07-05

Organic-inorganic hybrid solar cells based on n-type crystalline silicon and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) exhibited promising efficiency along with a low-cost fabrication process. In this work, ultrathin flexible silicon substrates, with a thickness as low as tens of micrometers, were employed to fabricate hybrid solar cells to reduce the use of silicon materials. To improve the light-trapping ability, nanostructures were built on the thin silicon substrates by a metal-assisted chemical etching method (MACE). However, nanostructured silicon resulted in a large amount of surface-defect states, causing detrimental charge recombination. Here, the surface was smoothed by solution-processed chemical treatment to reduce the surface/volume ratio of nanostructured silicon. Surface-charge recombination was dramatically suppressed after surface modification with a chemical, associated with improved minority charge-carrier lifetime. As a result, a power conversion efficiency of 9.1% was achieved in the flexible hybrid silicon solar cells, with a substrate thickness as low as ∼14 μm, indicating that interface engineering was essential to improve the hybrid junction quality and photovoltaic characteristics of the hybrid devices.

Recombination of open-f-shell tungsten ions

NASA Astrophysics Data System (ADS)

Krantz, C.; Badnell, N. R.; Müller, A.; Schippers, S.; Wolf, A.

2017-03-01

We review experimental and theoretical efforts aimed at a detailed understanding of the recombination of electrons with highly charged tungsten ions characterised by an open 4f sub-shell. Highly charged tungsten occurs as a plasma contaminant in ITER-like tokamak experiments, where it acts as an unwanted cooling agent. Modelling of the charge state populations in a plasma requires reliable thermal rate coefficients for charge-changing electron collisions. The electron recombination of medium-charged tungsten species with open 4f sub-shells is especially challenging to compute reliably. Storage-ring experiments have been conducted that yielded recombination rate coefficients at high energy resolution and well-understood systematics. Significant deviations compared to simplified, but prevalent, computational models have been found. A new class of ab initio numerical calculations has been developed that provides reliable predictions of the total plasma recombination rate coefficients for these ions.

Analysis of Recombination in CdTe Heterostructures With Time-Resolved Two-Photon Excitation Microscopy

DOE PAGES

Kuciauskas, Darius; Wernsing, Keith; Jensen, Soren Alkaersig; ...

2016-11-01

Here, we used time-resolved photoluminescence microscopy to analyze charge carrier transport and recombination in CdTe double heterostructures fabricated by molecular beam epitaxy (MBE). This allowed us to determine the charge carrier mobility in this system, which was found to be 500-625 cm 2/(V s). Charge carrier lifetimes in the 15-100 ns range are limited by the interface recombination, and the data indicate higher interface recombination velocity near extended defects. This study describes a new method to analyze the spatial distribution of the interface recombination velocity and the interface defects in semiconductor heterostructures.

Analysis of Recombination in CdTe Heterostructures With Time-Resolved Two-Photon Excitation Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuciauskas, Darius; Wernsing, Keith; Jensen, Soren Alkaersig

Here, we used time-resolved photoluminescence microscopy to analyze charge carrier transport and recombination in CdTe double heterostructures fabricated by molecular beam epitaxy (MBE). This allowed us to determine the charge carrier mobility in this system, which was found to be 500-625 cm 2/(V s). Charge carrier lifetimes in the 15-100 ns range are limited by the interface recombination, and the data indicate higher interface recombination velocity near extended defects. This study describes a new method to analyze the spatial distribution of the interface recombination velocity and the interface defects in semiconductor heterostructures.

Conditions for diffusion-limited and reaction-limited recombination in nanostructured solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ansari-Rad, Mehdi, E-mail: ansari.rad@ut.ac.ir; Department of Physics, University of Shahrood, Shahrood; Anta, Juan A., E-mail: anta@upo.es

2014-04-07

The performance of Dye-sensitized solar cells (DSC) and related devices made of nanostructured semiconductors relies on a good charge separation, which in turn is achieved by favoring charge transport against recombination. Although both processes occur at very different time scales, hence ensuring good charge separation, in certain cases the kinetics of transport and recombination can be connected, either in a direct or an indirect way. In this work, the connection between electron transport and recombination in nanostructured solar cells is studied both theoretically and by Monte Carlo simulation. Calculations using the Multiple-Trapping model and a realistic trap distribution for nanostructuredmore » TiO{sub 2} show that for attempt-to-jump frequencies higher than 10{sup 11}–10{sup 13} Hz, the system adopts a reaction limited (RL) regime, with a lifetime which is effectively independent from the speed of the electrons in the transport level. For frequencies lower than those, and depending on the concentration of recombination centers in the material, the system enters a diffusion-limited regime (DL), where the lifetime increases if the speed of free electrons decreases. In general, the conditions for RL or DL recombination depend critically on the time scale difference between recombination kinetics and free-electron transport. Hence, if the former is too rapid with respect to the latter, the system is in the DL regime and total thermalization of carriers is not possible. In the opposite situation, a RL regime arises. Numerical data available in the literature, and the behavior of the lifetime with respect to (1) density of recombination centers and (2) probability of recombination at a given center, suggest that a typical DSC in operation stays in the RL regime with complete thermalization, although a transition to the DL regime may occur for electrolytes or hole conductors where recombination is especially rapid or where there is a larger dispersion of energies of electron acceptors.« less

Origin of Reduced Open-Circuit Voltage in Highly Efficient Small-Molecule-Based Solar Cells upon Solvent Vapor Annealing.

PubMed

Deng, Wanyuan; Gao, Ke; Yan, Jun; Liang, Quanbin; Xie, Yuan; He, Zhicai; Wu, Hongbin; Peng, Xiaobin; Cao, Yong

2018-03-07

In this study, we demonstrate that remarkably reduced open-circuit voltage in highly efficient organic solar cells (OSCs) from a blend of phenyl-C 61 -butyric acid methyl ester and a recently developed conjugated small molecule (DPPEZnP-THD) upon solvent vapor annealing (SVA) is due to two independent sources: increased radiative recombination and increased nonradiative recombination. Through the measurements of electroluminescence due to the emission of the charge-transfer state and photovoltaic external quantum efficiency measurement, we can quantify that the open-circuit voltage losses in a device with SVA due to the radiative recombination and nonradiative recombination are 0.23 and 0.31 V, respectively, which are 0.04 and 0.07 V higher than those of the as-cast device. Despite of the reduced open-circuit voltage, the device with SVA exhibited enhanced dissociation of charge-transfer excitons, leading to an improved short-circuit current density and a remarkable power conversion efficiency (PCE) of 9.41%, one of the best for solution-processed OSCs based on small-molecule donor materials. Our study also clearly shows that removing the nonradiative recombination pathways and/or suppressing energetic disorder in the active layer would result in more long-lived charge carriers and enhanced open-circuit voltage, which are prerequisites for further improving the PCE.

A quantitative and spatially resolved analysis of the performance-bottleneck in high efficiency, planar hybrid perovskite solar cells

DOE PAGES

Draguta, Sergiu; Christians, Jeffrey A.; Morozov, Yurii V.; ...

2018-01-01

Hybrid perovskites represent a potential paradigm shift for the creation of low-cost solar cells. Current power conversion efficiencies (PCEs) exceed 22%. However, despite this, record PCEs are still far from their theoretical Shockley–Queisser limit of 31%. To increase these PCE values, there is a pressing need to understand, quantify and microscopically model charge recombination processes in full working devices. Here, we present a complete microscopic account of charge recombination processes in high efficiency (18–19% PCE) hybrid perovskite (mixed cation and methylammonium lead iodide) solar cells. We employ diffraction-limited optical measurements along with relevant kinetic modeling to establish, for the firstmore » time, local photoluminescence quantum yields, trap densities, trapping efficiencies, charge extraction efficiencies, quasi-Fermi-level splitting, and effective PCE estimates. Correlations between these spatially resolved parameters, in turn, allow us to conclude that intrinsic electron traps in the perovskite active layers limit the performance of these state-of-the-art hybrid perovskite solar cells.« less

A quantitative and spatially resolved analysis of the performance-bottleneck in high efficiency, planar hybrid perovskite solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Draguta, Sergiu; Christians, Jeffrey A.; Morozov, Yurii V.

Hybrid perovskites represent a potential paradigm shift for the creation of low-cost solar cells. Current power conversion efficiencies (PCEs) exceed 22%. However, despite this, record PCEs are still far from their theoretical Shockley–Queisser limit of 31%. To increase these PCE values, there is a pressing need to understand, quantify and microscopically model charge recombination processes in full working devices. Here, we present a complete microscopic account of charge recombination processes in high efficiency (18–19% PCE) hybrid perovskite (mixed cation and methylammonium lead iodide) solar cells. We employ diffraction-limited optical measurements along with relevant kinetic modeling to establish, for the firstmore » time, local photoluminescence quantum yields, trap densities, trapping efficiencies, charge extraction efficiencies, quasi-Fermi-level splitting, and effective PCE estimates. Correlations between these spatially resolved parameters, in turn, allow us to conclude that intrinsic electron traps in the perovskite active layers limit the performance of these state-of-the-art hybrid perovskite solar cells.« less

Charge carrier concentration dependence of encounter-limited bimolecular recombination in phase-separated organic semiconductor blends

NASA Astrophysics Data System (ADS)

Heiber, Michael C.; Nguyen, Thuc-Quyen; Deibel, Carsten

2016-05-01

Understanding how the complex intermolecular configurations and nanostructure present in organic semiconductor donor-acceptor blends impacts charge carrier motion, interactions, and recombination behavior is a critical fundamental issue with a particularly major impact on organic photovoltaic applications. In this study, kinetic Monte Carlo (KMC) simulations are used to numerically quantify the complex bimolecular charge carrier recombination behavior in idealized phase-separated blends. Recent KMC simulations have identified how the encounter-limited bimolecular recombination rate in these blends deviates from the often used Langevin model and have been used to construct the new power mean mobility model. Here, we make a challenging but crucial expansion to this work by determining the charge carrier concentration dependence of the encounter-limited bimolecular recombination coefficient. In doing so, we find that an accurate treatment of the long-range electrostatic interactions between charge carriers is critical, and we further argue that many previous KMC simulation studies have used a Coulomb cutoff radius that is too small, which causes a significant overestimation of the recombination rate. To shed more light on this issue, we determine the minimum cutoff radius required to reach an accuracy of less than ±10 % as a function of the domain size and the charge carrier concentration and then use this knowledge to accurately quantify the charge carrier concentration dependence of the recombination rate. Using these rigorous methods, we finally show that the parameters of the power mean mobility model are determined by a newly identified dimensionless ratio of the domain size to the average charge carrier separation distance.

Recombination in liquid filled ionisation chambers with multiple charge carrier species: Theoretical and numerical results

NASA Astrophysics Data System (ADS)

Aguiar, P.; González-Castaño, D. M.; Gómez, F.; Pardo-Montero, J.

2014-10-01

Liquid-filled ionisation chambers (LICs) are used in radiotherapy for dosimetry and quality assurance. Volume recombination can be quite important in LICs for moderate dose rates, causing non-linearities in the dose rate response of these detectors, and needs to be corrected for. This effect is usually described with Greening and Boag models for continuous and pulsed radiation respectively. Such models assume that the charge is carried by two different species, positive and negative ions, each of those species with a given mobility. However, LICs operating in non-ultrapure mode can contain different types of electronegative impurities with different mobilities, thus increasing the number of different charge carriers. If this is the case, Greening and Boag models can be no longer valid and need to be reformulated. In this work we present a theoretical and numerical study of volume recombination in parallel-plate LICs with multiple charge carrier species, extending Boag and Greening models. Results from a recent publication that reported three different mobilities in an isooctane-filled LIC have been used to study the effect of extra carrier species on recombination. We have found that in pulsed beams the inclusion of extra mobilities does not affect volume recombination much, a behaviour that was expected because Boag formula for charge collection efficiency does not depend on the mobilities of the charge carriers if the Debye relationship between mobilities and recombination constant holds. This is not the case in continuous radiation, where the presence of extra charge carrier species significantly affects the amount of volume recombination.

Modulating the fixed charge density in silicon nitride films while monitoring the surface recombination velocity by photoluminescence imaging

NASA Astrophysics Data System (ADS)

Bazilchuk, Molly; Haug, Halvard; Marstein, Erik Stensrud

2015-04-01

Several important semiconductor devices such as solar cells and photodetectors may be fabricated based on surface inversion layer junctions induced by fixed charge in a dielectric layer. Inversion layer junctions can easily be fabricated by depositing layers with a high density of fixed charge on a semiconducting substrate. Increasing the fixed charge improves such devices; for instance, the efficiency of a solar cell can be substantially increased by reducing the surface recombination velocity, which is a function of the fixed charge density. Methods for increasing the charge density are therefore of interest. In this work, the fixed charge density in silicon nitride layers deposited by plasma enhanced chemical vapor deposition is increased to very high values above 1 × 1013 cm-2 after the application of an external voltage to a gate electrode. The effect of the fixed charge density on the surface recombination velocity was experimentally observed using the combination of capacitance-voltage characterization and photoluminescence imaging, showing a significant reduction in the surface recombination velocity for increasing charge density. The surface recombination velocity vs. charge density data was analyzed using a numerical device model, which indicated the presence of a sub-surface damage region formed during deposition of the layers. Finally, we have demonstrated that the aluminum electrodes used for charge injection may be chemically removed in phosphoric acid without loss of the underlying charge. The injected charge was shown to be stable for a prolonged time period, leading us to propose charge injection in silicon nitride films by application of soaking voltage as a viable method for fabricating inversion layer devices.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meusel, O., E-mail: o.meusel@iap.uni-frankfurt.de; Droba, M.; Noll, D.

The transport of intense ion beams is affected by the collective behavior of this kind of multi-particle and multi-species system. The space charge expressed by the generalized perveance dominates the dynamical process of thermalisation, which leads to emittance growth. To prevent changes of intrinsic beam properties and to reduce the intensity dependent focusing forces, space charge compensation seems to be an adequate solution. In the case of positively charged ion beams, electrons produced by residual gas ionization and secondary electrons provide the space charge compensation. The influence of the compensation particles on the beam transport and the local degree ofmore » space charge compensation is given by different beam properties as well as the ion beam optics. Especially for highly charged ion beams, space charge compensation in combination with poor vacuum conditions leads to recombination processes and therefore increased beam losses. Strategies for providing a compensation-electron reservoir at very low residual gas pressures will be discussed.« less

Charge carrier recombination dynamics in perovskite and polymer solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paulke, Andreas; Kniepert, Juliane; Kurpiers, Jona

2016-03-14

Time-delayed collection field experiments are applied to planar organometal halide perovskite (CH{sub 3}NH{sub 3}PbI{sub 3}) based solar cells to investigate charge carrier recombination in a fully working solar cell at the nanosecond to microsecond time scale. Recombination of mobile (extractable) charges is shown to follow second-order recombination dynamics for all fluences and time scales tested. Most importantly, the bimolecular recombination coefficient is found to be time-dependent, with an initial value of ca. 10{sup −9} cm{sup 3}/s and a progressive reduction within the first tens of nanoseconds. Comparison to the prototypical organic bulk heterojunction device PTB7:PC{sub 71}BM yields important differences with regardmore » to the mechanism and time scale of free carrier recombination.« less

Highly Efficient Flexible Quantum Dot Solar Cells with Improved Electron Extraction Using MgZnO Nanocrystals.

PubMed

Zhang, Xiaoliang; Santra, Pralay Kanti; Tian, Lei; Johansson, Malin B; Rensmo, Håkan; Johansson, Erik M J

2017-08-22

Colloidal quantum dot (CQD) solar cells have high potential for realizing an efficient and lightweight energy supply for flexible or wearable electronic devices. To achieve highly efficient and flexible CQD solar cells, the electron transport layer (ETL), extracting electrons from the CQD solid layer, needs to be processed at a low-temperature and should also suppress interfacial recombination. Herein, a highly stable MgZnO nanocrystal (MZO-NC) layer is reported for efficient flexible PbS CQD solar cells. Solar cells fabricated with MZO-NC ETL give a high power conversion efficiency (PCE) of 10.4% and 9.4%, on glass and flexible plastic substrates, respectively. The reported flexible CQD solar cell has the record efficiency to date of flexible CQD solar cells. Detailed theoretical simulations and extensive characterizations reveal that the MZO-NCs significantly enhance charge extraction from CQD solids and diminish the charge accumulation at the ETL/CQD interface, suppressing charge interfacial recombination. These important results suggest that the low-temperature processed MZO-NCs are very promising for use in efficient flexible solar cells or other flexible optoelectronic devices.

Reduced Charge Transfer Exciton Recombination in Organic Semiconductor Heterojunctions by Molecular Doping

NASA Astrophysics Data System (ADS)

Deschler, Felix; da Como, Enrico; Limmer, Thomas; Tautz, Raphael; Godde, Tillmann; Bayer, Manfred; von Hauff, Elizabeth; Yilmaz, Seyfullah; Allard, Sybille; Scherf, Ullrich; Feldmann, Jochen

2011-09-01

We investigate the effect of molecular doping on the recombination of electrons and holes localized at conjugated-polymer-fullerene interfaces. We demonstrate that a low concentration of p-type dopant molecules (<4% weight) reduces the interfacial recombination via charge transfer excitons and results in a favored formation of separated carriers. This is observed by the ultrafast quenching of photoluminescence from charge transfer excitons and the increase in photoinduced polaron density by ˜70%. The results are consistent with a reduced formation of emissive charge transfer excitons, induced by state filling of tail states.

Dielectronic recombination of the 4p and 4d open sub-shell tungsten ions

NASA Astrophysics Data System (ADS)

Li, M. J.; Fu, Y. B.; Zhang, G. D.; Zhang, Y. Z.; Dong, C. Z.; Koike, F.

2014-04-01

Dielectronic recombination rate coefficients are given theoretically for several highly charged tungsten ions. As 4p open sub-shell ions, Ga-, Ge-, As-, Br-, Kr-like ions are considered. Rb-like ion is further considered as a 4d open sub-shell ion. Theoretical calculations are carried out using a relativistic atomic code FAC. The effect of configuration interaction is taking into account. Inner-shell electron excitations play a significant role for the dielectronic recombination process. Simple analytical formulae are given for the total rate coefficients by fitting to the presently obtained numerical results.

Optical determination of Shockley-Read-Hall and interface recombination currents in hybrid perovskites

PubMed Central

Sarritzu, Valerio; Sestu, Nicola; Marongiu, Daniela; Chang, Xueqing; Masi, Sofia; Rizzo, Aurora; Colella, Silvia; Quochi, Francesco; Saba, Michele; Mura, Andrea; Bongiovanni, Giovanni

2017-01-01

Metal-halide perovskite solar cells rival the best inorganic solar cells in power conversion efficiency, providing the outlook for efficient, cheap devices. In order for the technology to mature and approach the ideal Shockley-Queissier efficiency, experimental tools are needed to diagnose what processes limit performances, beyond simply measuring electrical characteristics often affected by parasitic effects and difficult to interpret. Here we study the microscopic origin of recombination currents causing photoconversion losses with an all-optical technique, measuring the electron-hole free energy as a function of the exciting light intensity. Our method allows assessing the ideality factor and breaks down the electron-hole recombination current into bulk defect and interface contributions, providing an estimate of the limit photoconversion efficiency, without any real charge current flowing through the device. We identify Shockley-Read-Hall recombination as the main decay process in insulated perovskite layers and quantify the additional performance degradation due to interface recombination in heterojunctions. PMID:28317883

Exciton localization in solution-processed organolead trihalide perovskites

PubMed Central

He, Haiping; Yu, Qianqian; Li, Hui; Li, Jing; Si, Junjie; Jin, Yizheng; Wang, Nana; Wang, Jianpu; He, Jingwen; Wang, Xinke; Zhang, Yan; Ye, Zhizhen

2016-01-01

Organolead trihalide perovskites have attracted great attention due to the stunning advances in both photovoltaic and light-emitting devices. However, the photophysical properties, especially the recombination dynamics of photogenerated carriers, of this class of materials are controversial. Here we report that under an excitation level close to the working regime of solar cells, the recombination of photogenerated carriers in solution-processed methylammonium–lead–halide films is dominated by excitons weakly localized in band tail states. This scenario is evidenced by experiments of spectral-dependent luminescence decay, excitation density-dependent luminescence and frequency-dependent terahertz photoconductivity. The exciton localization effect is found to be general for several solution-processed hybrid perovskite films prepared by different methods. Our results provide insights into the charge transport and recombination mechanism in perovskite films and help to unravel their potential for high-performance optoelectronic devices. PMID:26996605

Understanding charge transport and recombination losses in high performance polymer solar cells with non-fullerene acceptors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xuning; Zuo, Xiaobing; Xie, Shenkun

Photovoltaic characteristics, recombination and charge transport properties are investigated. The determined recombination reduction factor can reconcile the supreme device performance in organic solar cells using non-fullerene ITIC acceptor and severe carrier losses in all-polymer devices with P(NDI2OD-T2).

Exciton Recombination, Energy-, and Charge Transfer in Single- and Multilayer Quantum-Dot Films on Silver Plasmonic Resonators.

PubMed

Shin, Taeho; Cho, Kyung-Sang; Yun, Dong-Jin; Kim, Jinwoo; Li, Xiang-Shu; Moon, Eui-Seong; Baik, Chan-Wook; Il Kim, Sun; Kim, Miyoung; Choi, Jun Hee; Park, Gyeong-Su; Shin, Jai-Kwang; Hwang, Sungwoo; Jung, Tae-Sung

2016-05-17

We examine exciton recombination, energy-, and charge transfer in multilayer CdS/ZnS quantum dots (QDs) on silver plasmonic resonators using photoluminescence (PL) and excitation spectroscopy along with kinetic modeling and simulations. The exciton dynamics including all the processes are strongly affected by the separation distance between QDs and silver resonators, excitation wavelength, and QD film thickness. For a direct contact or very small distance, interfacial charge transfer and tunneling dominate over intrinsic radiative recombination and exciton energy transfer to surface plasmons (SPs), resulting in PL suppression. With increasing distance, however, tunneling diminishes dramatically, while long-range exciton-SP coupling takes place much faster (>6.5 ns) than intrinsic recombination (~200 ns) causing considerable PL enhancement. The exciton-SP coupling strength shows a strong dependence on excitation wavelengths, suggesting the state-specific dynamics of excitons and the down-conversion of surface plasmons involved. The overlayers as well as the bottom monolayer of QD multilayers exhibit significant PL enhancement mainly through long-range exciton-SP coupling. The overall emission behaviors from single- and multilayer QD films on silver resonators are described quantitatively by a photophysical kinetic model and simulations. The present experimental and simulation results provide important and useful design rules for QD-based light harvesting applications using the exciton-surface plasmon coupling.

Exciton Recombination, Energy-, and Charge Transfer in Single- and Multilayer Quantum-Dot Films on Silver Plasmonic Resonators

PubMed Central

Shin, Taeho; Cho, Kyung-Sang; Yun, Dong-Jin; Kim, Jinwoo; Li, Xiang-Shu; Moon, Eui-Seong; Baik, Chan-Wook; Il Kim, Sun; Kim, Miyoung; Choi, Jun Hee; Park, Gyeong-Su; Shin, Jai-Kwang; Hwang, Sungwoo; Jung, Tae-Sung

2016-01-01

We examine exciton recombination, energy-, and charge transfer in multilayer CdS/ZnS quantum dots (QDs) on silver plasmonic resonators using photoluminescence (PL) and excitation spectroscopy along with kinetic modeling and simulations. The exciton dynamics including all the processes are strongly affected by the separation distance between QDs and silver resonators, excitation wavelength, and QD film thickness. For a direct contact or very small distance, interfacial charge transfer and tunneling dominate over intrinsic radiative recombination and exciton energy transfer to surface plasmons (SPs), resulting in PL suppression. With increasing distance, however, tunneling diminishes dramatically, while long-range exciton-SP coupling takes place much faster (>6.5 ns) than intrinsic recombination (~200 ns) causing considerable PL enhancement. The exciton-SP coupling strength shows a strong dependence on excitation wavelengths, suggesting the state-specific dynamics of excitons and the down-conversion of surface plasmons involved. The overlayers as well as the bottom monolayer of QD multilayers exhibit significant PL enhancement mainly through long-range exciton-SP coupling. The overall emission behaviors from single- and multilayer QD films on silver resonators are described quantitatively by a photophysical kinetic model and simulations. The present experimental and simulation results provide important and useful design rules for QD-based light harvesting applications using the exciton-surface plasmon coupling. PMID:27184469

Effect of Molecular Coupling on Ultrafast Electron-Transfer and Charge-Recombination Dynamics in a Wide-Gap ZnS Nanoaggregate Sensitized by Triphenyl Methane Dyes.

PubMed

Debnath, Tushar; Maity, Partha; Dana, Jayanta; Ghosh, Hirendra N

2016-03-03

Wide-band-gap ZnS nanocrystals (NCs) were synthesized, and after sensitizing the NCs with series of triphenyl methane (TPM) dyes, ultrafast charge-transfer dynamics was demonstrated. HRTEM images of ZnS NCs show the formation of aggregate crystals with a flower-like structure. Exciton absorption and lumimescence, due to quantum confinement of the ZnS NCs, appear at approximately 310 and 340 nm, respectively. Interestingly, all the TPM dyes (pyrogallol red, bromopyrogallol red, and aurin tricarboxylic acid) form charge-transfer complexes with the ZnS NCs, with the appearance of a red-shifted band. Electron injection from the photoexcited TPM dyes into the conduction band of the ZnS NCs is shown to be a thermodynamically viable process, as confirmed by steady-state and time-resolved emission studies. To unravel charge-transfer (both electron injection and charge recombination) dynamics and the effect of molecular coupling, femtosecond transient absorption studies were carried out in TPM-sensitized ZnS NCs. The electron-injection dynamics is pulse-width-limited in all the ZnS/TPM dye systems, however, the back electron transfer differs, depending on the molecular coupling of the sensitizers (TPM dyes). The detailed mechanisms for the above-mentioned processes are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Low Temperature on Charge Transport in Operational Planar and Mesoporous Perovskite Solar Cells.

PubMed

Petrović, Miloš; Ye, Tao; Chellappan, Vijila; Ramakrishna, Seeram

2017-12-13

Low-temperature optoelectrical studies of perovskite solar cells using MAPbI 3 and mixed-perovskite absorbers implemented into planar and mesoporous architectures reveal fundamental charge transporting properties in fully assembled devices operating under light bias. Both types of devices exhibit inverse correlation of charge carrier lifetime as a function of temperature, extending carrier lifetimes upon temperature reduction, especially after exposure to high optical biases. Contribution of bimolecular channels to the overall recombination process should not be overlooked because the density of generated charge surpasses trap-filling concentration requirements. Bimolecular charge recombination coefficient in both device types is smaller than Langevin theory prediction, and its mean value is independent of the applied illumination intensity. In planar devices, charge extraction declines upon MAPbI 3 transition from a tetragonal to an orthorhombic phase, indicating a connection between the trapping/detrapping mechanism and temperature. Studies on charge extraction by linearly increasing voltage further support this assertion, as charge carrier mobility dependence on temperature follows multiple-trapping predictions for both device structures. The monotonously increasing trend following the rise in temperature opposes the behavior observed in neat perovskite films and indicates the importance of transporting layers and the effect they have on charge transport in fully assembled solar cells. Low-temperature phase transition shows no pattern of influence on thermally activated electron/hole transport.

Analysis of microscopic parameters of surface charging in polymer caused by defocused electron beam irradiation.

PubMed

Liu, Jing; Zhang, Hai-Bo

2014-12-01

The relationship between microscopic parameters and polymer charging caused by defocused electron beam irradiation is investigated using a dynamic scattering-transport model. The dynamic charging process of an irradiated polymer using a defocused 30 keV electron beam is conducted. In this study, the space charge distribution with a 30 keV non-penetrating e-beam is negative and supported by some existing experimental data. The internal potential is negative, but relatively high near the surface, and it decreases to a maximum negative value at z=6 μm and finally tend to 0 at the bottom of film. The leakage current and the surface potential behave similarly, and the secondary electron and leakage currents follow the charging equilibrium condition. The surface potential decreases with increasing beam current density, trap concentration, capture cross section, film thickness and electron-hole recombination rate, but with decreasing electron mobility and electron energy. The total charge density increases with increasing beam current density, trap concentration, capture cross section, film thickness and electron-hole recombination rate, but with decreasing electron mobility and electron energy. This study shows a comprehensive analysis of microscopic factors of surface charging characteristics in an electron-based surface microscopy and analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of charge trapping on geminate recombination and polymer solar cell performance.

PubMed

Groves, Chris; Blakesley, James C; Greenham, Neil C

2010-03-10

In this letter, we examine the effect of charge trapping on geminate recombination and organic photovoltaic performance using a Monte Carlo model. We alter the degree of charge trapping by considering energetic disorder to be spatially uncorrelated or correlated. On correlating energetic disorder, and so reducing the degree of trapping, it is found that power conversion efficiency of blend and bilayer devices improves by factors of 3.1 and 2.6, respectively. These results are related to the experimental data and quantum chemical calculations for poly[9,9-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine] (PFB)/poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) as well as poly(3-hexylthiophene) (P3HT)/(6,6)-phenyl-C(61)-butyric acid methyl ester (PCBM) solar cell systems. The minimization of traps at the heterojunction between electron- and hole-accepting materials, perhaps by molecular design, appears to be a promising strategy to achieve large gains in PV performance. It is also shown that macroscopically measurable quantities such as mobility and energetic disorder are not necessarily good predictors of nanoscale geminate recombination process.

A new scanning electron microscopy approach to image aerogels at the nanoscale

NASA Astrophysics Data System (ADS)

Solá, F.; Hurwitz, F.; Yang, J.

2011-04-01

A new scanning electron microscopy (SEM) technique to image poor electrically conductive aerogels is presented. The process can be performed by non-expert SEM users. We showed that negative charging effects on aerogels can be minimized significantly by inserting dry nitrogen gas close to the region of interest. The process involves the local recombination of accumulated negative charges with positive ions generated from ionization processes. This new technique made possible the acquisition of images of aerogels with pores down to approximately 3 nm in diameter using a positively biased Everhart-Thornley (ET) detector.

Recombination properties of dislocations in GaN

NASA Astrophysics Data System (ADS)

Yakimov, Eugene B.; Polyakov, Alexander Y.; Lee, In-Hwan; Pearton, Stephen J.

2018-04-01

The recombination activity of threading dislocations in n-GaN with different dislocation densities and different doping levels was studied using electron beam induced current (EBIC). The recombination velocity on a dislocation, also known as the dislocation recombination strength, was calculated. The results suggest that dislocations in n-GaN giving contrast in EBIC are charged and surrounded by a space charge region, as evidenced by the observed dependence of dislocation recombination strength on dopant concentration. For moderate (below ˜108 cm-2) dislocation densities, these defects do not primarily determine the average diffusion length of nonequilibrium charge carriers, although locally, dislocations are efficient recombination sites. In general, it is observed that the effect of the growth method [standard metalorganic chemical vapor deposition (MOCVD), epitaxial lateral overgrowth versions of MOCVD, and hydride vapor phase epitaxy] on the recombination activity of dislocations is not very pronounced, although the average diffusion lengths can widely differ for various samples. The glide of basal plane dislocations at room temperature promoted by low energy electron irradiation does not significantly change the recombination properties of dislocations.

Factors controlling charge recombination under dark and light conditions in dye sensitised solar cells.

PubMed

Barnes, Piers R F; Anderson, Assaf Y; Juozapavicius, Mindaugas; Liu, Lingxuan; Li, Xiaoe; Palomares, Emilio; Forneli, Amparo; O'Regan, Brian C

2011-02-28

A simple and powerful approach for assessing the recombination losses in dye sensitised solar cells (DSSCs) across the current voltage curve (j-V) as a function of TiO(2) electron concentration (n) is demonstrated. The total flux of electrons recombining with iodine species in the electrolyte and oxidised dye molecules can be thought of as a recombination current density, defined as j(rec) = j(inj)-j where j(inj) is the current of electrons injected from optically excited dye states and j is the current density collected at cell voltage (V). The electron concentration at any given operating conditions is determined by charge extraction. This allows comparison of factors influencing electron recombination rates at matched n. We show that j(rec) is typically 2-3 times higher under 1 sun equivalent illumination (j(inj) > 0) relative to dark (j(inj) = 0) conditions. This difference was increased by increasing light intensity, electrolyte iodine concentration and electrolyte solvent viscosity. The difference was reduced by increasing the electrolyte iodide concentration and increasing the temperature. These results allowed us to verify a numerical model of complete operational cells (Barnes et al., Phys. Chem. Chem. Phys., DOI: 10.1039/c0cp01554g) and to relate the differences in j(rec) to physical processes in the devices. The difference between j(rec) in the light and dark can be explained by two factors: (1) an increase in the concentration of electron acceptor species (I(3)(-) and/or I(2)) when current is flowing under illumination relative to dark conditions where the current is flowing in the opposite direction, and (2) a non-trivial contribution from electron recombination to oxidised dye molecules under light conditions. More generally, the technique helps to assign the observed relationship between the components, processing and performance of DSSCs to more fundamental physical processes.

Design principle for efficient charge separation at the donor-acceptor interface for high performance organic solar cell device

NASA Astrophysics Data System (ADS)

Nie, Wanyi; Gupta, Gautam; Crone, Brian; Wang, Hsing-Lin; Mohite, Aditya; MPA-11 Material synthesis and integrated device Team; MPA-chemistry Team

2014-03-01

The performance of donor (D) /acceptor (A) structure based organic electronic devices, such as solar cell, light emitting devices etc., relays on the charge transfer process at the interface dramatically. In organic solar cell, the photo-induced electron-hole pair is tightly bonded and will form a charge transfer (CT) state at the D/A interface after dissociation. There is a large chance for them to recombine through CT state and thus is a major loss that limit the overall performance. Here, we report three different strategies that allow us to completely suppress the exciplex (or charge transfer state) recombination between any D/A system. We observe that the photocurrent increases by 300% and the power conversion efficiency increases by 4-5 times simply by inserting a spacer layer in the form of an a) insulator b) Oliogomer or using a c) heavy atom at the donor-acceptor interface in a P3HT/C60 bilayer device. By using those different functional mono layers, we successfully suppressed the exciplex recombination in evidence of increased photocurrent and open circuit voltage. Moreover, these strategies are applicable universally to any donor-acceptor interface. And we demonstrated such strategies in a bulk-heterojunction device which improved the power conversion efficiency from 3.5% up to 4.6%.

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films.

PubMed

Moia, Davide; Szumska, Anna; Vaissier, Valérie; Planells, Miquel; Robertson, Neil; O'Regan, Brian C; Nelson, Jenny; Barnes, Piers R F

2016-10-12

Charge recombination between oxidized dyes attached to mesoporous TiO 2 and electrons in the TiO 2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO 2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts.

Molecular Electronic Coupling Controls Charge Recombination Kinetics in Organic Solar Cells of Low Bandgap Diketopyrrolopyrrole, Carbazole, and Thiophene Polymers

PubMed Central

2013-01-01

Low-bandgap diketopyrrolopyrrole- and carbazole-based polymer bulk-heterojunction solar cells exhibit much faster charge carrier recombination kinetics than that encountered for less-recombining poly(3-hexylthiophene). Solar cells comprising these polymers exhibit energy losses caused by carrier recombination of approximately 100 mV, expressed as reduction in open-circuit voltage, and consequently photovoltaic conversion efficiency lowers in more than 20%. The analysis presented here unravels the origin of that energy loss by connecting the limiting mechanism governing recombination dynamics to the electronic coupling occurring at the donor polymer and acceptor fullerene interfaces. Previous approaches correlate carrier transport properties and recombination kinetics by means of Langevin-like mechanisms. However, neither carrier mobility nor polymer ionization energy helps understanding the variation of the recombination coefficient among the studied polymers. In the framework of the charge transfer Marcus theory, it is proposed that recombination time scale is linked with charge transfer molecular mechanisms at the polymer/fullerene interfaces. As expected for efficient organic solar cells, small electronic coupling existing between donor polymers and acceptor fullerene (Vif < 1 meV) and large reorganization energy (λ ≈ 0.7 eV) are encountered. Differences in the electronic coupling among polymer/fullerene blends suffice to explain the slowest recombination exhibited by poly(3-hexylthiophene)-based solar cells. Our approach reveals how to directly connect photovoltaic parameters as open-circuit voltage to molecular properties of blended materials. PMID:23662167

Dissociative recombination of N2/+/ in the ionosphere

NASA Technical Reports Server (NTRS)

Torr, M. R.; Torr, D. G.

1979-01-01

N2(+) ion measurements are examined which were made with the Atmospheric Explorer-C satellite during a phase of solar activity in 1978 that was significantly higher than near the earlier minimum. It is found that the major source of N2(+) is photoionization, rather than charge exchange with O(+) (2D), and that the major loss process above 300 km is dissociative recombination with electrons. A data sample for which the electron temperature (T sub e) covered the range from 1000 to 3400 K is used to evaluate the rate constant, alpha, for the dissociative-recombination process. The results show good agreement with laboratory measurements given by the expression: alpha = 1.8 x 10 to the -7th (T sub e/300) to the -0.39th cu cm/sec.

Carrier dynamics and surface vibration-assisted Auger recombination in porous silicon

NASA Astrophysics Data System (ADS)

Zakar, Ammar; Wu, Rihan; Chekulaev, Dimitri; Zerova, Vera; He, Wei; Canham, Leigh; Kaplan, Andrey

2018-04-01

Excitation and recombination dynamics of the photoexcited charge carriers in porous silicon membranes were studied using a femtosecond pump-probe technique. Near-infrared pulses (800 nm, 60 fs) were used for the pump while, for the probe, we employed different wavelengths in the range between 3.4 and 5 μ m covering the medium wavelength infrared range. The data acquired in these experiments consist of simultaneous measurements of the transmittance and reflectance as a function of the delay time between the pump and probe for different pump fluences and probe wavelengths. To evaluate the results, we developed an optical model based on the two-dimensional Maxwell-Garnett formula, incorporating the free-carrier Drude contribution and nonuniformity of the excitation by the Wentzel-Kramers-Brillouin model. This model allowed the retrieval of information about the carrier density as a function of the pump fluence, time, and wavelength. The carrier density data were analyzed to reveal that the recombination dynamics is governed by Shockley-Read-Hall and Auger processes, whereas the diffusion has an insignificant contribution. We show that, in porous silicon samples, the Auger recombination process is greatly enhanced at the wavelength corresponding to the infrared-active vibrational modes of the molecular impurities on the surface of the pores. This observation of surface-vibration-assisted Auger recombination is not only for porous silicon in particular, but for low-dimension and bulk semiconductors in general. We estimate the time constants of Shockley-Read-Hall and Auger processes, and demonstrate their wavelength dependence for the excited carrier density in the range of 1018-10191 /cm3 . We demonstrate that both processes are enhanced by up to three orders of magnitude with respect to the bulk counterpart. In addition, we provide a plethora of the physical parameters evaluated from the experimental data, such as the dielectric function and its dependence on the injection level of the free carriers, charge-carrier scattering time related high-frequency conductivity, and the free-carrier absorption at the midwave infrared range.

Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions.

PubMed

Mukherjee, Tamal; Ito, Naoki; Gould, Ian R

2011-03-17

The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

Photocarrier drift distance in organic solar cells and photodetectors

PubMed Central

Stolterfoht, Martin; Armin, Ardalan; Philippa, Bronson; White, Ronald D.; Burn, Paul L.; Meredith, Paul; Juška, Gytis; Pivrikas, Almantas

2015-01-01

Light harvesting systems based upon disordered materials are not only widespread in nature, but are also increasingly prevalent in solar cells and photodetectors. Examples include organic semiconductors, which typically possess low charge carrier mobilities and Langevin-type recombination dynamics – both of which negatively impact the device performance. It is accepted wisdom that the “drift distance” (i.e., the distance a photocarrier drifts before recombination) is defined by the mobility-lifetime product in solar cells. We demonstrate that this traditional figure of merit is inadequate for describing the charge transport physics of organic light harvesting systems. It is experimentally shown that the onset of the photocarrier recombination is determined by the electrode charge and we propose the mobility-recombination coefficient product as an alternative figure of merit. The implications of these findings are relevant to a wide range of light harvesting systems and will necessitate a rethink of the critical parameters of charge transport. PMID:25919439

Photoelectrical, photophysical and photocatalytic properties of Al based MOFs: MIL-53(Al) and MIL-53-NH{sub 2}(Al)

DOE Office of Scientific and Technical Information (OSTI.GOV)

An, Yang; Li, Huiliang; Liu, Yuanyuan, E-mail: yyliu@sdu.edu.cn

Two Al based MOFs (MIL-53(Al) and MIL-53-NH{sub 2} (Al)) were synthesized, and their photoelectrical, photophysical and photocatalytic properties towards oxygen evolution from water were investigated. Different from the ligand to metal charge transfer process previously reported, we proposes a new photocatalytic mechanism based on electron tunneling according to the results of theoretical calculation, steady state and time resolved fluorescence spectra. The organic linkers absorb photons, giving rise to electrons and holes. Then, the photogenerated electrons tunnel through the AlO{sub 6}-octahedra, which not only inhibit the recombination of photogenerated charge carriers, but also is a key factor to the photocatalytic activitymore » of Al based MOFs. - Graphical abstract: The photoelectrical, photophysical and photocatalytic properties towards oxygen evolution from water of two Al based MOFs were investigated. A new photocatalytic mechanism was proposed based on electron tunneling according to the results of both theoretical calculation and steady state, time resolved fluorescence spectra. The electron tunneling process not only inhibit the recombination of photogenerated charge carriers, but also is a key factor to the photocatalytic activity of Al based MOFs.« less

The physics of background discrimination in liquid xenon, and first results from Xenon10 in the hunt for WIMP dark matter

NASA Astrophysics Data System (ADS)

Dahl, Carl Eric

2009-06-01

The WIMP limit set by the Xenon10 experiment in 2007 signals a new era in direct detection of dark matter, with several large-scale liquid target detectors now under construction. A major challenge in these detectors will be to understand backgrounds at the level necessary to claim a positive WIMP signal. In liquid xenon, these backgrounds are dominated by electron recoils, which may be distinguished from the WIMP signal (nuclear recoils) by their higher charge-to-light ratio. During the construction and operation of Xenon10, the prototype detector Xed probed the physics of this discrimination. Particle interactions in liquid xenon both ionize and excite xenon atoms, giving charge and scintillation signals, respectively. Some fraction of ions recombine, reducing the charge signal and creating additional scintillation. The charge-to-light ratio, determined by the initial exciton-ion ratio and the ion recombination fraction, provides the basis for discrimination between electron and nuclear recoils. Intrinsic fluctuations in the recombination fraction limit discrimination. Changes in recombination induce an exact anti-correlation between charge and light, and when calibrated this anti-correlation distinguishes recombination fluctuations from uncorrelated fluctuations in the measured signals. We determine the mean recombination and recombination fluctuations as a function of energy and applied field for electron and nuclear recoils, finding that recombination fluctuations are already the limiting factor for discrimination above ~12 keVr (nuclear recoil energy). Below 12 keVr statistical fluctuations in the number of scintillation photons counted dominate, and we project a x6 improvement in background rejection with a x2 increase in light collection efficiency. We also build a simple recombination model that successfully reproduces the mean recombination in electron and nuclear recoils, including the surprising reversal of the expected trend for recombination with ionization density in low energy electron recoils. The model also reproduces the measured recombination fluctuations to within a factor of two at high energies. Surprisingly, the model suggests that recombination at low energies is independent of ionization density, and our observed discrimination is due not to the different stopping powers of electrons and nuclei as was thought, but rather to a different initial exciton-ion ratio. We suggest two possible physical models for this new result.

Ultrafast recombination dynamics in dye-sensitized SnO 2/TiO 2 core/shell films

DOE PAGES

Gish, Melissa K.; Lapides, Alexander M.; Brennaman, M. Kyle; ...

2016-12-02

In dye-sensitized photoelectrosynthesis cells (DSPECs), molecular chromophores and catalysts are integrated on a semiconductor surface to perform water oxidation or CO 2 reduction after a series of light-induced electron transfer events. Unfortunately, recombination of the charge separated state (CSS) is competitive with productive catalysis. To overcome this major obstacle, implementation of photoanodic core/shell films within these devices improve electrochemical behavior and slow recombination through the introduction of an energetic barrier between the semiconductor core and oxidized species on the surface. In this study, interfacial dynamics are investigated in SnO 2/TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([RuII(bpy)2(4,4'-(PO 3Hmore » 2) 2bpy)] 2+, RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived CSS depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of DSPECs.« less

Exciton delocalization incorporated drift-diffusion model for bulk-heterojunction organic solar cells

NASA Astrophysics Data System (ADS)

Wang, Zi Shuai; Sha, Wei E. I.; Choy, Wallace C. H.

2016-12-01

Modeling the charge-generation process is highly important to understand device physics and optimize power conversion efficiency of bulk-heterojunction organic solar cells (OSCs). Free carriers are generated by both ultrafast exciton delocalization and slow exciton diffusion and dissociation at the heterojunction interface. In this work, we developed a systematic numerical simulation to describe the charge-generation process by a modified drift-diffusion model. The transport, recombination, and collection of free carriers are incorporated to fully capture the device response. The theoretical results match well with the state-of-the-art high-performance organic solar cells. It is demonstrated that the increase of exciton delocalization ratio reduces the energy loss in the exciton diffusion-dissociation process, and thus, significantly improves the device efficiency, especially for the short-circuit current. By changing the exciton delocalization ratio, OSC performances are comprehensively investigated under the conditions of short-circuit and open-circuit. Particularly, bulk recombination dependent fill factor saturation is unveiled and understood. As a fundamental electrical analysis of the delocalization mechanism, our work is important to understand and optimize the high-performance OSCs.

Spin-dependent recombination probed through the dielectric polarizability

PubMed Central

Bayliss, Sam L.; Greenham, Neil C.; Friend, Richard H.; Bouchiat, Hélène; Chepelianskii, Alexei D

2015-01-01

Despite residing in an energetically and structurally disordered landscape, the spin degree of freedom remains a robust quantity in organic semiconductor materials due to the weak coupling of spin and orbital states. This enforces spin-selectivity in recombination processes which plays a crucial role in optoelectronic devices, for example, in the spin-dependent recombination of weakly bound electron-hole pairs, or charge-transfer states, which form in a photovoltaic blend. Here, we implement a detection scheme to probe the spin-selective recombination of these states through changes in their dielectric polarizability under magnetic resonance. Using this technique, we access a regime in which the usual mixing of spin-singlet and spin-triplet states due to hyperfine fields is suppressed by microwave driving. We present a quantitative model for this behaviour which allows us to estimate the spin-dependent recombination rate, and draw parallels with the Majorana–Brossel resonances observed in atomic physics experiments. PMID:26439933

High yield of secondary B-side electron transfer in mutant Rhodobacter capsulatus reaction centers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kressel, Lucas; Faries, Kaitlyn M.; Wander, Marc J.

2014-08-01

From the crystal structures of reaction centers (RCs) from purple photosynthetic bacteria, two pathways for electron transfer (ET) are apparent but only one pathway (the A side) operates in the native protein-cofactor complex. Partial activation of the B-side pathway has unveiled the true inefficiencies of ET processes on that side in comparison to analogous reactions on the A side. Of significance are the relative rate constants for forward ET and the competing charge recombination reactions. On the B side, these rate constants are nearly equal for the secondary charge-separation step (ET from bacteriopheophytin to quinone), relegating the yield of thismore » process to < 50%. Herein we report efforts to optimize this step. In surveying all possible residues at position 131 in the M subunit, we discovered that when glutamic acid replaces the native valine the efficiency of the secondary ET is nearly two-fold higher than in the wild-type RC. The positive effect of M131 Glu is likely due to formation of a hydrogen bond with the ring V keto group of the B-side bacteriopheophytin leading to stabilization of the charge-separated state involving this cofactor. In conclusion, this change slows charge recombination by roughly a factor of two and affords the improved yield of the desired forward ET to the B-side quinone terminal acceptor.« less

Excited state and charge-carrier dynamics in perovskite solar cell materials

NASA Astrophysics Data System (ADS)

Ponseca, Carlito S., Jr.; Tian, Yuxi; Sundström, Villy; Scheblykin, Ivan G.

2016-02-01

Organo-metal halide perovskites (OMHPs) have attracted enormous interest in recent years as materials for application in optoelectronics and solar energy conversion. These hybrid semiconductors seem to have the potential to challenge traditional silicon technology. In this review we will give an account of the recent development in the understanding of the fundamental light-induced processes in OMHPs from charge-photo generation, migration of charge carries through the materials and finally their recombination. Our and other literature reports on time-resolved conductivity, transient absorption and photoluminescence properties are used to paint a picture of how we currently see the fundamental excited state and charge-carrier dynamics. We will also show that there is still no fully coherent picture of the processes in OMHPs and we will indicate the problems to be solved by future research.

Correction: The effect of recombination under short-circuit conditions on the determination of charge transport properties in nanostructured photoelectrodes.

PubMed

Villanueva-Cab, J; Anta, J A; Oskam, G

2016-05-28

Correction for 'The effect of recombination under short-circuit conditions on the determination of charge transport properties in nanostructured photoelectrodes' by J. Villanueva-Cab et al., Phys. Chem. Chem. Phys., 2016, 18, 2303-2308.

Effects of quantum interference between radiative and dielectronic recombination on photorecombination cross-section profiles for the He-like ions Ar{sup 16+} and Fe{sup 24+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Behar, Ehud; Jacobs, Verne L.; Oreg, Joseph

Total cross sections for electron-ion photorecombination (PR) processes are calculated using a projection-operator and resolvent-operator approach. This approach provides a unified quantum-mechanical description of the combined electron-ion PR process, including radiative and dielectronic recombination as coherent, interfering components. An especially adapted version of the Hebrew-University Lawrence-Livermore Atomic Code HULLAC is developed and employed for the calculations. In particular, PR cross sections for He-like argon and iron ions are calculated for incident-electron energies in the vicinity of the 1s2l2l{sup '} and 1s2l3l{sup '} doubly-excited, autoionizing levels of the Li-like ions. Significant effects of quantum interference between radiative and dielectronic recombination, inmore » the form of asymmetric PR cross-section profiles, are predicted, especially for weak transitions. The general behavior of the interference effect, as a function of the ion charge q and as a function of the principal quantum number n{sup '} of the outer electron in the autoionizing state, is investigated using a hydrogenic-scaling analysis. It is found that the degree of asymmetry in the PR cross-section profile can be substantial for close-to-neutral ions and also for very highly-charged ions. In the intermediate-charge regime, on the other hand, the asymmetry is anticipated to be less prominent. The dependence of the quantum-interference effect on n{sup '} is predicted to be much weaker.« less

Competition between recombination and extraction of free charges determines the fill factor of organic solar cells

PubMed Central

Bartesaghi, Davide; Pérez, Irene del Carmen; Kniepert, Juliane; Roland, Steffen; Turbiez, Mathieu; Neher, Dieter; Koster, L. Jan Anton

2015-01-01

Among the parameters that characterize a solar cell and define its power-conversion efficiency, the fill factor is the least well understood, making targeted improvements difficult. Here we quantify the competition between charge extraction and recombination by using a single parameter θ, and we demonstrate that this parameter is directly related to the fill factor of many different bulk-heterojunction solar cells. Our finding is supported by experimental measurements on 15 different donor:acceptor combinations, as well as by drift-diffusion simulations of organic solar cells in which charge-carrier mobilities, recombination rate, light intensity, energy levels and active-layer thickness are all varied over wide ranges to reproduce typical experimental conditions. The results unify the fill factors of several very different donor:acceptor combinations and give insight into why fill factors change so much with thickness, light intensity and materials properties. To achieve fill factors larger than 0.8 requires further improvements in charge transport while reducing recombination. PMID:25947637

Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

NASA Astrophysics Data System (ADS)

Ponseca, C. S., Jr.; Sundström, V.

2016-03-01

Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

Elementary process and meteor train spectra

NASA Technical Reports Server (NTRS)

Ovezgeldyev, O. G.

1987-01-01

Mechanisms of excitation of individual spectral line radiation were studied experimentally and theoretically and it was demonstrated that such processes as oxidation, resonant charge exchange, dissociative recombination and others play an important part in the chemistry of excited particles. The foundation was laid toward simulating the elementary processes of meteor physics. Having a number of advantages and possibilities, this method is sure to find a wide use in the future.

Impact of interfacial molecular orientation on radiative recombination and charge generation efficiency

DOE PAGES

Ran, Niva A.; Roland, Steffen; Love, John A.; ...

2017-07-19

Here, a long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics—however, the results have important implications on the operation of all optoelectronic devices with donor/acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting inmore » larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.« less

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

NASA Astrophysics Data System (ADS)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

Persistent photoconductivity due to trapping of induced charges in Sn/ZnO thin film based UV photodetector

NASA Astrophysics Data System (ADS)

Yadav, Harish Kumar; Sreenivas, K.; Gupta, Vinay

2010-05-01

Photoconductivity relaxation in rf magnetron sputtered ZnO thin films integrated with ultrathin tin metal overlayer is investigated. Charge carriers induced at the ZnO-metal interface by the tin metal overlayer compensates the surface lying trap centers and leads to the enhanced photoresponse. On termination of ultraviolet radiation, recombination of the photoexcited electrons with the valence band holes leaves the excess carriers deeply trapped at the recombination center and holds the dark conductivity level at a higher value. Equilibrium between the recombination centers and valence band, due to trapped charges, eventually stimulates the persistent photoconductivity in the Sn/ZnO photodetectors.

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery – Part 1

PubMed Central

Purushothaman, B. K.; Wainright, J. S.

2012-01-01

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H2 storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1st hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body. PMID:22423175

Analysis of Pressure Variations in a Low-Pressure Nickel-Hydrogen Battery - Part 1.

PubMed

Purushothaman, B K; Wainright, J S

2012-05-15

A low pressure nickel-hydrogen battery using either a metal hydride or gaseous hydrogen for H(2) storage has been developed for use in implantable neuroprosthetic devices. In this paper, pressure variations inside the cell for the gaseous hydrogen version are analyzed and correlated with oxygen evolution side reaction at the end of charging, the recombination of oxygen with hydrogen during charging and a subsequent rest period, and the self-discharge of the nickel electrode. About 70% of the recombination occurred simultaneously with oxygen evolution during charging and the remaining oxygen recombined with hydrogen during the 1(st) hour after charging. Self-discharge of the cell varies linearly with hydrogen pressure at a given state of charge and increased with increasing battery charge levels. The coulometric efficiency calculated based on analysis of the pressure-time data agreed well with the efficiency calculated based on the current-time data. Pressure variations in the battery are simulated accurately to predict coulometric efficiency and the state of charge of the cell, factors of extreme importance for a battery intended for implantation within the human body.

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination.

PubMed

Horwitz, Noah E; Phelan, Brian T; Nelson, Jordan N; Mauck, Catherine M; Krzyaniak, Matthew D; Wasielewski, Michael R

2017-06-15

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA • -mPD-ANI-NDI, where BDPA • is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized. Photoexcitation of ANI produces the triradical BDPA • -mPD +• -ANI-NDI -• in which the mPD +• -ANI-NDI -• radical ion pair is spin coupled to the BDPA • stable radical. BDPA • -mPD +• -ANI-NDI -• and its counterpart lacking the stable radical are found to exhibit spin-selective charge recombination in which the triplet radical ion pair 3 (mPD +• -ANI-NDI -• ) is in equilibrium with the 3 *NDI charge recombination product. Time-resolved EPR measurements show that this process is associated with an inversion of the sign of the polarization transferred to BDPA • over time. The polarization transfer rates are found to be strongly solvent dependent, as shifts in this equilibrium affect the spin dynamics. These results demonstrate that even small changes in electron transfer dynamics can have a large effect on the spin dynamics of photogenerated multispin systems.

New Approach to Image Aerogels by Scanning Electron Microscopy

NASA Astrophysics Data System (ADS)

Solá, Francisco; Hurwitz, Frances; Yang, Jijing

2011-03-01

A new scanning electron microscopy (SEM) technique to image poor electrically conductive aerogels is presented. The process can be performed by non-expert SEM users. We showed that negative charging effects on aerogels can be minimized significantly by inserting dry nitrogen gas close to the region of interest. The process involves the local recombination of accumulated negative charges with positive ions generated from ionization processes. This new technique made possible the acquisition of images of aerogels with pores down to approximately 3nm in diameter using a positively biased Everhart-Thornley (E-T) detector. Well-founded concepts based on known models will also be presented with the aim to explain the results qualitatively.

Optical emission of GaN/AlN quantum-wires - the role of charge transfer from a nanowire template.

PubMed

Müßener, Jan; Greif, Ludwig A Th; Kalinowski, Stefan; Callsen, Gordon; Hille, Pascal; Schörmann, Jörg; Wagner, Markus R; Schliwa, Andrei; Martí-Sánchez, Sara; Arbiol, Jordi; Hoffmann, Axel; Eickhoff, Martin

2018-03-28

We show that one-dimensional (1d) GaN quantum-wires (QWRs) exhibit intense and spectrally sharp emission lines. These QWRs are realized in an entirely self-assembled growth process by molecular beam epitaxy (MBE) on the side facets of GaN/AlN nanowire (NW) heterostructures. Time-integrated and time-resolved photoluminescence (PL) data in combination with numerical calculations allow the identification and assignment of the manifold emission features to three different spatial recombination centers within the NWs. The recombination processes in the QWRs are driven by efficient charge carrier transfer effects between the different optically active regions, providing high intense QWR luminescence despite their small volume. This is deduced by a fast rise time of the QWR PL, which is similar to the fast decay-time of adjacent carrier reservoirs. Such processes, feeding the ultra-narrow QWRs with carriers from the relatively large NWs, can be the key feature towards the realization of future QWR-based devices. While processing of single quantum structures with diameters in the nm range presents a serious obstacle with respect to their integration into electronic or photonic devices, the QWRs presented here can be analyzed and processed using existing techniques developed for single NWs.

Tungsten-doped TiO2/reduced Graphene Oxide nano-composite photocatalyst for degradation of phenol: A system to reduce surface and bulk electron-hole recombination.

PubMed

Yadav, Manisha; Yadav, Asha; Fernandes, Rohan; Popat, Yaksh; Orlandi, Michele; Dashora, Alpa; Kothari, D C; Miotello, Antonio; Ahuja, B L; Patel, Nainesh

2017-12-01

Recombination of photogenerated charges is the main factor affecting the photocatalytic activity of TiO 2 . Here, we report a combined strategy of suppressing both the bulk as well as the surface recombination processes by doping TiO 2 with tungsten and forming a nanocomposite with reduced graphene oxide (rGO), respectively. Sol-gel method was used to dope and optimize the concentration of W in TiO 2 powder. UV-Vis, XPS, PL and time resolved PL spectra along with DFT calculations indicate that W 6+ in TiO 2 lattice creates an impurity level just below the conduction band of TiO 2 to act as a trapping site of electrons, which causes to improve the lifetime of the photo-generated charges. Maximum reduction in the PL intensity and the improvement in charge carrier lifetime was observed for TiO 2 doped with 1 at.% W (1W-TiO 2 ), which also displayed the highest photo-activity for the degradation of p-nitro phenol pollutant in water. Tuning of rGO/TiO 2 ratio (weight) disclosed that the highest activity can be achieved with the composite formed by taking equal amounts of TiO 2 and rGO (1:1), in which the strong interaction between TiO 2 and rGO causes an effective charge transfer via bonds formed near the interface as indicated by XPS. Both these optimized concentrations were utilized to form the composite rGO/1W-TiO 2 , which showed the highest activity in photo-degradation of p-nitro phenol (87%) as compared to rGO/TiO 2 (42%), 1W-TiO 2 (62%) and pure TiO 2 (29%) in 180 min. XPS and PL results revealed that in the present nanocomposite, tungsten species traps the excited electron to reduce the interband recombination in the bulk, while the interaction between TiO 2 and rGO creates a channel for fast transfer of excited electrons towards the latter before being recombined on the surface defect sites. Copyright © 2017 Elsevier Ltd. All rights reserved.

Charge carrier dynamics investigation of CuInS2 quantum dots films using injected charge extraction by linearly increasing voltage (i-CELIV): the role of ZnS Shell

NASA Astrophysics Data System (ADS)

Bi, Ke; Sui, Ning; Zhang, Liquan; Wang, Yinghui; Liu, Qinghui; Tan, Mingrui; Zhou, Qiang; Zhang, Hanzhuang

2016-12-01

The role of ZnS shell on the photo-physical properties within CuInS2/ZnS quantum dots (QDs) is carefully studied in optoelectronic devices. Linearly increasing voltage technique has been employed to investigate the charge carrier dynamics of both CuInS2 and CuInS2/ZnS QDs films. This study shows that charge carriers follow a similar behavior of monomolecular recombination in this film, with their charge transfer rate correlates to the increase of applied voltage. It turns out that the ZnS shell could affect the carrier diffusion process through depressing the trapping states and would build up a potential barrier.

Amplified Sensitivity of Nitrogen-Vacancy Spins in Nanodiamonds Using All-Optical Charge Readout.

PubMed

Hopper, David A; Grote, Richard R; Parks, Samuel M; Bassett, Lee C

2018-04-23

Nanodiamonds containing nitrogen-vacancy (NV) centers offer a versatile platform for sensing applications spanning from nanomagnetism to in vivo monitoring of cellular processes. In many cases, however, weak optical signals and poor contrast demand long acquisition times that prevent the measurement of environmental dynamics. Here, we demonstrate the ability to perform fast, high-contrast optical measurements of charge distributions in ensembles of NV centers in nanodiamonds and use the technique to improve the spin-readout signal-to-noise ratio through spin-to-charge conversion. A study of 38 nanodiamonds with sizes ranging between 20 and 70 nm, each hosting a small ensemble of NV centers, uncovers complex, multiple time scale dynamics due to radiative and nonradiative ionization and recombination processes. Nonetheless, the NV-containing nanodiamonds universally exhibit charge-dependent photoluminescence contrasts and the potential for enhanced spin readout using spin-to-charge conversion. We use the technique to speed up a T 1 relaxometry measurement by a factor of 5.

Excitation correlation photoluminescence in the presence of Shockley-Read-Hall recombination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borgwardt, M., E-mail: mario.borgwardt@helmholtz-berlin.de; Sippel, P.; Eichberger, R.

Excitation correlation photoluminescence (ECPL) measurements are often analyzed in the approximation of a cross correlation of charge carrier populations generated by the two delayed pulses. In semiconductors, this approach is valid for a linear non-radiative recombination path, but not for a non-linear recombination rate as in the general Shockley-Read-Hall recombination scenario. Here, the evolution of the ECPL signal was studied for deep trap recombination following Shockley-Read-Hall statistics. Analytic solutions can be obtained for a fast minority trapping regime and steady state recombination. For the steady state case, our results show that the quadratic radiative term plays only a minor role,more » and that the shape of the measured signal is mostly determined by the non-linearity of the recombination itself. We find that measurements with unbalanced intense pump and probe pulses can directly provide information about the dominant non-radiative recombination mechanism. The signal traces follow the charge carrier concentrations, despite the complex origins of the signal, thus showing that ECPL can be applied to study charge carrier dynamics in semiconductors without requiring elaborate calculations. The model is compared with measurements on a reference sample with alternating layers of InGaAs/InAlAs that were additionally cross-checked with time resolved optical pump terahertz probe measurements and found to be in excellent agreement.« less

Long term stability of c-Si surface passivation using corona charged SiO2

NASA Astrophysics Data System (ADS)

Bonilla, Ruy S.; Reichel, Christian; Hermle, Martin; Hamer, Phillip; Wilshaw, Peter R.

2017-08-01

Recombination at the semiconductor surface continues to be a major limit to optoelectronic device performance, in particular for solar cells. Passivation films reduce surface recombination by a combination of chemical and electric field effect components. Dielectric films used for this purpose, however, must also accomplish optical functions at the cell surface. In this paper, corona charge is seen as a potential method to enhance the passivation properties of a dielectric film while maintaining its optical characteristics. It is observed that corona charge can produce extreme reductions in surface recombination via field effect, in the best case leading to lifetimes exceeding 5 ms at an injection of 1015 cm-3. For a 200 μm n-type 1 Ω cm c-Si wafer, this equates to surface recombination velocities below 0.65 cm/s and J0e values of 0.92 fA/cm2. The average improvement in passivation after corona charging gave lifetimes of 1-3 ms. This was stabilised for a period of 3 years by chemically treating the films to prevent water absorption. Surface recombination was kept below 7 cm/s, and J0e < 16.28 fA/cm2 for 3 years, with a decay time constant of 8.7 years. Simulations of back-contacted n-type cells show that front surface recombination represents less than 2% of the total internally generated power in the cell (the loss in power output) when the passivation is kept better than 16 fA/cm2, and as high as 10% if front recombination is worse than 100 fA/cm2.

Surface modifications of photoanodes in dye sensitized solar cells: enhanced light harvesting and reduced recombination

NASA Astrophysics Data System (ADS)

Saxena, Vibha; Aswal, D. K.

2015-06-01

In a quest to harvest solar power, dye-sensitized solar cells (DSSCs) have potential for low-cost eco-friendly photovoltaic devices. The major processes which govern the efficiency of a DSSC are photoelectron generation, injection of photo-generated electrons to the conduction band (CB) of the mesoporous nanocrystalline semiconductor (nc-SC); transport of CB electrons through nc-SC and subsequent collection of CB electrons at the counter electrode (CE) through the external circuit; and dye regeneration by redox couple or hole transport layer (HTL). Most of these processes occur at various interfaces of the photoanode. In addition, recombination losses of photo-generated electrons with either dye or redox molecules take place at the interfaces. Therefore, one of the key requirements for high efficiency is to improve light harvesting of the photoanode and to reduce the recombination losses at various interfaces. In this direction, surface modification of the photoanode is the simplest method among the various other approaches available in the literature. In this review, we present a comprehensive discussion on surface modification of the photoanode, which has been adopted in the literature for not only enhancing light harvesting but also reducing recombination. Various approaches towards surface modification of the photoanode discussed are (i) fluorine-doped tin oxide (FTO)/nc-SC interface modified via a compact layer of semiconductor material which blocks exposed sites of FTO to electrolyte (or HTL), (ii) nc-SC/dye interface modification either through acid treatment resulting in enhanced dye loading due to a positively charged surface or by depositing insulating/semiconducting blocking layer on the nc-SC surface, which acts as a tunneling barrier for recombination, (iii) nc-SC/dye interface modified by employing co-adsorbents which helps in reducing the dye aggregation and thereby recombination, and (iv) dye/electrolyte (or dye/HTL) interface modification using additives which provides surface passivation as well as positive movement of the nc-SC Fermi level owing to negative charge at the surface and hence improves light harvesting and reduced recombination. Finally, we discuss the advantages and disadvantages of various approaches towards high-efficiency DSSCs.

Effect of molecular properties on the performance of polymer light-emitting diodes

NASA Astrophysics Data System (ADS)

Ramos, Marta M. D.; Almeida, A. M.; Correia, Helena M. G.; Ribeiro, R. Mendes; Stoneham, A. M.

2004-11-01

The performance of a single layer polymer light-emitting diode depends on several interdependent factors, although recombination between electrons and holes within the polymer layer is believed to play an important role. Our aim is to carry out computer experiments in which bipolar charge carriers are injected in polymer networks made of poly(p-phenylene vinylene) chains randomly oriented. In these simulations, we follow the charge evolution in time from some initial state to the steady state. The intra-molecular properties of the polymer molecules obtained from self-consistent quantum molecular dynamics calculations are used in the mesoscopic model. The purpose of the present work is to clarify the effects of intra-molecular charge mobility and energy disorder on recombination efficiency. In particular, we find that charge mobility along the polymer chains has a serious influence on recombination within the polymer layer. Our results also show that energy disorder due to differences in ionization potential and electron affinity of neighbouring molecules affects mainly recombinations that occur near the electrodes at polymer chains parallel to them.

Fast calculator for X-ray emission due to Radiative Recombination and Radiative Electron Capture in relativistic heavy-ion atom collisions

NASA Astrophysics Data System (ADS)

Herdrich, M. O.; Weber, G.; Gumberidze, A.; Wu, Z. W.; Stöhlker, Th.

2017-10-01

In experiments with highly charged, fast heavy ions the Radiative Recombination (RR) and Radiative Electron Capture (REC) processes have significant cross sections in an energy range of up to a few GeV / u . They are some of the most important charge changing processes in collisions of heavy ions with atoms and electrons, leading to the emission of a photon along with the formation of the ground and excited atomic states. Hence, for the understanding and planning of experiments, in particular for X-ray spectroscopy studies, at accelerator ring facilities, such as FAIR, it is crucial to have a good knowledge of these cross sections and the associated radiation characteristics. In the frame of this work a fast calculator, named RECAL, for the RR and REC process is presented and its capabilities are demonstrated with the analysis of a recently conducted experiment at the Experimental Storage Ring (ESR) at the GSI Helmholtz Center for Heavy Ion Research in Darmstadt, Germany. A method is presented to determine unknown X-ray emission cross sections via normalization of the recorded spectra to REC cross sections calculated by RECAL.

Controlling the influence of Auger recombination on the performance of quantum-dot light-emitting diodes

PubMed Central

Bae, Wan Ki; Park, Young-Shin; Lim, Jaehoon; Lee, Donggu; Padilha, Lazaro A.; McDaniel, Hunter; Robel, Istvan; Lee, Changhee; Pietryga, Jeffrey M.; Klimov, Victor I.

2013-01-01

Development of light-emitting diodes (LEDs) based on colloidal quantum dots is driven by attractive properties of these fluorophores such as spectrally narrow, tunable emission and facile processibility via solution-based methods. A current obstacle towards improved LED performance is an incomplete understanding of the roles of extrinsic factors, such as non-radiative recombination at surface defects, versus intrinsic processes, such as multicarrier Auger recombination or electron-hole separation due to applied electric field. Here we address this problem with studies that correlate the excited state dynamics of structurally engineered quantum dots with their emissive performance within LEDs. We find that because of significant charging of quantum dots with extra electrons, Auger recombination greatly impacts both LED efficiency and the onset of efficiency roll-off at high currents. Further, we demonstrate two specific approaches for mitigating this problem using heterostructured quantum dots, either by suppressing Auger decay through the introduction of an intermediate alloyed layer, or by using an additional shell that impedes electron transfer into the quantum dot to help balance electron and hole injection. PMID:24157692

Direct observation of electron emission and recombination processes by time domain measurements of charge pumping current

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hori, Masahiro, E-mail: hori@eng.u-toyama.ac.jp; Watanabe, Tokinobu; Ono, Yukinori

2015-01-26

To analyze the charge pumping (CP) sequence in detail, the source/drain electron current and the substrate hole current under the CP mode of transistors are simultaneously monitored in the time domain. Peaks are observed in both the electron and hole currents, which are, respectively, attributed to the electron emission from the interface defects and to the recombination with holes. The peak caused by the electron emission is found to consist of two components, strongly suggesting that the present time-domain measurement can enable us to resolve different kinds of interface defects. Investigating the correlation between the number of emitted and recombinedmore » electrons reveals that only one of the two components contributes to the CP current for the gate-pulse fall time from 6.25 × 10{sup −4} to 1.25 × 10{sup −2} s.« less

Effect of Proton Radiation on the Kinetics of Phosphorescence Decay in the Ceramic Material ZnS-Cu

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuchakova, T.A.; Vesna, G.V.; Makara, V.A.

2004-11-01

The results of studying the dose dependences of the decay kinetics of phosphorescence excited by X-ray radiation in luminescent ZnS-Cu ceramic material before and after irradiation with 50-MeV protons are considered. An anomalous variation in the exponent of the hyperbolic phosphorescence curves was observed experimentally as the accumulated light sum increased. It is found from an analysis of the data obtained that two processes are involved in the decay: one of these is monomolecular and corresponds to the first-order kinetics; the other is bimolecular and corresponds to the second-order kinetics. Transitions of charge carriers delocalized from traps occur at themore » nonradiative-recombination centers induced by proton radiation. Recombination of these charge carriers at the emission centers in the course of decay is described by the second-order kinetics.« less

Time-resolved correlative optical microscopy of charge-carrier transport, recombination, and space-charge fields in CdTe heterostructures

DOE PAGES

Kuciauskas, Darius; Myers, Thomas H.; Barnes, Teresa M.; ...

2017-02-20

From time- and spatially resolved optical measurements, we show that extended defects can have a large effect on the charge-carrier recombination in II-VI semiconductors. In CdTe double heterostructures grown by molecular beam epitaxy on the InSb (100)-orientation substrates, we characterized the extended defects and found that near stacking faults the space-charge field extends by 2-5 μm. Charge carriers drift (with the space-charge field strength of 730-1,360 V cm -1) and diffuse (with the mobility of 260 ± 30 cm 2 V -1 s -1) toward the extended defects, where the minority-carrier lifetime is reduced from 560 ns to 0.25 ns.more » Furthermore, the extended defects are nonradiative recombination sinks that affect areas significantly larger than the typical crystalline grains in II-VI solar cells. From the correlative time-resolved photoluminescence and second-harmonic generation microscopy data, we developed a band-diagram model that can be used to analyze the impact of extended defects on solar cells and other electronic devices.« less

Time-resolved correlative optical microscopy of charge-carrier transport, recombination, and space-charge fields in CdTe heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuciauskas, Darius; Myers, Thomas H.; Barnes, Teresa M.

From time- and spatially resolved optical measurements, we show that extended defects can have a large effect on the charge-carrier recombination in II-VI semiconductors. In CdTe double heterostructures grown by molecular beam epitaxy on the InSb (100)-orientation substrates, we characterized the extended defects and found that near stacking faults the space-charge field extends by 2-5 μm. Charge carriers drift (with the space-charge field strength of 730-1,360 V cm -1) and diffuse (with the mobility of 260 ± 30 cm 2 V -1 s -1) toward the extended defects, where the minority-carrier lifetime is reduced from 560 ns to 0.25 ns.more » Furthermore, the extended defects are nonradiative recombination sinks that affect areas significantly larger than the typical crystalline grains in II-VI solar cells. From the correlative time-resolved photoluminescence and second-harmonic generation microscopy data, we developed a band-diagram model that can be used to analyze the impact of extended defects on solar cells and other electronic devices.« less

Do grain boundaries dominate non-radiative recombination in CH 3NH 3PbI 3 perovskite thin films?

DOE PAGES

Yang, Mengjin; Zeng, Yining; Li, Zhen; ...

2017-01-13

Here, we examine GBs with respect to non-GB regions (grain surfaces (GSs) and grain interiors (GIs)) in high-quality micrometer-sized perovskite CH 3NH 3PbI 3 (or MAPbI 3) thin films using high-resolution confocal fluorescence-lifetime imaging microscopy in conjunction with kinetic modeling of charge-transport and recombination processes. We show that, contrary to previous studies, GBs in our perovskite MAPbI3 thin films do not lead to increased recombination but that recombination in these films happens primarily in the non-GB regions (i.e., GSs or GIs). We also find that GBs in these films are not transparent to photogenerated carriers, which is likely associated withmore » a potential barrier at GBs. Lastly, even though GBs generally display lower luminescence intensities than GSs/GIs, the lifetimes at GBs are no worse than those at GSs/GIs, further suggesting that GBs do not dominate non-radiative recombination in MAPbI 3 thin films.« less

Electron Mobility and Trapping in Ferrihydrite Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soltis, Jennifer A.; Schwartzberg, Adam M.; Zarzycki, Piotr

Iron is the most abundant transition metal in the Earth's crust, and naturally occurring iron oxide minerals play a commanding role in environmental redox reactions. Although iron oxide redox reactions are well studied, their precise mechanisms are not fully understood. Recent work has shown that these involve electron transfer pathways within the solid, suggesting that overall reaction rates could be dependent on electron mobility. Initial ultrafast spectroscopy studies of iron oxide nanoparticles sensitized by fluorescein derivatives supported a model for electron mobility based on polaronic hopping of electron charge carriers between iron sites, but the constitutive relationships between hopping mobilitiesmore » and interfacial charge transfer processes has remained obscured. We developed a coarse-grained lattice Monte Carlo model to simulate the collective mobilities and lifetimes of these photoinjected electrons with respect to recombination with adsorbed dye molecules for the essential nanophase ferrihydrite, and tested predictions made by the simulations using pump-probe spectroscopy. We acquired optical transient absorption spectra as a function of particle size and under a variety of solution conditions, and used cryogenic transmission electron microscopy to determine the aggregation state of the nanoparticles. We observed biphasic electron recombination kinetics over timescales that spanned picoseconds to microseconds, the slower regime of which was fit with a stretched exponential decay function. The recombination rates were weakly affected by nanoparticle size and aggregation state, suspension pH, and the injection of multiple electrons per nanoparticle. We conclude that electron mobility indeed limits the rate of interfacial electron transfer in these systems with the slowest processes relating to escape from deep traps, the presence of which outweighs the influence of environmental factors such as pH-dependent surface charge.« less

Electron Mobility and Trapping in Ferrihydrite Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soltis, Jennifer A.; Schwartzberg, Adam M.; Zarzycki, Piotr

Iron is the most abundant transition metal in the Earth’s crust, and naturally occurring iron oxide minerals play a commanding role in environmental redox reactions. Although iron oxide redox reactions are well-studied, their precise mechanisms are not fully understood. Recent work has shown that these involve electron transfer pathways within the solid, suggesting that overall reaction rates could be dependent upon electron mobility. Initial ultrafast spectroscopy studies of iron oxide nanoparticles sensitized by fluorescein derivatives supported a model for electron mobility based on polaronic hopping of electron charge carriers between iron sites, but the constitutive relationships between hopping mobilities andmore » interfacial charge transfer processes has remained obscured. In this paper, we developed a coarse-grained lattice Monte Carlo model to simulate the collective mobilities and lifetimes of these photoinjected electrons with respect to recombination with adsorbed dye molecules for essential nanophase ferrihydrite and tested predictions made by the simulations using pump–probe spectroscopy. We acquired optical transient absorption spectra as a function of the particle size and under a variety of solution conditions and used cryogenic transmission electron microscopy to determine the aggregation state of the nanoparticles. We observed biphasic electron recombination kinetics over time scales that spanned from picoseconds to microseconds, the slower regime of which was fit with a stretched exponential decay function. The recombination rates were weakly affected by the nanoparticle size and aggregation state, suspension pH, and injection of multiple electrons per nanoparticle. Finally, we conclude that electron mobility indeed limits the rate of interfacial electron transfer in these systems, with the slowest processes relating to escape from deep traps, the presence of which outweighs the influence of environmental factors, such as pH-dependent surface charge.« less

Electron Mobility and Trapping in Ferrihydrite Nanoparticles

DOE PAGES

Soltis, Jennifer A.; Schwartzberg, Adam M.; Zarzycki, Piotr; ...

2017-05-18

Iron is the most abundant transition metal in the Earth’s crust, and naturally occurring iron oxide minerals play a commanding role in environmental redox reactions. Although iron oxide redox reactions are well-studied, their precise mechanisms are not fully understood. Recent work has shown that these involve electron transfer pathways within the solid, suggesting that overall reaction rates could be dependent upon electron mobility. Initial ultrafast spectroscopy studies of iron oxide nanoparticles sensitized by fluorescein derivatives supported a model for electron mobility based on polaronic hopping of electron charge carriers between iron sites, but the constitutive relationships between hopping mobilities andmore » interfacial charge transfer processes has remained obscured. In this paper, we developed a coarse-grained lattice Monte Carlo model to simulate the collective mobilities and lifetimes of these photoinjected electrons with respect to recombination with adsorbed dye molecules for essential nanophase ferrihydrite and tested predictions made by the simulations using pump–probe spectroscopy. We acquired optical transient absorption spectra as a function of the particle size and under a variety of solution conditions and used cryogenic transmission electron microscopy to determine the aggregation state of the nanoparticles. We observed biphasic electron recombination kinetics over time scales that spanned from picoseconds to microseconds, the slower regime of which was fit with a stretched exponential decay function. The recombination rates were weakly affected by the nanoparticle size and aggregation state, suspension pH, and injection of multiple electrons per nanoparticle. Finally, we conclude that electron mobility indeed limits the rate of interfacial electron transfer in these systems, with the slowest processes relating to escape from deep traps, the presence of which outweighs the influence of environmental factors, such as pH-dependent surface charge.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnett, C.F.; Gauster, W.B.; Ray, J.A.

A graphical compilation is presented of atomic and molecular cross sections of interest to controlled thermonuclear research. The cross sections are shown, as a function of energy, for collision processes involving molecular ion dissociation, charge exchange, excitation, ionization, photoionization, scattering, energy loss, and recombination. Pertinent nuclear cross sections are also included. A bibliography is given covering the literature since 1950. (auth)

Interfacial Electron Transfer at Sensitized Nanocrystalline TiO2 Electrolyte Interfaces: Influence of Surface Electric Fields and Lewis-Acidic Cations

NASA Astrophysics Data System (ADS)

Barr, Timothy J.

Interfacial electron transfer reactions facilitate charge separation and recombination in dye-sensitized solar cells (DSSCs). Understanding what controls these electron transfer reactions is necessary to develop efficient DSSCs. Gerischer proposed a theory for interfacial electron transfer where the rate constant was related to the energetic overlap between the donor and acceptor states. The present work focuses on understanding how the composition of the CH3CN electrolyte influenced this overlap. It was found that the identity of the electrolyte cation tuned the energetic position of TiO2 electron acceptor states, similar to how pH influences the flatband potential of bulk semiconductors in aqueous electrolytes. For example, the onset for absorption changes, that were attributed to electrons in the TiO2 thin film, were 0.5 V more positive in Mg2+ containing electrolyte than TBA+, where TBA+ is tetrabutylammonium. Similar studies performed on mesoporous, nanocrystalline SnO2 thin films reported a similar cation dependence, but also found evidence for electrons that did not absorb in the visible region that were termed ‘phantom electrons.’. Electron injection is known to generate surface electric fields on the order of 2 MV/cm. The rearrangement of cations in response to surface electric fields, termed screening, was investigated. It was found that magnitude of the electric field and the screening dynamics were dependent on the identity of the electrolyte cation. The rate of charge recombination to the anionic iodide/triiodide redox mediator correlated with the screening ability of the cation, and was initially thought to control charge recombination. However, it was difficult to determine whether electron diffusion or driving force were also cation dependent. Therefore, a in-lab built apparatus, termed STRiVE, was constructed that could disentangle the influence electron diffusion, driving force, and electric fields had on charge recombination. It was found that electron diffusion was independent of the electrolyte cation. Furthermore, charge recombination displayed the same cation-sensitivity using both anionic and cationic redox mediators, indicating electric fields did not cause the cation-dependence of charge recombination. Instead, it was found that the electrolyte cation tuned the energetic position of the TiO2 acceptor states and modulated the driving force for charge recombination.

Sacrificial hydrogen generation from aqueous triethanolamine with Eosin Y-sensitized Pt/TiO2 photocatalyst in UV, visible and solar light irradiation.

PubMed

Chowdhury, Pankaj; Gomaa, Hassan; Ray, Ajay K

2015-02-01

In this paper, we have studied Eosin Y-sensitized sacrificial hydrogen generation with triethanolamine as electron donor in UV, visible, and solar light irradiation. Aeroxide TiO2 was loaded with platinum metal via solar photo-deposition method to reduce the electron hole recombination process. Photocatalytic sacrificial hydrogen generation was influenced by several factors such as platinum loading (wt%) on TiO2, solution pH, Eosin Y to Pt/TiO2 mass ratio, triethanolamine concentration, and light (UV, visible and solar) intensities. Detailed reaction mechanisms in visible and solar light irradiation were established. Oxidation of triethanolamine and formaldehyde formation was correlated with hydrogen generation in both visible and solar lights. Hydrogen generation kinetics followed a Langmuir-type isotherm with reaction rate constant and adsorption constant of 6.77×10(-6) mol min(-1) and 14.45 M(-1), respectively. Sacrificial hydrogen generation and charge recombination processes were studied as a function of light intensities. Apparent quantum yields (QYs) were compared for UV, visible, and solar light at four different light intensities. Highest QYs were attained at lower light intensity because of trivial charge recombination. At 30 mW cm(-2) we achieved QYs of 10.82%, 12.23% and 11.33% in UV, visible and solar light respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Mengjin; Zeng, Yining; Li, Zhen

Here, we examine GBs with respect to non-GB regions (grain surfaces (GSs) and grain interiors (GIs)) in high-quality micrometer-sized perovskite CH 3NH 3PbI 3 (or MAPbI 3) thin films using high-resolution confocal fluorescence-lifetime imaging microscopy in conjunction with kinetic modeling of charge-transport and recombination processes. We show that, contrary to previous studies, GBs in our perovskite MAPbI3 thin films do not lead to increased recombination but that recombination in these films happens primarily in the non-GB regions (i.e., GSs or GIs). We also find that GBs in these films are not transparent to photogenerated carriers, which is likely associated withmore » a potential barrier at GBs. Lastly, even though GBs generally display lower luminescence intensities than GSs/GIs, the lifetimes at GBs are no worse than those at GSs/GIs, further suggesting that GBs do not dominate non-radiative recombination in MAPbI 3 thin films.« less

Interfacial Engineering and Charge Carrier Dynamics in Extremely Thin Absorber Solar Cells

NASA Astrophysics Data System (ADS)

Edley, Michael

Photovoltaic energy is a clean and renewable source of electricity; however, it faces resistance to widespread use due to cost. Nanostructuring decouples constraints related to light absorption and charge separation, potentially reducing cost by allowing a wider variety of processing techniques and materials to be used. However, the large interfacial areas also cause an increased dark current which negatively affects cell efficiency. This work focuses on extremely thin absorber (ETA) solar cells that used a ZnO nanowire array as a scaffold for an extremely thin CdSe absorber layer. Photoexcited electrons generated in the CdSe absorber are transferred to the ZnO layer, while photogenerated holes are transferred to the liquid electrolyte. The transfer of photoexcited carriers to their transport layer competes with bulk recombination in the absorber layer. After charge separation, transport of charge carriers to their respective contacts must occur faster than interfacial recombination for efficient collection. Charge separation and collection depend sensitively on the dimensions of the materials as well as their interfaces. We demonstrated that an optimal absorber thickness can balance light absorption and charge separation. By treating the ZnO/CdSe interface with a CdS buffer layer, we were able to improve the Voc and fill factor, increasing the ETA cell's efficiency from 0.53% to 1.34%, which is higher than that achievable using planar films of the same material. We have gained additional insight into designing ETA cells through the use of dynamic measurements. Ultrafast transient absorption spectroscopy revealed that characteristic times for electron injection from CdSe to ZnO are less than 1 ps. Electron injection is rapid compared to the 2 ns bulk lifetime in CdSe. Optoelectronic measurements such as transient photocurrent/photovoltage and electrochemical impedance spectroscopy were applied to study the processes of charge transport and interfacial recombination. With these techniques, the extension of the depletion layer from CdSe into ZnO was determined to be vital to suppression of interfacial recombination. However, depletion of the ZnO also restricted the effective diffusion core for electrons and slowed their transport. Thus, materials and geometries should be chosen to allow for a depletion layer that suppresses interfacial recombination without impeding electron transport to the point that it is detrimental to cell performance. Thin film solar cells are another promising technology that can reduce costs by relaxing material processing requirements. CuInxGa (1-x)Se (CIGS) is a well studied thin film solar cell material that has achieved good efficiencies of 22.6%. However, use of rare elements raise concerns over the use of CIGS for global power production. CuSbS2 shares chemistry with CuInSe2 and also presents desirable properties for thin film absorbers such as optimal band gap (1.5 eV), high absorption coefficient, and Earth-abundant and non-toxic elements. Despite the promise of CuSbS2, direct characterization of the material for solar cell application is scarce in the literature. CuSbS2 nanoplates were synthesized by a colloidal hot-injection method at 220 °C in oleylamine. The CuSbS2 platelets synthesized for 30 minutes had dimensions of 300 nm by 400 nm with a thickness of 50 nm and were capped with the insulating oleylamine synthesis ligand. The oleylamine synthesis ligand provides control over nanocrystal growth but is detrimental to intercrystal charge transport that is necessary for optoelectronic device applications. Solid-state and solution phase ligand exchange of oleylamine with S2- were used to fabricate mesoporous films of CuSbS2 nanoplates for application in solar cells. Exchange of the synthesis ligand with S2- resulted in a two order of magnitude increase in 4-point probe conductivity. Photoexcited carrier lifetimes of 1.4 ns were measured by time-resolved terahertz spectroscopy, indicating potential for CuSbS2 as a solar cell absorber material.

Nonequilibrium mechanisms of weak electrolyte electrification under the action of constant voltage

NASA Astrophysics Data System (ADS)

Stishkov, Yu. K.; Chirkov, V. A.

2016-07-01

The formation of space charge in weak electrolytes, specifically in liquid dielectrics, has been considered. An analytical solution is given to a simplified set of Nernst-Planck equations that describe the formation of nonequilibrium recombination layers in weak electrolytes. This approximate analytical solution is compared with computer simulation data for a complete set of Poisson-Nernst-Planck equations. It has been shown that the current passage in weak electrolytes can be described by a single dimensionless parameter that equals the length of a near-electrode recombination layer divided by the width of the interelectrode gap. The formation mechanism and the structure of charged nonequilibrium near-electrode layers in the nonstationary regime have been analyzed for different injection-to-conduction current ratios. It has been found that almost all charge structures encountered in weak dielectrics can be accounted for by the nonequilibrium dissociation-recombination mechanism of space charge formation.

Spectral Diagnostics of Galactic and Stellar X-Ray Emission from Charge Exchange Recombination

NASA Technical Reports Server (NTRS)

Wargelin, B.

2003-01-01

The proposed research uses the electron beam ion trap at the Lawrence Livermore National Laboratory to study the X-ray emission from charge-exchange recombination of highly charged ions with neutral gases. The resulting data fill a void in the existing experimental and theoretical data and are needed to explain all or part of the observed X-ray emission from the Galactic Ridge, solar and stellar winds, the Galactic Center, supernova ejecta, and photoionized nebulae.

Recombination in polymer-fullerene bulk heterojunction solar cells

NASA Astrophysics Data System (ADS)

Cowan, Sarah R.; Roy, Anshuman; Heeger, Alan J.

2010-12-01

Recombination of photogenerated charge carriers in polymer bulk heterojunction (BHJ) solar cells reduces the short circuit current (Jsc) and the fill factor (FF). Identifying the mechanism of recombination is, therefore, fundamentally important for increasing the power conversion efficiency. Light intensity and temperature-dependent current-voltage measurements on polymer BHJ cells made from a variety of different semiconducting polymers and fullerenes show that the recombination kinetics are voltage dependent and evolve from first-order recombination at short circuit to bimolecular recombination at open circuit as a result of increasing the voltage-dependent charge carrier density in the cell. The “missing 0.3 V” inferred from comparison of the band gaps of the bulk heterojunction materials and the measured open-circuit voltage at room-temperature results from the temperature dependence of the quasi-Fermi levels in the polymer and fullerene domains—a conclusion based on the fundamental statistics of fermions.

Differential effects of DEAE negative mode chromatography and gel-filtration chromatography on the charge status of Helicobacter pylori neutrophil-activating protein

PubMed Central

Pan, Timothy; Tzeng, Huey-Fen

2017-01-01

Helicobacter pylori neutrophil-activating protein (HP-NAP) is involved in H. pylori-associated gastric inflammation. HP-NAP is also a vaccine candidate, a possible drug target, and a potential diagnostic marker for H. pylori-associated diseases. Previously, we purified recombinant HP-NAP by one-step diethylaminoethyl (DEAE) negative mode chromatography by collecting the unbound fraction at pH 8.0 at 4°C. It remains unclear why HP-NAP does not bind to DEAE resins at the pH above its isoelectric point during the purification. To investigate how pH affects the surface net charge of HP-NAP and its binding to DEAE resins during the purification, recombinant HP-NAP expressed in Escherichia coli was subjected to DEAE negative mode chromatography at pH ranging from 7.0 to 9.0 at 25°C and the surface charge of purified HP-NAP was determined by capillary electrophoresis. A minimal amount of HP-NAP was detected in the elution fraction of DEAE Sepharose resin at pH 8.5, whereas recombinant HP-NAP was detected in the elution fraction of DEAE Sephadex resin only at pH 7.0 and 8.0. The purified recombinant HP-NAP obtained from the unbound fractions was not able to bind to DEAE resins at pH 7.0 to 9.0. In addition, the surface charge of the purified HP-NAP was neutral at pH 7.0 to 8.0 and was either neutral or slightly negative at pH 8.5 and 9.0. However, recombinant HP-NAP purified from gel-filtration chromatography was able to bind to DEAE Sepharose resin at pH 7.0 to 9.0 and DEAE Sephadex resin at pH 7.0. At pH 8.5 and 9.0, only the negatively charged species of HP-NAP were found. Thus, recombinant HP-NAP with different charge status can be differentially purified by DEAE negative mode chromatography and gel-filtration chromatography. Furthermore, the charge distribution on the surface of HP-NAP, the presence of impure proteins, and the overall net charge of the resins all affect the binding of HP-NAP to DEAE resins during the negative purification. PMID:28328957

Differential effects of DEAE negative mode chromatography and gel-filtration chromatography on the charge status of Helicobacter pylori neutrophil-activating protein.

PubMed

Hong, Zhi-Wei; Yang, Yu-Chi; Pan, Timothy; Tzeng, Huey-Fen; Fu, Hua-Wen

2017-01-01

Helicobacter pylori neutrophil-activating protein (HP-NAP) is involved in H. pylori-associated gastric inflammation. HP-NAP is also a vaccine candidate, a possible drug target, and a potential diagnostic marker for H. pylori-associated diseases. Previously, we purified recombinant HP-NAP by one-step diethylaminoethyl (DEAE) negative mode chromatography by collecting the unbound fraction at pH 8.0 at 4°C. It remains unclear why HP-NAP does not bind to DEAE resins at the pH above its isoelectric point during the purification. To investigate how pH affects the surface net charge of HP-NAP and its binding to DEAE resins during the purification, recombinant HP-NAP expressed in Escherichia coli was subjected to DEAE negative mode chromatography at pH ranging from 7.0 to 9.0 at 25°C and the surface charge of purified HP-NAP was determined by capillary electrophoresis. A minimal amount of HP-NAP was detected in the elution fraction of DEAE Sepharose resin at pH 8.5, whereas recombinant HP-NAP was detected in the elution fraction of DEAE Sephadex resin only at pH 7.0 and 8.0. The purified recombinant HP-NAP obtained from the unbound fractions was not able to bind to DEAE resins at pH 7.0 to 9.0. In addition, the surface charge of the purified HP-NAP was neutral at pH 7.0 to 8.0 and was either neutral or slightly negative at pH 8.5 and 9.0. However, recombinant HP-NAP purified from gel-filtration chromatography was able to bind to DEAE Sepharose resin at pH 7.0 to 9.0 and DEAE Sephadex resin at pH 7.0. At pH 8.5 and 9.0, only the negatively charged species of HP-NAP were found. Thus, recombinant HP-NAP with different charge status can be differentially purified by DEAE negative mode chromatography and gel-filtration chromatography. Furthermore, the charge distribution on the surface of HP-NAP, the presence of impure proteins, and the overall net charge of the resins all affect the binding of HP-NAP to DEAE resins during the negative purification.

The OI/1S/ state - Its quenching by O2 and formation by the dissociative recombination of vibrationally excited O2/+/ ions

NASA Technical Reports Server (NTRS)

Zipf, E. C.

1979-01-01

The rate coefficient for the quenching of metastable O(1S) atoms by O2 was measured as a function of temperature from 250 to 550 K. The resulting Arrhenius expression correlates well with previous laboratory work. It is suggested that the much larger value of the rate coefficient inferred from an analysis of artificial auroral experiment, Precede, may be explained by overestimation of the contribution of O(1S) production from O2(+) dissociative recombination. The possibility that O(1S) atoms are produced only by the dissociative recombination of vibrationally excited O2(+) ions is examined; such excited ions would not exist in the Precede experiment because of the rapid cooling of the ions by resonant charge transfer processes.

Boosting the efficiency of quantum dot sensitized solar cells through modulation of interfacial charge transfer.

PubMed

Kamat, Prashant V

2012-11-20

The demand for clean energy will require the design of nanostructure-based light-harvesting assemblies for the conversion of solar energy into chemical energy (solar fuels) and electrical energy (solar cells). Semiconductor nanocrystals serve as the building blocks for designing next generation solar cells, and metal chalcogenides (e.g., CdS, CdSe, PbS, and PbSe) are particularly useful for harnessing size-dependent optical and electronic properties in these nanostructures. This Account focuses on photoinduced electron transfer processes in quantum dot sensitized solar cells (QDSCs) and discusses strategies to overcome the limitations of various interfacial electron transfer processes. The heterojunction of two semiconductor nanocrystals with matched band energies (e.g., TiO(2) and CdSe) facilitates charge separation. The rate at which these separated charge carriers are driven toward opposing electrodes is a major factor that dictates the overall photocurrent generation efficiency. The hole transfer at the semiconductor remains a major bottleneck in QDSCs. For example, the rate constant for hole transfer is 2-3 orders of magnitude lower than the electron injection from excited CdSe into oxide (e.g., TiO(2)) semiconductor. Disparity between the electron and hole scavenging rate leads to further accumulation of holes within the CdSe QD and increases the rate of electron-hole recombination. To overcome the losses due to charge recombination processes at the interface, researchers need to accelerate electron and hole transport. The power conversion efficiency for liquid junction and solid state quantum dot solar cells, which is in the range of 5-6%, represents a significant advance toward effective utilization of nanomaterials for solar cells. The design of new semiconductor architectures could address many of the issues related to modulation of various charge transfer steps. With the resolution of those problems, the efficiencies of QDSCs could approach those of dye sensitized solar cells (DSSC) and organic photovoltaics.

Dual functional passivating layer of graphene/TiO2 for improved performance of dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Shahid, Muhammad Umair; Mohamed, Norani Muti; Muhsan, Ali Samer; Khatani, Mehboob; Bashiri, Robabeh; Zaine, Siti Nur Azella; Shamsudin, Adel Eskandar

2018-02-01

The FTO/TiO2 interface plays a crucial role in the performance of dye-sensitized solar cells (DSSCs). The uneven microstructure morphology of FTO (fluorine-doped tin oxide) glass surface and high porosity of TiO2 layer produce tiny gaps and voids at the FTO/TiO2 interface that breaks the connectivity, leading to an increase in the recombination process. In the current work, a dual functional passivating layer is introduced by the combination of the graphene/TiO2 compact layer. The excellent mobility and flexibility of graphene is capitalized using its layer to fill the voids in the FTO surface, which can consequently reduce the charge transfer resistance at the interface, while the added TiO2 compact layer avoids direct contact with the electrolyte thus reducing the recombination. Graphene was synthesized by the facile solvent exfoliation method with the assistance of the probe sonication process. The parameters of sonication were optimized to achieve high-quality concentrated graphene inks (0.177-0.51 mg/ml). Raman spectroscopy and transmission electron microscopy (TEM) revealed that the graphene obtained is of a few-layer type. Electrochemical impedance spectroscopy (EIS) analysis indicated that the incorporated compact layer of graphene/TiO2 was capable of accelerating the charge transfer and reducing the recombination process at the FTO/TiO2 interface. Consequently, the photoconversion efficiency (PCE) for the device (1 cm2 active area) with double-coated graphene layer under one sun irradiation (AM 1.5) was found to be 49.49% higher than the conventional one.

Charge separation at disordered semiconductor heterojunctions from random walk numerical simulations.

PubMed

Mandujano-Ramírez, Humberto J; González-Vázquez, José P; Oskam, Gerko; Dittrich, Thomas; Garcia-Belmonte, Germa; Mora-Seró, Iván; Bisquert, Juan; Anta, Juan A

2014-03-07

Many recent advances in novel solar cell technologies are based on charge separation in disordered semiconductor heterojunctions. In this work we use the Random Walk Numerical Simulation (RWNS) method to model the dynamics of electrons and holes in two disordered semiconductors in contact. Miller-Abrahams hopping rates and a tunnelling distance-dependent electron-hole annihilation mechanism are used to model transport and recombination, respectively. To test the validity of the model, three numerical "experiments" have been devised: (1) in the absence of constant illumination, charge separation has been quantified by computing surface photovoltage (SPV) transients. (2) By applying a continuous generation of electron-hole pairs, the model can be used to simulate a solar cell under steady-state conditions. This has been exploited to calculate open-circuit voltages and recombination currents for an archetypical bulk heterojunction solar cell (BHJ). (3) The calculations have been extended to nanostructured solar cells with inorganic sensitizers to study, specifically, non-ideality in the recombination rate. The RWNS model in combination with exponential disorder and an activated tunnelling mechanism for transport and recombination is shown to reproduce correctly charge separation parameters in these three "experiments". This provides a theoretical basis to study relevant features of novel solar cell technologies.

Distance dependence in photoinduced intramolecular electron transfer. Additional remarks and calculations

NASA Astrophysics Data System (ADS)

Larsson, Sven; Volosov, Andrey

1987-12-01

Rate constants for photoinduced intramolecular electron transfer are calculated for four of the molecules studied by Hush et al. The electronic factor is obtained in quantum chemical calculations using the CNDO/S method. The results agree reasonably well with experiments for the forward reaction. Possible reasons for the disagreement for the charge recombination process are offered.

Polaron pair mediated triplet generation in polymer/fullerene blends

PubMed Central

Dimitrov, Stoichko D.; Wheeler, Scot; Niedzialek, Dorota; Schroeder, Bob C.; Utzat, Hendrik; Frost, Jarvist M.; Yao, Jizhong; Gillett, Alexander; Tuladhar, Pabitra S.; McCulloch, Iain; Nelson, Jenny; Durrant, James R.

2015-01-01

Electron spin is a key consideration for the function of organic semiconductors in light-emitting diodes and solar cells, as well as spintronic applications relying on organic magnetoresistance. A mechanism for triplet excited state generation in such systems is by recombination of electron-hole pairs. However, the exact charge recombination mechanism, whether geminate or nongeminate and whether it involves spin-state mixing is not well understood. In this work, the dynamics of free charge separation competing with recombination to polymer triplet states is studied in two closely related polymer-fullerene blends with differing polymer fluorination and photovoltaic performance. Using time-resolved laser spectroscopic techniques and quantum chemical calculations, we show that lower charge separation in the fluorinated system is associated with the formation of bound electron-hole pairs, which undergo spin-state mixing on the nanosecond timescale and subsequent geminate recombination to triplet excitons. We find that these bound electron-hole pairs can be dissociated by electric fields. PMID:25735188

Numerical study on electronic and optical properties of organic light emitting diodes.

PubMed

Kim, Kwangsik; Hwang, Youngwook; Won, Taeyoung

2013-08-01

In this paper, we present a finite element method (FEM) study of space charge effects in organic light emitting diodes. Our model includes a Gaussian density of states to account for the energetic disorder in organic semiconductors and the Fermi-Dirac statistics to account for the charge hopping process between uncorrelated sites. The physical model cover all the key physical processes in OLEDs, namely charge injection, transport and recombination, exciton diffusion, transfer and decay as well as light coupling, and thin-film-optics. The exciton model includes generation, diffusion, and energy transfer as well as annihilation. We assumed that the light emission originates from oscillating and thus embodied as excitons and embedded in a stack of multilayer. The out-coupled emission spectrum has been numerically calculated as a function of viewing angle, polarization, and dipole orientation. We discuss the accumulation of charges at internal interfaces and their signature in the transient response as well as the electric field distribution.

On the c-Si/SiO2 interface recombination parameters from photo-conductance decay measurements

NASA Astrophysics Data System (ADS)

Bonilla, Ruy S.; Wilshaw, Peter R.

2017-04-01

The recombination of electric charge carriers at semiconductor surfaces continues to be a limiting factor in achieving high performance optoelectronic devices, including solar cells, laser diodes, and photodetectors. The theoretical model and a solution algorithm for surface recombination have been previously reported. However, their successful application to experimental data for a wide range of both minority excess carrier concentrations and dielectric fixed charge densities has not previously been shown. Here, a parametrisation for the semiconductor-dielectric interface charge Q i t is used in a Shockley-Read-Hall extended formalism to describe recombination at the c-Si/SiO2 interface, and estimate the physical parameters relating to the interface trap density D i t , and the electron and hole capture cross-sections σ n and σ p . This approach gives an excellent description of the experimental data without the need to invoke a surface damage region in the c-Si/SiO2 system. Band-gap tail states have been observed to limit strongly the effectiveness of field effect passivation. This approach provides a methodology to determine interface recombination parameters in any semiconductor-insulator system using macro scale measuring techniques.

Charge transport and recombination in bulk heterojunction solar cells studied by the photoinduced charge extraction in linearly increasing voltage technique

NASA Astrophysics Data System (ADS)

Mozer, A. J.; Sariciftci, N. S.; Lutsen, L.; Vanderzande, D.; Österbacka, R.; Westerling, M.; Juška, G.

2005-03-01

Charge carrier mobility and recombination in a bulk heterojunction solar cell based on the mixture of poly[2-methoxy-5-(3,7-dimethyloctyloxy)-phenylene vinylene] (MDMO-PPV) and 1-(3-methoxycarbonyl)propyl-1-phenyl-(6,6)-C61 (PCBM) has been studied using the novel technique of photoinduced charge carrier extraction in a linearly increasing voltage (Photo-CELIV). In this technique, charge carriers are photogenerated by a short laser flash, and extracted under a reverse bias voltage ramp after an adjustable delay time (tdel). The Photo-CELIV mobility at room temperature is found to be μ =2×10-4cm2V-1s-1, which is almost independent on charge carrier density, but slightly dependent on tdel. Furthermore, determination of charge carrier lifetime and demonstration of an electric field dependent mobility is presented.

Charge recombination in the muon collider cooling channel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernow, R. C.; Palmer, R. B.

2012-12-21

The final stage of the ionization cooling channel for the muon collider must transversely recombine the positively and negatively charged bunches into a single beam before the muons can be accelerated. It is particularly important to minimize any emittance growth in this system since no further cooling takes place before the bunches are collided. We have found that emittance growth could be minimized by using symmetric pairs of bent solenoids and careful matching. We show that a practical design can be found that has transmission {approx}99%, emittance growth less than 0.1%, and minimal dispersion in the recombined bunches.

Analysis of the kinetics of P+ HA- recombination in membrane-embedded wild-type and mutant Rhodobacter sphaeroides reaction centers between 298 and 77 K indicates that the adjacent negatively charged QA ubiquinone modulates the free energy of P+ HA- and may influence the rate of the protein dielectric response.

PubMed

Gibasiewicz, Krzysztof; Pajzderska, Maria; Dobek, Andrzej; Brettel, Klaus; Jones, Michael R

2013-09-26

Time-resolved spectroscopic studies of recombination of the P(+)HA(-) radical pair in photosynthetic reaction centers (RCs) from Rhodobacter sphaeroides give an opportunity to study protein dynamics triggered by light and occurring over the lifetime of P(+)HA(-). The state P(+)HA(-) is formed after the ultrafast light-induced electron transfer from the primary donor pair of bacteriochlorophylls (P) to the acceptor bacteriopheophytin (HA). In order to increase the lifetime of this state, and thus increase the temporal window for the examination of protein dynamics, it is possible to block forward electron transfer from HA(-) to the secondary electron acceptor QA. In this contribution, the dynamics of P(+)HA(-) recombination were compared at a range of temperatures from 77 K to room temperature, electron transfer from HA(-) to QA being blocked either by prereduction of QA or by genetic removal of QA. The observed P(+)HA(-) charge recombination was significantly slower in the QA-deficient RCs, and in both types of complexes, lowering the temperature from RT to 77 K led to a slowing of charge recombination. The effects are explained in the frame of a model in which charge recombination occurs via competing pathways, one of which is thermally activated and includes transient formation of a higher-energy state, P(+)BA(-). An internal electrostatic field supplied by the negative charge on QA increases the free energy levels of the state P(+)HA(-), thus decreasing its energetic distance to the state P(+)BA(-). In addition, the dielectric response of the protein environment to the appearance of the state P(+)HA(-) is accelerated from ∼50-100 ns in the QA-deficient mutant RCs to ∼1-16 ns in WT RCs with a negatively charged QA(-). In both cases, the temperature dependence of the protein dynamics is weak.

Superposition Principle in Auger Recombination of Charged and Neutral Multicarrier States in Semiconductor Quantum Dots

DOE PAGES

Wu, Kaifeng; Lim, Jaehoon; Klimov, Victor I.

2017-07-19

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdSmore » QDs with two distinct core/shell interfacial profiles (“sharp” versus “smooth”). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. Furthermore, by comparing the measurements on the QDs with the “sharp” versus “smooth” interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. Our findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states, suggesting its generality to quantum-confined nanocrystals of arbitrary compositions and complexities.« less

Superposition Principle in Auger Recombination of Charged and Neutral Multicarrier States in Semiconductor Quantum Dots.

PubMed

Wu, Kaifeng; Lim, Jaehoon; Klimov, Victor I

2017-08-22

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdS QDs with two distinct core/shell interfacial profiles ("sharp" versus "smooth"). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. By comparing the measurements on the QDs with the "sharp" versus "smooth" interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. These findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states, suggesting its generality to quantum-confined nanocrystals of arbitrary compositions and complexities.

Excitonic processes at organic heterojunctions

NASA Astrophysics Data System (ADS)

He, ShouJie; Lu, ZhengHong

2018-02-01

Understanding excitonic processes at organic heterojunctions is crucial for development of organic semiconductor devices. This article reviews recent research on excitonic physics that involve intermolecular charge transfer (CT) excitons, and progress on understanding relationships between various interface energy levels and key parameters governing various competing interface excitonic processes. These interface excitonic processes include radiative exciplex emission, nonradiative recombination, Auger electron emission, and CT exciton dissociation. This article also reviews various device applications involving interface CT excitons, such as organic light-emitting diodes (OLEDs), organic photovoltaic cells, organic rectifying diodes, and ultralow-voltage Auger OLEDs.

Evolved phase separation toward balanced charge transport and high efficiency in polymer solar cells.

PubMed

Fan, Haijun; Zhang, Maojie; Guo, Xia; Li, Yongfang; Zhan, Xiaowei

2011-09-01

Understanding effect of morphology on charge carrier transport within polymer/fullerene bulk heterojunction is necessary to develop high-performance polymer solar cells. In this work, we synthesized a new benzodithiophene-based polymer with good self-organization behavior as well as favorable morphology evolution of its blend films with PC(71)BM under improved processing conditions. Charge carrier transport behavior of blend films was characterized by space charge limited current method. Evolved blend film morphology by controlling blend composition and additive content gradually reaches an optimized state, featured with nanoscale fibrilla polymer phase in moderate size and balanced mobility ratio close to 1:1 for hole and electron. This optimized morphology toward more balanced charge carrier transport accounts for the best power conversion efficiency of 3.2%, measured under simulated AM 1.5 solar irradiation 100 mW/cm(2), through enhancing short circuit current and reducing geminate recombination loss.

Core/shell colloidal quantum dot exciplex states for the development of highly efficient quantum-dot-sensitized solar cells.

PubMed

Wang, Jin; Mora-Seró, Iván; Pan, Zhenxiao; Zhao, Ke; Zhang, Hua; Feng, Yaoyu; Yang, Guang; Zhong, Xinhua; Bisquert, Juan

2013-10-23

Searching suitable panchromatic QD sensitizers for expanding the light-harvesting range, accelerating charge separation, and retarding charge recombination is an effective way to improve power conversion efficiency (PCE) of quantum-dot-sensitized solar cells (QDSCs). One possible way to obtain a wide absorption range is to use the exciplex state of a type-II core/shell-structured QDs. In addition, this system could also provide a fast charge separation and low charge-recombination rate. Herein, we report on using a CdTe/CdSe type-II core/shell QD sensitizer with an absorption range extending into the infrared region because of its exciplex state, which is covalently linked to TiO2 mesoporous electrodes by dropping a bifunctional linker molecule mercaptopropionic acid (MPA)-capped QD aqueous solution onto the film electrode. High loading and a uniform distribution of QD sensitizer throughout the film electrode thickness have been confirmed by energy dispersive X-ray (EDX) elemental mapping. The accelerated electron injection and retarded charge-recombination pathway in the built CdTe/CdSe QD cells in comparison with reference CdSe QD-based cells have been confirmed by impedance spectroscopy, fluorescence decay, and intensity-modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) analysis. With the combination of the high QD loading and intrinsically superior optoelectronic properties of type-II core/shell QD (wide absorption range, fast charge separation, and slow charge recombination), the resulting CdTe/CdSe QD-based regenerative sandwich solar cells exhibit a record PCE of 6.76% (J(sc) = 19.59 mA cm(-2), V(oc) = 0.606 V, and FF = 0.569) with a mask around the active film under a full 1 sun illumination (simulated AM 1.5), which is the highest reported to date for liquid-junction QDSCs.

Light intensity dependence of open-circuit voltage and short-circuit current of polymer/fullerene solar cells

NASA Astrophysics Data System (ADS)

Koster, L. Jan A.; Mihailetchi, Valentin D.; Ramaker, Robert; Xie, Hangxing; Blom, Paul W. M.

2006-04-01

The open-circuit voltage (Voc) of polymer/fullerene bulk heterojunction solar cells is investigated as a function of light intensity for different temperatures. The observed photogenerated current and V oc are at variance with classical p-n junctionbased models. The influence of light intensity and recombination strength on V oc is consistently explained by a model based on the notion that the quasi-Fermi levels are constant throughout the device, including both drift and diffusion of charge carriers. The light intensity dependence of the short-circuit current density (J sc) is also addressed. A typical feature of polymer/fullerene based solar cells is that Jsc does not scale exactly linearly with light intensity (I). Instead, a power law relationship is found given by Jsc~ Iα, where α ranges from 0.9 to 1. In a number of reports this deviation from unity is attributed to the occurrence of bimolecular recombination. We demonstrate that the dependence of the photocurrent in bulk heterojunction solar cells is governed by the build-up of space charge in the device. The occurrence of space-charge stems from the difference in charge carrier mobility of electrons and holes. In blends of poly(3-hexylthiophene) and 6,6- phenyl C61-butyric acid methyl ester this mobility difference can be tuned in between one and three orders of magnitude, depending on the annealing conditions. This allows us to experimentally verify the relation between space charge build-up and intensity dependence of Jsc. Model calculations confirm that bimolecular recombination leads only to a typical loss of 1% of all free charge carriers at Jsc for these devices. Therefore, bimolecular recombination plays only a minor role as compared to the effect of space charge in the intensity dependence of J sc.

Interfacial charge separation and recombination in InP and quasi-type II InP/CdS core/shell quantum dot-molecular acceptor complexes.

PubMed

Wu, Kaifeng; Song, Nianhui; Liu, Zheng; Zhu, Haiming; Rodríguez-Córdoba, William; Lian, Tianquan

2013-08-15

Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

Proton-hydrogen collisions for Rydberg n,l-changing transitions in the early Universe

NASA Astrophysics Data System (ADS)

Vrinceanu, Daniel

2013-05-01

Cosmic Microwave Background (CMB) is a vestige radiation generated during the Recombination era, some 390,000 years after the Big Bang, when the Universe had become transparent for the first time. Initial observations of CMB made by the Wilkinson Microwave Anisotropy Probe (WMAP) led to determining the age of the Universe. The mechanisms that drove the recombination have been discovered by using modeling of the primordial plasma and seeking agreement with the observations. The new Plank Surveyor Instrument launched in 2009 is expected to produce data about the recombination era of an unprecedented accuracy, that require including better information regarding the basic atomic physics processes into the present models. In this talk, I will review the results for various Rydberg atom - charge particle collisions and establish their relative importance during the stages of recombination era, with respect to each other and to radiative processes. Energy changing and angular momentum changing collisions with electrons and ions are considered. This work has been supported by NSF through grants to the Institute for Theoretical Atomic and Molecular Physics at Harvard Smithsonian Center for Astrophysics and to the Center for Research on Complex Networks at Texas Southern University.

Modulating Excitonic Recombination Effects through One-Step Synthesis of Perovskite Nanoparticles for Light-Emitting Diodes.

PubMed

Kulkarni, Sneha A; Muduli, Subas; Xing, Guichuan; Yantara, Natalia; Li, Mingjie; Chen, Shi; Sum, Tze Chien; Mathews, Nripan; White, Tim J; Mhaisalkar, Subodh G

2017-10-09

The primary advantages of halide perovskites for light-emitting diodes (LEDs) are solution processability, direct band gap, good charge-carrier diffusion lengths, low trap density, and reasonable carrier mobility. The luminescence in 3 D halide perovskite thin films originates from free electron-hole bimolecular recombination. However, the slow bimolecular recombination rate is a fundamental performance limitation. Perovskite nanoparticles could result in improved performance but processability and cumbersome synthetic procedures remain challenges. Herein, these constraints are overcome by tailoring the 3 D perovskite as a near monodisperse nanoparticle film prepared through a one-step in situ deposition method. Replacing methyl ammonium bromide (CH 3 NH 3 Br, MABr) partially by octyl ammonium bromide [CH 3 (CH 2 ) 7 NH 3 Br, OABr] in defined mole ratios in the perovskite precursor proved crucial for the nanoparticle formation. Films consisting of the in situ formed nanoparticles displayed signatures associated with excitonic recombination, rather than that of bimolecular recombination associated with 3 D perovskites. This transition was accompanied by enhanced photoluminescence quantum yield (PLQY≈20.5 % vs. 3.40 %). Perovskite LEDs fabricated from the nanoparticle films exhibit a one order of magnitude improvement in current efficiency and doubling in luminance efficiency. The material processing systematics derived from this study provides the means to control perovskite morphologies through the selection and mixing of appropriate additives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermoluminescent Mechanisms in Calcium Sulphate Doped with Dysprosium.

NASA Astrophysics Data System (ADS)

Matthews, Robert James

Thermoluminescent (TL) mechanisms in CaSO(,4):Dy caused by ionizing irradiation are investigated. Influences of the background impurities on the structure of the glow curve are determined and are correlated with known electron spin resonance (ESR) results. These are combined with fading studies that determine the TL process as bimolecular or monomolecular and the order of the kinetics involved. The TL emission spectrum is determined for all temperature regions of the TL emission to 400(DEGREES)C; optical absorption (OA) in the visible provides information on the valence state of the Dy ion. Photo stimulated transfer of TL (PTTL) helps determine the influence of traps deeper than 400(DEGREES)C, while studies of CaSO(,4):Dy in the scanning electron microscope (SEM) operated in the cathodoluminescent (CL) mode provide information on processes occurring during electron bombardment and on the distribution of Dy in CaSO(,4). The information from these studies is combined to form comprehensive models of the TL mechanisms responsible for the TL glow peaks.(,). The glow peak occurring between 130(DEGREES)C and 260(DEGREES)C, usually designated as the dosimetric peak, was determined to be the result of two primary processes. In the first mechanism, the SO(,3)('-) radical recombines with an oxygen interstitial (O(,i)('-)) associated with the Dy('3+) in charge compensation. The recombination energy is given up as TL. In the second mechanism, it is concluded that divalent Dy release electrons to the conduction band in a non-radiative process. The liberated electron recombines with a hole center at a remote SO(,4)(' -) site. The recombination energy is either transferred to trivalent Dy, which emits TL, or this energy causes the (SO(,4)('-))* to disassociate and form an SO(,3)(' -) and an O(,i)('-). These defects are thought to recombine at about 300(DEGREES)C. In the low temperature region (room temperature to 130(DEGREES)C), the monovalent cation, particularly Na('+) acting as charge compensation for the trivalent Dy, stabilizes the SO(,4)('-) radical and the SO(,2)(' -) radical produced during irradiation. These are determined to be monomolecular type defect comples. The TL mechanisms proposed for the dosimetric region (130(DEGREES)C - 260(DEGREES)C) and the low temperature region (RT - 130(DEGREES)C) are those most consistent with all the results of the various methods of research.

A lower isoelectric point increases signal sequence-mediated secretion of recombinant proteins through a bacterial ABC transporter.

PubMed

Byun, Hyunjong; Park, Jiyeon; Kim, Sun Chang; Ahn, Jung Hoon

2017-12-01

Efficient protein production for industrial and academic purposes often involves engineering microorganisms to produce and secrete target proteins into the culture. Pseudomonas fluorescens has a TliDEF ATP-binding cassette transporter, a type I secretion system, which recognizes C-terminal LARD3 signal sequence of thermostable lipase TliA. Many proteins are secreted by TliDEF in vivo when recombined with LARD3, but there are still others that cannot be secreted by TliDEF even when LARD3 is attached. However, the factors that determine whether or not a recombinant protein can be secreted through TliDEF are still unknown. Here, we recombined LARD3 with several proteins and examined their secretion through TliDEF. We found that the proteins secreted via LARD3 are highly negatively charged with highly-acidic isoelectric points (pI) lower than 5.5. Attaching oligo-aspartate to lower the pI of negatively-charged recombinant proteins improved their secretion, and attaching oligo-arginine to negatively-charged proteins blocked their secretion by LARD3. In addition, negatively supercharged green fluorescent protein (GFP) showed improved secretion, whereas positively supercharged GFP did not secrete. These results disclosed that proteins' acidic pI and net negative charge are major factors that determine their secretion through TliDEF. Homology modeling for TliDEF revealed that TliD dimer forms evolutionarily-conserved positively-charged clusters in its pore and substrate entrance site, which also partially explains the pI dependence of the TliDEF-dependent secretions. In conclusion, lowering the isoelectric point improved LARD3-mediated protein secretion, both widening the range of protein targets for efficient production via secretion and signifying an important aspect of ABC transporter-mediated secretions. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Designing ternary blend bulk heterojunction solar cells with reduced carrier recombination and a fill factor of 77%

NASA Astrophysics Data System (ADS)

Gasparini, Nicola; Jiao, Xuechen; Heumueller, Thomas; Baran, Derya; Matt, Gebhard J.; Fladischer, Stefanie; Spiecker, Erdmann; Ade, Harald; Brabec, Christoph J.; Ameri, Tayebeh

2016-09-01

In recent years the concept of ternary blend bulk heterojunction (BHJ) solar cells based on organic semiconductors has been widely used to achieve a better match to the solar irradiance spectrum, and power conversion efficiencies beyond 10% have been reported. However, the fill factor of organic solar cells is still limited by the competition between recombination and extraction of free charges. Here, we design advanced material composites leading to a high fill factor of 77% in ternary blends, thus demonstrating how the recombination thresholds can be overcome. Extending beyond the typical sensitization concept, we add a highly ordered polymer that, in addition to enhanced absorption, overcomes limits predicted by classical recombination models. An effective charge transfer from the disordered host system onto the highly ordered sensitizer effectively avoids traps of the host matrix and features an almost ideal recombination behaviour.

A comparative study on charge carrier recombination across the junction region of Cu{sub 2}ZnSn(S,Se){sub 4} and Cu(In,Ga)Se{sub 2} thin film solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halim, Mohammad Abdul, E-mail: halimtsukuba2012@gmail.com; Islam, Muhammad Monirul; Luo, Xianjia

A comparative study with focusing on carrier recombination properties in Cu{sub 2}ZnSn(S,Se){sub 4} (CZTSSe) and the CuInGaSe{sub 2} (CIGS) solar cells has been carried out. For this purpose, electroluminescence (EL) and also bias-dependent time resolved photoluminescence (TRPL) using femtosecond (fs) laser source were performed. For the similar forward current density, the EL-intensity of the CZTSSe sample was obtained significantly lower than that of the CIGS sample. Primarily, it can be attributed to the existence of excess amount of non-radiative recombination center in the CZTSSe, and/or CZTSSe/CdS interface comparing to that of CIGS sample. In case of CIGS sample, TRPL decaymore » time was found to increase with the application of forward-bias. This can be attributed to the reduced charge separation rate resulting from the reduced electric-field at the junction. However, in CZTSSe sample, TRPL decay time has been found almost independent under the forward and reverse-bias conditions. This phenomenon indicates that the charge recombination rate strongly dominates over the charge separation rate across the junction of the CZTSSe sample. Finally, temperature dependent V{sub OC} suggests that interface related recombination in the CZTSSe solar cell structure might be one of the major factors that affect EL-intensity and also, TRPL decay curves.« less

Recombination energy for negatively charged excitons inside type-II core/shell spherical quantum dots

NASA Astrophysics Data System (ADS)

Chafai, A.; Essaoudi, I.; Ainane, A.; Dujardin, F.; Ahuja, R.

2018-07-01

The recombination energy of isolated neutral exciton and that of isolated negatively charged exciton inside a type-II core/shell spherical quantum dot are studied. Our investigation considers the charge-carriers effective mass discontinuity at the surface contact between the core and shell materials. Although our model omits the effect of the surface polarization, the dielectric-constant mismatch at the nanodot boundaries was taken into account. In order to achieve the exciton and negative trion energies, we proceed by a variational calculation in the framework of the envelope approximation. Our results reveal a strong correlation between the nanodot morphology and the energy spectrum of the neutral and negatively charged exciton.

Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D

DOE PAGES

Haskey, S. R.; Grierson, B. A.; Burrell, K. H.; ...

2016-09-26

Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region inmore » H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. Finally, these challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model. Published by AIP Publishing.« less

Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D.

PubMed

Haskey, S R; Grierson, B A; Burrell, K H; Chrystal, C; Groebner, R J; Kaplan, D H; Pablant, N A; Stagner, L

2016-11-01

Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak [J. L. Luxon, Nucl. Fusion 42, 614 (2002)] enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region in H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. These challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model.

Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haskey, S. R.; Grierson, B. A.; Burrell, K. H.

Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region inmore » H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. Finally, these challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model. Published by AIP Publishing.« less

Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D

NASA Astrophysics Data System (ADS)

Haskey, S. R.; Grierson, B. A.; Burrell, K. H.; Chrystal, C.; Groebner, R. J.; Kaplan, D. H.; Pablant, N. A.; Stagner, L.

2016-11-01

Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak [J. L. Luxon, Nucl. Fusion 42, 614 (2002)] enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region in H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. These challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model.

On the role of local charge carrier mobility in the charge separation mechanism of organic photovoltaics.

PubMed

Yoshikawa, Saya; Saeki, Akinori; Saito, Masahiko; Osaka, Itaru; Seki, Shu

2015-07-21

Although the charge separation (CS) and transport processes that compete with geminate and non-geminate recombination are commonly regarded as the governing factors of organic photovoltaic (OPV) efficiency, the details of the CS mechanism remain largely unexplored. Here we provide a systematic investigation on the role of local charge carrier mobility in bulk heterojunction films of ten different low-bandgap polymers and polythiophene analogues blended with methanofullerene (PCBM). By correlating with the OPV performances, we demonstrated that the local mobility of the blend measured by time-resolved microwave conductivity is more important for the OPV output than those of the pure polymers. Furthermore, the results revealed two separate trends for crystalline and semi-crystalline polymers. This work offers guidance in the design of high-performance organic solar cells.

Influence of excitons interaction with charge carriers on photovoltaic parameters in organic solar cells

NASA Astrophysics Data System (ADS)

Głowienka, Damian; Szmytkowski, Jędrzej

2018-03-01

We report on theoretical analysis of excitons annihilation on charge carriers in organic solar cells. Numerical calculations based on transient one-dimensional drift-diffusion model have been carried out. An impact of three quantities (an annihilation rate constant, an exciton mobility and a recombination reduction factor) on current density and concentrations of charge carriers and excitons is investigated. Finally, we discuss the influence of excitons interaction with electrons and holes on four photovoltaic parameters (a short-circuit current, an open-circuit voltage, a fill factor and a power conversion efficiency). The conclusion is that the annihilation process visibly decreases the efficiency of organic photocells, if the annihilation rate constant is greater than 10-15m3s-1 .

Effects of carboxypeptidase B treatment and elevated temperature on recombinant monoclonal antibody charge variants in cation-exchange chromatography analysis.

PubMed

Kim, Do Gyun; Kim, Hyoung Jin; Kim, Hong-Jin

2016-10-01

Charge variants (acidic and basic) of recombinant monoclonal antibodies (Mabs) have received much attention due to their potential biological effects. C-terminal lysine variants are common in Mabs and their proportion is affected by the manufacturing process. In the present study, changes of trastuzumab charge variants brought about by carboxypeptidase B treatment and subsequent storage at 8 or 37 °C for up to 24 h were monitored by cation-exchange chromatography analysis to investigate the effects of C-terminal lysine cleavage and its subsequent reaction at 8 or 37 °C. C-terminal lysine cleavage at 8 °C reduced the fraction of basic species and had little effect on the fraction of acidic species. Analysis of individual peaks demonstrated that C-terminal lysine cleavage induced both increases and decreases in individual acidic variants, with the result that there was little overall change in the overall proportion of acidic species. It appeared that most of the basic variant Mab molecules but only a fraction of the acidic variant molecules had C-terminal lysines. Increasing the temperature to 37 °C appeared to increase the fraction of acidic species and decrease main species significantly, without a similar change in basic species. These results indicate that length of exposure to elevated temperature is a critical consideration in charge variant analysis.

Photoinduced Dynamics of Charge Separation: From Photosynthesis to Polymer–Fullerene Bulk Heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niklas, Jens; Beaupré, Serge; Leclerc, Mario

2015-06-18

Understanding charge separation and charge transport is crucial for improving the efficiency of organic solar cells. Their active media are based on organic molecules and polymers, serving as both light-absorbing and transport layers. The charge-transfer (CT) states play an important role, being intermediate for free carrier generation and charge recombination. Here, we use light-induced electron paramagnetic resonance spectroscopy to study the CT dynamics in blends of the polymers P3HT, PCDTBT, and PTB7 with the fullerene derivative C-60-PCBM. Time-resolved EPR measurements show strong spin-polarization patterns for all polymer-fullerene blends, confirming predominant generation of singlet CT states and partial orientation ordering nearmore » the donor-acceptor interface. These observations allow a comparison with charge separation processes in molecular donor-acceptor systems and in natural and artificial photosynthetic assemblies, and thus the elucidation of the initial steps of sequential CT in organic photovoltaic materials.« less

Charge transfer transitions in optical spectra of NicMg1-cO oxides

NASA Astrophysics Data System (ADS)

Churmanov, V. N.; Sokolov, V. I.; Pustovarov, V. A.; Gruzdev, N. B.; Uimin, M. A.; Byzov, I. V.; Druzhinin, A. V.; Korolyov, A. V.; Kim, G. A.; Zatsepin, A. F.; Kuznetsova, J. A.

2017-04-01

Radiative recombination with charge transfer was observed in NicMg1-cO (c = 0.008) oxides over the 8-300 K temperature range. This recombination occurs as a result of strong hybridization of the Ni2+ ion 3d-states and the band states. The charge transfer radiation excitation spectrum shows vibrational LO repeats of two exciton lines having charge transfer energy intervals of about 35 meV. The NiO nanocrystal absorption spectrum shows two weak peaks with energies of 3.510 and 3.543 eV, which are highly dependent on temperature. They are interpreted as charge transfer excitons at the edge of NiO fundamental absorption. The distance between the charge transfer exciton lines in the NicMg1-cO oxide spectra are caused by spin-orbit splitting of the valence band peak that was formed by the p-states of the oxygen ion.

Effect Of Auger Recombination In An Ion Track

NASA Technical Reports Server (NTRS)

Edmonds, Larry D.

1993-01-01

Report presents theoretical calculations of contribution of Auger recombination to depletion of charge carriers from ionization track left by passage of energetic heavy ion through silicon-based electronic device.

Analysis of S2QA- charge recombination with the Arrhenius, Eyring and Marcus theories.

PubMed

Rantamäki, Susanne; Tyystjärvi, Esa

2011-01-01

The Q band of photosynthetic thermoluminescence, measured in the presence of a herbicide that blocks electron transfer from PSII, is associated with recombination of the S(2)Q(A)(-) charge pair. The same charge recombination reaction can be monitored with chlorophyll fluorescence. It has been shown that the recombination occurs via three competing routes of which one produces luminescence. In the present study, we measured the thermoluminescence Q band and the decay of chlorophyll fluorescence yield after a single turnover flash at different temperatures from spinach thylakoids. The data were analyzed using the commonly used Arrhenius theory, the Eyring rate theory and the Marcus theory of electron transfer. The fitting error was minimized for both thermoluminescence and fluorescence by adjusting the global, phenomenological constants obtained when the reaction rate theories were applied to the multi-step recombination reaction. For chlorophyll fluorescence, all three theories give decent fits. The peak position of the thermoluminescence Q band is correct by all theories but the form of the Q band is somewhat different in curves predicted by the three theories. The Eyring and Marcus theories give good fits for the decreasing part of the thermoluminescence curve and Marcus theory gives the closest fit for the rising part. Copyright © 2011 Elsevier B.V. All rights reserved.

TiO2 nanocrystals decorated Z-schemed core-shell CdS-CdO nanorod arrays as high efficiency anodes for photoelectrochemical hydrogen generation.

PubMed

Li, Chia-Hsun; Hsu, Chan-Wei; Lu, Shih-Yuan

2018-07-01

TiO 2 nanocrystals decorated core-shell CdS-CdO nanorod arrays, TiO 2 @CdO/CdS NR, were fabricated as high efficiency anodes for photoelctrochemical hydrogen generation. The novel sandwich heterostructure was constructed from first growth of CdS nanorod arrays on a fluorine doped tin oxide (FTO) substrate with a hydrothermal process, followed by in situ generation of CdO thin films of single digit nanometers from the CdS nanorod surfaces through thermal oxidation, and final decoration of TiO 2 nanocrystals of 10-20 nm via a successive ionic layer absorption and reaction process. The core-shell CdS-CdO heterostructure possesses a Z-scheme band structure to enhance interfacial charge transfer, facilitating effective charge separation to suppress electron-hole recombination within CdS for much improved current density generation. The final decoration of TiO 2 nanocrystals passivates surface defects and trap states of CdO, further suppressing surface charge recombination for even higher photovoltaic conversion efficiencies. The photoelectrochemical performances of the plain CdS nanorod array were significantly improved with the formation of the sandwich heterostructure, achieving a photo current density of 3.2 mA/cm 2 at 1.23 V (vs. RHE), a 141% improvement over the plain CdS nanorod array and a 32% improvement over the CdO/CdS nanorod array. Copyright © 2018 Elsevier Inc. All rights reserved.

Adverse Effects of Excess Residual PbI2 on Photovoltaic Performance, Charge Separation, and Trap-State Properties in Mesoporous Structured Perovskite Solar Cells.

PubMed

Wang, Hao-Yi; Hao, Ming-Yang; Han, Jun; Yu, Man; Qin, Yujun; Zhang, Pu; Guo, Zhi-Xin; Ai, Xi-Cheng; Zhang, Jian-Ping

2017-03-17

Organic-inorganic halide perovskite solar cells have rapidly come to prominence in the photovoltaic field. In this context, CH 3 NH 3 PbI 3 , as the most widely adopted active layer, has been attracting great attention. Generally, in a CH 3 NH 3 PbI 3 layer, unreacted PbI 2 inevitably coexists with the perovskite crystals, especially following a two-step fabrication process. There appears to be a consensus that an appropriate amount of unreacted PbI 2 is beneficial to the overall photovoltaic performance of a device, the only disadvantageous aspect of excess residual PbI 2 being viewed as its insulating nature. However, the further development of such perovskite-based devices requires a deeper understanding of the role of residual PbI 2 . In this work, PbI 2 -enriched and PbI 2 -controlled perovskite films, as two extreme cases, have been prepared by modulating the crystallinity of a pre-deposited PbI 2 film. The effects of excess residual PbI 2 have been elucidated on the basis of spectroscopic and optoelectronic studies. The initial charge separation, the trap-state density, and the trap-state distribution have all been found to be adversely affected in PbI 2 -enriched devices, to the detriment of photovoltaic performance. This leads to a biphasic recombination process and accelerates the charge carrier recombination dynamics. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Halide perovskite solar cells using monocrystalline TiO2 nanorod arrays as electron transport layers: impact of nanorod morphology

NASA Astrophysics Data System (ADS)

Thakur, Ujwal Kumar; Askar, Abdelrahman M.; Kisslinger, Ryan; Wiltshire, Benjamin D.; Kar, Piyush; Shankar, Karthik

2017-07-01

This is the first report of a 17.6% champion efficiency solar cell architecture comprising monocrystalline TiO2 nanorods (TNRs) coupled with perovskite, and formed using facile solution processing without non-routine surface conditioning. Vertically oriented TNR ensembles are desirable as electron transporting layers (ETLs) in halide perovskite solar cells (HPSCs) because of potential advantages such as vectorial electron percolation pathways to balance the longer hole diffusion lengths in certain halide perovskite semiconductors, ease of incorporating nanophotonic enhancements, and optimization between a high contact surface area for charge transfer (good) versus high interfacial recombination (bad). These advantages arise from the tunable morphology of hydrothermally grown rutile TNRs, which is a strong function of the growth conditions. Fluorescence lifetime imaging microscopy of the HPSCs demonstrated a stronger quenching of the perovskite PL when using TNRs as compared to mesoporous/compact TiO2 thin films. Due to increased interfacial contact area between the ETL and perovskite with easier pore filling, charge separation efficiency is dramatically enhanced. Additionally, solid-state impedance spectroscopy results strongly suggested the suppression of interfacial charge recombination between TNRs and perovskite layer, compared to other ETLs. The optimal ETL morphology in this study was found to consist of an array of TNRs ∼300 nm in length and ∼40 nm in width. This work highlights the potential of TNR ETLs to achieve high performance solution-processed HPSCs.

Numerical simulation of quantum efficiency and surface recombination in HgCdTe IR photon-trapping structures

NASA Astrophysics Data System (ADS)

Schuster, Jonathan; Bellotti, Enrico

2013-06-01

We have investigated the quantum effiency in HgCdTe photovoltaic pixel arrays employing a photon-trapping structure realized with a periodic array of pillars intended to provide broadband operation. We have found that the quantum efficiency depends heavily on the passivation of the pillar surface. Pillars passivated with anodicoxide have a large fixed positive charge on the pillar surface. We use our three-dimensional numerical simulation model to study the effect of surface charge and surface recombination velocity on the exterior of the pillars. We then evaluate the quantum efficiency of this structure subject to different surface conditions. We have found that by themselves, the surface charge and surface recombination are detrimental to the quantum efficiency but the quantum efficiency is recovered when both phenomena are present. We will discuss the effects of these phenomena and the trade offs that exist between the two.

A low-frequency noise model with carrier generation-recombination process for pentacene organic thin-film transistor

NASA Astrophysics Data System (ADS)

Han, C. Y.; Qian, L. X.; Leung, C. H.; Che, C. M.; Lai, P. T.

2013-07-01

By including the generation-recombination process of charge carriers in conduction channel, a model for low-frequency noise in pentacene organic thin-film transistors (OTFTs) is proposed. In this model, the slope and magnitude of power spectral density for low-frequency noise are related to the traps in the gate dielectric and accumulation layer of the OTFT for the first time. The model can well fit the measured low-frequency noise data of pentacene OTFTs with HfO2 or HfLaO gate dielectric, which validates this model, thus providing an estimate on the densities of traps in the gate dielectric and accumulation layer. It is revealed that the traps in the accumulation layer are much more than those in the gate dielectric, and so dominate the low-frequency noise of pentacene OTFTs.

The dissociative recombination of O2/+/ in the ionosphere

NASA Technical Reports Server (NTRS)

Torr, M. R.; Torr, D. G.

1981-01-01

Aeronomical determinations of the dissociative recombination reaction rate coefficient for O2(+) and alpha depend directly on a knowledge of the rate coefficient for the charge exchange of O(+) with O2 and k. The aeronomical determination of alpha is reevaluated using Atmosphere Explorer satellite data in light of a subsequent laboratory measurement of k (Chen et al., 1978). The results are found to be in good agreement with laboratory determinations of the coefficient for night-time conditions. For data obtained under sunlit conditions, however, the results differed significantly with those of the laboratory measurements. These results imply that the state of the O2(+) molecule major thermospheric processes needs to be examined in greater detail.

Generating free charges by carrier multiplication in quantum dots for highly efficient photovoltaics.

PubMed

Ten Cate, Sybren; Sandeep, C S Suchand; Liu, Yao; Law, Matt; Kinge, Sachin; Houtepen, Arjan J; Schins, Juleon M; Siebbeles, Laurens D A

2015-02-17

CONSPECTUS: In a conventional photovoltaic device (solar cell or photodiode) photons are absorbed in a bulk semiconductor layer, leading to excitation of an electron from a valence band to a conduction band. Directly after photoexcitation, the hole in the valence band and the electron in the conduction band have excess energy given by the difference between the photon energy and the semiconductor band gap. In a bulk semiconductor, the initially hot charges rapidly lose their excess energy as heat. This heat loss is the main reason that the theoretical efficiency of a conventional solar cell is limited to the Shockley-Queisser limit of ∼33%. The efficiency of a photovoltaic device can be increased if the excess energy is utilized to excite additional electrons across the band gap. A sufficiently hot charge can produce an electron-hole pair by Coulomb scattering on a valence electron. This process of carrier multiplication (CM) leads to formation of two or more electron-hole pairs for the absorption of one photon. In bulk semiconductors such as silicon, the energetic threshold for CM is too high to be of practical use. However, CM in nanometer sized semiconductor quantum dots (QDs) offers prospects for exploitation in photovoltaics. CM leads to formation of two or more electron-hole pairs that are initially in close proximity. For photovoltaic applications, these charges must escape from recombination. This Account outlines our recent progress in the generation of free mobile charges that result from CM in QDs. Studies of charge carrier photogeneration and mobility were carried out using (ultrafast) time-resolved laser techniques with optical or ac conductivity detection. We found that charges can be extracted from photoexcited PbS QDs by bringing them into contact with organic electron and hole accepting materials. However, charge localization on the QD produces a strong Coulomb attraction to its counter charge in the organic material. This limits the production of free charges that can contribute to the photocurrent in a device. We show that free mobile charges can be efficiently produced via CM in solids of strongly coupled PbSe QDs. Strong electronic coupling between the QDs resulted in a charge carrier mobility of the order of 1 cm(2) V(-1) s(-1). This mobility is sufficiently high so that virtually all electron-hole pairs escape from recombination. The impact of temperature on the CM efficiency in PbSe QD solids was also studied. We inferred that temperature has no observable effect on the rate of cooling of hot charges nor on the CM rate. We conclude that exploitation of CM requires that charges have sufficiently high mobility to escape from recombination. The contribution of CM to the efficiency of photovoltaic devices can be further enhanced by an increase of the CM efficiency above the energetic threshold of twice the band gap. For large-scale applications in photovoltaic devices, it is important to develop abundant and nontoxic materials that exhibit efficient CM.

Cascading electron and hole transfer dynamics in a CdS/CdTe core-shell sensitized with bromo-pyrogallol red (Br-PGR): slow charge recombination in type II regime.

PubMed

Maity, Partha; Debnath, Tushar; Chopra, Uday; Ghosh, Hirendra Nath

2015-02-14

Ultrafast cascading hole and electron transfer dynamics have been demonstrated in a CdS/CdTe type II core-shell sensitized with Br-PGR using transient absorption spectroscopy and the charge recombination dynamics have been compared with those of CdS/Br-PGR composite materials. Steady state optical absorption studies suggest that Br-PGR forms strong charge transfer (CT) complexes with both the CdS QD and CdS/CdTe core-shell. Hole transfer from the photo-excited QD and QD core-shell to Br-PGR was confirmed by both steady state and time-resolved emission spectroscopy. Charge separation was also confirmed by detecting electrons in the conduction band of the QD and the cation radical of Br-PGR as measured from femtosecond transient absorption spectroscopy. Charge separation in the CdS/Br-PGR composite materials was found to take place in three different pathways, by transferring the photo-excited hole of CdS to Br-PGR, electron injection from the photo-excited Br-PGR to the CdS QD, and direct electron transfer from the HOMO of Br-PGR to the conduction band of the CdS QD. However, in the CdS/CdTe/Br-PGR system hole transfer from the photo-excited CdS to Br-PGR and electron injection from the photo-excited Br-PGR to CdS take place after cascading through the CdTe shell QD. Charge separation also takes place via direct electron transfer from the Br-PGR HOMO to the conduction band of CdS/CdTe. Charge recombination (CR) dynamics between the electron in the conduction band of the CdS QD and the Br-PGR cation radical were determined by monitoring the bleach recovery kinetics. The CR dynamics were found to be much slower in the CdS/CdTe/Br-PGR system than in the CdS/Br-PGR system. The formation of the strong CT complex and the separation of charges cascading through the CdTe shell help to slow down charge recombination in the type II regime.

Recombination dynamics in In{sub x}Ga{sub 1−x}N quantum wells—Contribution of excited subband recombination to carrier leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulz, T.; Markurt, T.; Albrecht, M.

2014-11-03

The recombination dynamics of In{sub x}Ga{sub 1−x}N single quantum wells are investigated. By comparing the photoluminescence (PL) decay spectra with simulated emission spectra obtained by a Schrödinger-Poisson approach, we give evidence that recombination from higher subbands contributes the emission of the quantum well at high excitation densities. This recombination path appears as a shoulder on the high energy side of the spectrum at high charge carrier densities and exhibits decay in the range of ps. Due to the lower confinement of the excited subband states, a distinct proportion of the probability density function lies outside the quantum well, thus contributingmore » to charge carrier loss. By estimating the current density in our time resolved PL experiments, we show that the onset of this loss mechanism occurs in the droop relevant regime above 20 A/cm{sup 2}.« less

Profiling of the injected charge drift current transients by cross-sectional scanning technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaubas, E., E-mail: eugenijus.gaubas@ff.vu.lt; Ceponis, T.; Pavlov, J.

2014-02-07

The electric field distribution and charge drift currents in Si particle detectors are analyzed. Profiling of the injected charge drift current transients has been implemented by varying charge injection position within a cross-sectional boundary of the particle detector. The obtained profiles of the induction current density and duration of the injected charge drift pulses fit well the simulated current variations. Induction current transients have been interpreted by different stages of the bipolar and monopolar drift of the injected carriers. Profiles of the injected charge current transients registered in the non-irradiated and neutron irradiated Si diodes are compared. It has beenmore » shown that the mixed regime of the competing processes of drift, recombination, and diffusion appears in the measured current profiles on the irradiated samples. The impact of the avalanche effects can be ignored based on the investigations presented. It has been shown that even a simplified dynamic model enabled us to reproduce the main features of the profiled transients of induced charge drift current.« less

REVISED BIG BANG NUCLEOSYNTHESIS WITH LONG-LIVED, NEGATIVELY CHARGED MASSIVE PARTICLES: UPDATED RECOMBINATION RATES, PRIMORDIAL {sup 9}Be NUCLEOSYNTHESIS, AND IMPACT OF NEW {sup 6}Li LIMITS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kusakabe, Motohiko; Kim, K. S.; Cheoun, Myung-Ki

We extensively reanalyze the effects of a long-lived, negatively charged massive particle, X {sup –}, on big bang nucleosynthesis (BBN). The BBN model with an X {sup –} particle was originally motivated by the discrepancy between the {sup 6,} {sup 7}Li abundances predicted in the standard BBN model and those inferred from observations of metal-poor stars. In this model, {sup 7}Be is destroyed via the recombination with an X {sup –} particle followed by radiative proton capture. We calculate precise rates for the radiative recombinations of {sup 7}Be, {sup 7}Li, {sup 9}Be, and {sup 4}He with X {sup –}. Inmore » nonresonant rates, we take into account respective partial waves of scattering states and respective bound states. The finite sizes of nuclear charge distributions cause deviations in wave functions from those of point-charge nuclei. For a heavy X {sup –} mass, m{sub X} ≳ 100 GeV, the d-wave → 2P transition is most important for {sup 7}Li and {sup 7,} {sup 9}Be, unlike recombination with electrons. Our new nonresonant rate of the {sup 7}Be recombination for m{sub X} = 1000 GeV is more than six times larger than the existing rate. Moreover, we suggest a new important reaction for {sup 9}Be production: the recombination of {sup 7}Li and X {sup –} followed by deuteron capture. We derive binding energies of X nuclei along with reaction rates and Q values. We then calculate BBN and find that the amount of {sup 7}Be destruction depends significantly on the charge distribution of {sup 7}Be. Finally, updated constraints on the initial abundance and the lifetime of the X {sup –} are derived in the context of revised upper limits to the primordial {sup 6}Li abundance. Parameter regions for the solution to the {sup 7}Li problem and the primordial {sup 9}Be abundances are revised.« less

Improved photovoltaic performance and stability of quantum dot sensitized solar cells using Mn-ZnSe shell structure with enhanced light absorption and recombination control.

PubMed

Gopi, Chandu V V M; Venkata-Haritha, M; Kim, Soo-Kyoung; Kim, Hee-Je

2015-08-07

To make quantum-dot-sensitized solar cells (QDSSCs) competitive, photovoltaic parameters comparable to those of other emerging solar cell technologies are necessary. In the present study, ZnSe was used as an alternative to ZnS, one of the most widely used passivation materials in QDSSCs. ZnSe was deposited on a TiO2-CdS-CdSe photoanode to form a core-shell structure, which was more efficient in terms of reducing the electron recombination in QDSSCs. The development of an efficient passivation layer is a requirement for preventing recombination processes in order to attain high-performance and stable QDSSCs. A layer of inorganic Mn-ZnSe was applied to a QD-sensitized photoanode to enhance the adsorption and strongly inhibit interfacial recombination processes in QDSSCs, which greatly improved the power conversion efficiency. Impedance spectroscopy revealed that the combined Mn doping with ZnSe treatment reduces interfacial recombination and increases charge collection efficiency compared with Mn-ZnS, ZnS, and ZnSe. A solar cell based on the CdS-CdSe-Mn-ZnSe photoanode yielded excellent performance with a solar power conversion efficiency of 5.67%, Voc of 0.584 V, and Jsc of 17.59 mA cm(-2). Enhanced electron transport and reduced electron recombination are responsible for the improved Jsc and Voc of the QDSSCs. The effective electron lifetime of the device with Mn-ZnSe was higher than those with Mn-ZnS, ZnSe, and ZnS, leading to more efficient electron-hole separation and slower electron recombination.

Charge collection and pore filling in solid-state dye-sensitized solar cells.

PubMed

Snaith, Henry J; Humphry-Baker, Robin; Chen, Peter; Cesar, Ilkay; Zakeeruddin, Shaik M; Grätzel, Michael

2008-10-22

The solar to electrical power conversion efficiency for dye-sensitized solar cells (DSCs) incorporating a solid-state organic hole-transporter can be over 5%. However, this is for devices significantly thinner than the optical depth of the active composites and by comparison to the liquid electrolyte based DSCs, which exhibit efficiencies in excess of 10%, more than doubling of this efficiency is clearly attainable if all the steps in the photovoltaic process can be optimized. Two issues are currently being addressed by the field. The first aims at enhancing the electron diffusion length by either reducing the charge recombination or enhancing the charge transport rates. This should enable a larger fraction of photogenerated charges to be collected. The second, though less actively investigated, aims to improve the physical composite formation, which in this instance is the infiltration of mesoporous TiO(2) with the organic hole-transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxypheny-amine)-9,9'-spirobifluorene (spiro-MeOTAD). Here, we perform a broad experimental study to elucidate the limiting factors to the solar cell performance. We first investigate the charge transport and recombination in the solid-state dye-sensitized solar cell under realistic working conditions via small perturbation photovoltage and photocurrent decay measurements. From these measurements we deduce that the electron diffusion length near short-circuit is as long as 20 µm. However, at applied biases approaching open-circuit potential under realistic solar conditions, the diffusion length becomes comparable with the film thickness, ∼2 µm, illustrating that real losses to open-circuit voltage, fill factor and hence efficiency are occurring due to ineffective charge collection. The long diffusion length near short-circuit, on the other hand, illustrates that another process, separate from ineffective charge collection, is rendering the solar cell less than ideal. We investigate the process of TiO(2) mesopore infiltration with spiro-MeOTAD by examining the cross-sectional images of and performing photo-induced absorption spectroscopy on devices with a range of thickness, infiltrated with spiro-MeOTAD with a range of concentrations. We present our interpretation of the mechanism for material infiltration, and by improving the casting conditions demonstrate efficient charge collection through devices of over 7 µm in thickness. This investigation represents an improvement in our understanding of the limiting factors to the dye-sensitized solar cell. However, much work, focused on composite formation and improved kinetic competition, is required to realize the true potential of this concept.

Simulation of solution phase electron transfer in a compact donor-acceptor dyad.

PubMed

Kowalczyk, Tim; Wang, Lee-Ping; Van Voorhis, Troy

2011-10-27

Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the underlying electron-transfer (ET) process, including the role of the environment. Toward this goal, we introduce a QM/MM protocol for ET simulations and use it to characterize CR in the formanilide-anthraquinone dyad (FAAQ). Our simulations predict fast recombination of the charge-transfer excited state, in agreement with recent experiments. The computed electronic couplings show an electronic state dependence and are weaker in solution than in the gas phase. We explore the role of cis-trans isomerization on the CR kinetics, and we find strong correlation between the vertical energy gaps of the full simulations and a collective solvent polarization coordinate. Our approach relies on constrained density functional theory to obtain accurate diabatic electronic states on the fly for molecular dynamics simulations, while orientational and electronic polarization of the solvent is captured by a polarizable force field based on a Drude oscillator model. The method offers a unified approach to the characterization of driving forces, reorganization energies, electronic couplings, and nonlinear solvent effects in light-harvesting systems.

Production of bare argon, manganese, iron and nickel nuclei in the Dresden EBIT

NASA Astrophysics Data System (ADS)

Kentsch, U.; Zschornack, G.; Großmann, F.; Ovsyannikov, V. P.; Ullmann, F.; Fritzsche, S.; Surzhykov, A.

2002-02-01

The production of highly charged argon, manganese, iron and nickel ions in a room-temperature electron beam ion trap (EBIT), the Dresden EBIT, has been investigated by means of energy dispersive X-ray spectroscopy of the direct excitation (DE) and radiative recombination (RR) processes. To derive the charge state distributions of the ions in the trap, direct excitation and radiative recombination cross-sections were calculated at electron energies of 8 and 14.4 keV. Based on these theoretical cross-sections and the measured X-ray spectra, the ion densities and the absolute number of ions, which are trapped in the electron beam, are determined for argon, manganese, iron and nickel. Emphasis has been paid to the highly charged ions, including the helium-like and hydrogen-like ions and bare nuclei. In the case of iron we also determined the contributions from lower ionization stages from DE transition lines. It is shown, that in the Dresden EBIT elements at least up to nickel can be fully ionized. Beside energy dispersive spectroscopy it is shown for iron by wavelength dispersive X-ray spectroscopy that with a comparably high gas pressure in the order of 10 -8 mbar carbon-, boron-, beryllium-, lithium- and helium-like iron ions can be produced.

CXSFIT Code Application to Process Charge-Exchange Recombination Spectroscopy Data at the T-10 Tokamak

NASA Astrophysics Data System (ADS)

Serov, S. V.; Tugarinov, S. N.; Klyuchnikov, L. A.; Krupin, V. A.; von Hellermann, M.

2017-12-01

The applicability of the CXSFIT code to process experimental data from Charge-eXchange Recombination Spectroscopy (CXRS) diagnostics at the T-10 tokamak is studied with a view to its further use for processing experimental data at the ITER facility. The design and operating principle of the CXRS diagnostics are described. The main methods for processing the CXRS spectra of the 5291-Å line of C5+ ions at the T-10 tokamak (with and without subtraction of parasitic emission from the edge plasma) are analyzed. The method of averaging the CXRS spectra over several shots, which is used at the T-10 tokamak to increase the signal-to-noise ratio, is described. The approximation of the spectrum by a set of Gaussian components is used to identify the active CXRS line in the measured spectrum. Using the CXSFIT code, the ion temperature in ohmic discharges and discharges with auxiliary electron cyclotron resonance heating (ECRH) at the T-10 tokamak is calculated from the CXRS spectra of the 5291-Å line. The time behavior of the ion temperature profile in different ohmic heating modes is studied. The temperature profile dependence on the ECRH power is measured, and the dynamics of ECR removal of carbon nuclei from the T-10 plasma is described. Experimental data from the CXRS diagnostics at T-10 substantially contribute to the implementation of physical programs of studies on heat and particle transport in tokamak plasmas and investigation of geodesic acoustic mode properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ran, Niva A.; Roland, Steffen; Love, John A.

Here, a long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics—however, the results have important implications on the operation of all optoelectronic devices with donor/acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting inmore » larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.« less

Ion-ion Recombination and Chemiion Concentrations In Aircraft Exhaust

NASA Astrophysics Data System (ADS)

Turco, R. P.; Yu, F.

Jet aircraft emit large quantities of ultrafine volatile aerosols, as well as soot parti- cles, into the environment. To determine the long-term effects of these emissions, a better understanding of the mechanisms that control particle formation and evolution is needed, including the number and size dispersion. A recent explanation for aerosol nucleation in a jet wake involves the condensation of sulfuric acid vapor, and cer- tain organic compounds, onto charged molecular clusters (chemiions) generated in the engine combustors (Yu and Turco, 1997). Massive charged aggregates, along with sulfuric acid and organic precursor vapors, have been detected in jet plumes under cruise conditions. In developing the chemiion nucleation theory, Yu and Turco noted that ion-ion recombination in the engine train and jet core should limit the chemiion emission index to 1017/kg-fuel. This value is consistent with ion-ion recombination coefficients of 1×10-7 cm3/s over time scales of 10-2 s. However, the evolution of the ions through the engine has not been adequately studied. The conditions at the combustor exit are extreme-temperatures approach 1500 K, and pressures can reach 30 atmospheres. In this presentation, we show that as the combustion gases expand and cool, two- and three-body ion-ion recombination processes control the chemiion concentration. The concepts of mutual neutralization and Thomson recombination are first summarized, and appropriate temperature and pressure dependent recombination rate coefficients are derived for the aircraft problem. A model for ion losses in jet exhaust is then formulated using an "invariance" principle discussed by Turco and Yu (1997) in the context of a coagulating aerosol in an expanding plume. This recombina- tion model is applied to estimate chemiion emission indices for a range of operational engine conditions. The predicted ion emission rates are found to be consistent with observations. We discuss the sources of variance in chemiion exhaust concentrations based on the physical processes occurring in the exhaust stream. References: Turco, R. P., and F. Yu, Aerosol invariance in expanding, coagulating plumes, Geo- phys. Res. Lett., 24, 1223-1226, 1997. Yu, F., and R. P. Turco, The role of ions in the formation and evolution of particles in aircraft plumes, Geophys. Res. Lett., 24, 1927-1930, 1997.

Effect of the sample annealing temperature and sample crystallographic orientation on the charge kinetics of MgO single crystals subjected to keV electron irradiation.

PubMed

Boughariou, A; Damamme, G; Kallel, A

2015-04-01

This paper focuses on the effect of sample annealing temperature and crystallographic orientation on the secondary electron yield of MgO during charging by a defocused electron beam irradiation. The experimental results show that there are two regimes during the charging process that are better identified by plotting the logarithm of the secondary electron emission yield, lnσ, as function of the total trapped charge in the material QT. The impact of the annealing temperature and crystallographic orientation on the evolution of lnσ is presented here. The slope of the asymptotic regime of the curve lnσ as function of QT, expressed in cm(2) per trapped charge, is probably linked to the elementary cross section of electron-hole recombination, σhole, which controls the trapping evolution in the reach of the stationary flow regime. © 2014 The Authors Journal of Microscopy © 2014 Royal Microscopical Society.

Enhanced emission of charged-exciton polaritons from colloidal quantum dots on a SiN/SiO2 slab waveguide

PubMed Central

Xu, Xingsheng; Li, Xingyun

2015-01-01

We investigate the photoluminescence (PL) spectra and the time-resolved PL decay process from colloidal quantum dots on SiN/SiO2 wet etched via BOE (HF:NH4F:H2O). The spectrum displays multi-peak shapes that vary with irradiation time. The evolution of the spectral peaks with irradiation time and collection angle demonstrates that the strong coupling of the charged-exciton emission to the leaky modes of the SiN/SiO2 slab waveguide predominantly produces short-wavelength spectral peaks, resulting in multi-peak spectra. We conclude that BOE etching enhances the charged-exciton emission efficiency and its contribution to the total emission compared with the unetched case. BOE etching smoothes the electron confinement potential, thus decreasing the Auger recombination rate. Therefore, the charged-exciton emission efficiency is high, and the charged-exciton-polariton emission can be further enhanced through strong coupling to the leaky mode of the slab waveguide. PMID:25988709

Comparing photoelectrochemical water oxidation, recombination kinetics and charge trapping in the three polymorphs of TiO2.

PubMed

Moss, Benjamin; Lim, Kee Kean; Beltram, Alessandro; Moniz, Savio; Tang, Junwang; Fornasiero, Paolo; Barnes, Piers; Durrant, James; Kafizas, Andreas

2017-06-07

In this article we present the first comparative study of the transient decay dynamics of photo-generated charges for the three polymorphs of TiO 2 . To our knowledge, this is the first such study of the brookite phase of TiO 2 over timescales relevant to the kinetics of water splitting. We find that the behavior of brookite, both in the dynamics of relaxation of photo-generated charges and in energetic distribution, is similar to the anatase phase of TiO 2 . Moreover, links between the rate of recombination of charge carriers, their energetic distribution and the mode of transport are made in light of our findings and used to account for the differences in water splitting efficiency observed across the three polymorphs.

Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane

DOE PAGES

Spenst, Peter; Young, Ryan M.; Wasielewski, Michael R.; ...

2016-05-18

Cofacial positioning of two perylene bisimide (PBI) chromophores at a distance of 6.5 Å in a cyclophane structure prohibits the otherwise common excimer formation and directs photoexcited singlet state relaxation towards intramolecular symmetry-breaking charge separation (τ CS = 161 ± 4 ps) in polar CH 2Cl 2, which is thermodynamically favored with a Gibbs free energy of ΔG CS = –0.32 eV. The charges then recombine slowly in τ CR = 8.90 ± 0.06 ns to form the PBI triplet excited state, which can be used subsequently to generate singlet oxygen in 27% quantum yield. This sequence of events ismore » eliminated by dissolving the PBI cyclophane in non-polar toluene, where only excited singlet state decay occurs. In contrast, complexation of electron-rich aromatic hydrocarbons by the host PBI cyclophane followed by photoexcitation of PBI results in ultrafast electron transfer (<10 ps) from the guest to the PBI in CH 2Cl 2. As a result, the rate constants for charge separation and recombination increase as the guest molecules become easier to oxidize, demonstrating that charge separation occurs close to the peak of the Marcus curve and the recombination lies far into the Marcus inverted region.« less

Investigating Recombination and Charge Carrier Dynamics in a One-Dimensional Nanopillared Perovskite Absorber.

PubMed

Kwon, Hyeok-Chan; Yang, Wooseok; Lee, Daehee; Ahn, Jihoon; Lee, Eunsong; Ma, Sunihl; Kim, Kyungmi; Yun, Seong-Cheol; Moon, Jooho

2018-05-22

Organometal halide perovskite materials have become an exciting research topic as manifested by intense development of thin film solar cells. Although high-performance solar-cell-based planar and mesoscopic configurations have been reported, one-dimensional (1-D) nanostructured perovskite solar cells are rarely investigated despite their expected promising optoelectrical properties, such as enhanced charge transport/extraction. Herein, we have analyzed the 1-D nanostructure effects of organometal halide perovskite (CH 3 NH 3 PbI 3- x Cl x ) on recombination and charge carrier dynamics by utilizing a nanoporous anodized alumina oxide scaffold to fabricate a vertically aligned 1-D nanopillared array with controllable diameters. It was observed that the 1-D perovskite exhibits faster charge transport/extraction characteristics, lower defect density, and lower bulk resistance than the planar counterpart. As the aspect ratio increases in the 1-D structures, in addition, the charge transport/extraction rate is enhanced and the resistance further decreases. However, when the aspect ratio reaches 6.67 (diameter ∼30 nm), the recombination rate is aggravated due to high interface-to-volume ratio-induced defect generation. To obtain the full benefits of 1-D perovskite nanostructuring, our study provides a design rule to choose the appropriate aspect ratio of 1-D perovskite structures for improved photovoltaic and other optoelectrical applications.

Multiple exciton generation and recombination in carbon nanotubes and nanocrystals.

PubMed

Kanemitsu, Yoshihiko

2013-06-18

Semiconducting nanomaterials such as single-walled carbon nanotubes (SWCNTs) and nanocrystals (NCs) exhibit unique size-dependent quantum properties. They have therefore attracted considerable attention from the viewpoints of fundamental physics and functional device applications. SWCNTs and NCs also provide an excellent new stage for experimental studies of many-body effects of electrons and excitons on optical processes in nanomaterials. In this Account, we discuss multiple exciton generation and recombination in SWCNTs and NCs for next-generation photovoltaics. Strongly correlated ensembles of conduction-band electrons and valence-band holes in semiconductors are complex quantum systems that exhibit unique optical phenomena. In bulk crystals, the carrier recombination dynamics can be described by a simple model, which includes the nonradiative single-carrier trapping rate, the radiative two-carrier recombination rate, and the nonradiative three-carrier Auger recombination rate. The nonradiative Auger recombination rate determines the carrier recombination dynamics at high carrier density and depends on the spatial localization of carriers in two-dimensional quantum wells. The Auger recombination and multiple exciton generation rates can be advantageously manipulated by nanomaterials with designated energy structures. In addition, SWCNTs and NCs show quantized recombination dynamics of multiple excitons and carriers. In one-dimensional SWCNTs, excitons have large binding energies and are very stable at room temperature. The extremely rapid Auger recombination between excitons determines the photoluminescence (PL) intensity, the PL linewidth, and the PL lifetime. SWCNTs can undergo multiple exciton generation, while strong exciton-exciton interactions and complicated exciton structures affect the quantized Auger rate and the multiple exciton generation efficiency. Interestingly, in zero-dimensional NC quantum dots, quantized Auger recombination causes unique optical phenomena. The breakdown of the k-conversion rule and strong Coulomb interactions between carriers in NCs enhance Auger recombination rate and decrease the energy threshold for multiple exciton generation. We discuss this impact of the k-conservation rule on two-carrier radiative recombination and the three-carrier Auger recombination processes in indirect-gap semiconductor Si NCs. In NCs and SWCNTs, multiple exciton generation competes with Auger recombination, surface trapping of excitons, and cooling of hot electrons or excitons. In addition, we explore heterostructured NCs and impurity-doped NCs in the context of the optimization of charge carrier extraction from excitons in NCs.

Efficient barrier for charge injection in polyethylene by silver nanoparticles/plasma polymer stack

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milliere, L.; Makasheva, K., E-mail: kremena.makasheva@laplace.univ-tlse.fr; Laurent, C.

2014-09-22

Charge injection from a metal/insulator contact is a process promoting the formation of space charge in polymeric insulation largely used in thick layers in high voltage equipment. The internal charge perturbs the field distribution and can lead to catastrophic failure either through its electrostatic effects or through energetic processes initiated under charge recombination and/or hot electrons effects. Injection is still ill-described in polymeric insulation due to the complexity of the contact between the polymer chains and the electrodes. Barrier heights derived from the metal work function and the polymer electronic affinity do not provide a good description of the measurementsmore » [Taleb et al., IEEE Trans. Dielectr. Electr. Insul. 20, 311–320 (2013)]. Considering the difficulty to describe the contact properties and the need to prevent charge injection in polymers for high voltage applications, we developed an alternative approach by tailoring the interface properties by the silver nanoparticles (AgNPs)/plasma polymer stack, deposited on the polymer film. Due to their small size, the AgNPs, covered by a very thin film of plasma polymer, act as deep traps for the injected charges thereby stabilizing the interface from the point of view of charge injection. After a quick description of the method for elaborating the nanostructured layer near the contact, it is demonstrated how the AgNPs/plasma polymer stack effectively prevents, in a spectacular way, the formation of bulk space charge.« less

High reduction of interfacial charge recombination in colloidal quantum dot solar cells by metal oxide surface passivation.

PubMed

Chang, Jin; Kuga, Yuki; Mora-Seró, Iván; Toyoda, Taro; Ogomi, Yuhei; Hayase, Shuzi; Bisquert, Juan; Shen, Qing

2015-03-12

Bulk heterojunction (BHJ) solar cells based on colloidal QDs and metal oxide nanowires (NWs) possess unique and outstanding advantages in enhancing light harvesting and charge collection in comparison to planar architectures. However, the high surface area of the NW structure often brings about a large amount of recombination (especially interfacial recombination) and limits the open-circuit voltage in BHJ solar cells. This problem is solved here by passivating the surface of the metal oxide component in PbS colloidal quantum dot solar cells (CQDSCs). By coating thin TiO2 layers onto ZnO-NW surfaces, the open-circuit voltage and power conversion efficiency have been improved by over 40% in PbS CQDSCs. Characterization by transient photovoltage decay and impedance spectroscopy indicated that the interfacial recombination was significantly reduced by the surface passivation strategy. An efficiency as high as 6.13% was achieved through the passivation approach and optimization for the length of the ZnO-NW arrays (device active area: 16 mm2). All solar cells were tested in air, and exhibited excellent air storage stability (without any performance decline over more than 130 days). This work highlights the significance of metal oxide passivation in achieving high performance BHJ solar cells. The charge recombination mechanism uncovered in this work could shed light on the further improvement of PbS CQDSCs and/or other types of solar cells.

Improved understanding of the recombination rate at inverted p+ silicon surfaces

NASA Astrophysics Data System (ADS)

To, Alexander; Ma, Fajun; Hoex, Bram

2017-08-01

The effect of positive fixed charge on the recombination rate at SiN x -passivated p+ surfaces is studied in this work. It is shown that a high positive fixed charge on a low defect density, passivated doped surface can result in a near injection level independent lifetime in a certain injection level range. This behaviour is modelled with advanced computer simulations using Sentaurus TCAD, which replicates the measurements conditions during a photoconductance based effective minority carrier lifetime measurement. The resulting simulations show that the shape of the injection level dependent lifetime is a result of the surface recombination rate, which is non-linear due to the surfaces moving into inversion with increasing injection level. As a result, the surface recombination rate switches from being limited by electrons to holes. Equations describing the surface saturation current density, J 0s, during this regime are also derived in this work.

Direct Observation of Photoinduced Charge Separation in Ruthenium Complex/Ni(OH) 2 Nanoparticle Hybrid

DOE PAGES

Tang, Yu; Pattengale, Brian A.; Ludwig, John M.; ...

2015-12-17

We report that Ni(OH) 2 have emerged as important functional materials for solar fuel conversion because of their potential as cost-effective bifunctional catalysts for both hydrogen and oxygen evolution reactions. However, their roles as photocatalysts in the photoinduced charge separation (CS) reactions remain unexplored. In this paper, we investigate the CS dynamics of a newly designed hybrid catalyst by integrating a Ru complex with Ni(OH) 2 nanoparticles (NPs). Using time resolved X-ray absorption spectroscopy (XTA), we directly observed the formation of the reduced Ni metal site (~60 ps), unambiguously demonstrating CS process in the hybrid through ultrafast electron transfer frommore » Ru complex to Ni(OH) 2 NPs. Compared to the ultrafast CS process, the charge recombination in the hybrid is ultraslow (>>50 ns). These results not only suggest the possibility of developing Ni(OH) 2 as solar fuel catalysts, but also represent the first time direct observation of efficient CS in a hybrid catalyst using XTA.« less

Effect of low thermal budget annealing on surface passivation of silicon by ALD based aluminum oxide films.

PubMed

Vandana; Batra, Neha; Gope, Jhuma; Singh, Rajbir; Panigrahi, Jagannath; Tyagi, Sanjay; Pathi, P; Srivastava, S K; Rauthan, C M S; Singh, P K

2014-10-21

Thermal ALD deposited Al2O3 films on silicon show a marked difference in surface passivation quality as a function of annealing time (using a rapid thermal process). An effective and quality passivation is realized in short anneal duration (∼100 s) in nitrogen ambient which is reflected in the low surface recombination velocity (SRV <10 cm s(-1)). The deduced values are close to the best reported SRV obtained by the high thermal budget process (with annealing time between 10-30 min), conventionally used for improved surface passivation. Both as-deposited and low thermal budget annealed films show the presence of positive fixed charges and this is never been reported in the literature before. The role of field and chemical passivation is investigated in terms of fixed charge and interface defect densities. Further, the importance of the annealing step sequence in the MIS structure fabrication protocol is also investigated from the view point of its effect on the nature of fixed charges.

Effects of Magnetic Nanoparticles and External Magnetostatic Field on the Bulk Heterojunction Polymer Solar Cells

DOE PAGES

Wang, Kai; Yi, Chao; Liu, Chang; ...

2015-03-18

The price of energy to separate tightly bound electron-hole pair (or charge-transfer state) and extract freely movable charges from low-mobility materials represents fundamental losses for many low-cost photovoltaic devices. In bulk heterojunction (BHJ) polymer solar cells (PSCs), approximately 50% of the total efficiency lost among all energy loss pathways is due to the photogenerated charge carrier recombination within PSCs and low charge carrier mobility of disordered organic materials. To address these issues, we introduce magnetic nanoparticles (MNPs) and orientate these MNPS within BHJ composite by an external magnetostatic field. Over 50% enhanced efficiency was observed from BHJ PSCs incorporated withmore » MNPs and an external magnetostatic field alignment when compared to the control BHJ PSCs. The optimization of BHJ thin film morphology, suppression of charge carrier recombination, and enhancement in charge carrier collection result in a greatly increased short-circuit current density and fill factor, as a result, enhanced power conversion efficiency.« less

Polarization spectroscopy of positive and negative trions in an InAs quantum dot

NASA Astrophysics Data System (ADS)

Ware, Morgan E.; Bracker, Allan S.; Stinaff, Eric; Gammon, Daniel; Gershoni, David; Korenev, Vladimir L.

2005-02-01

Using polarization-sensitive photoluminescence and photoluminescence excitation spectroscopy, we study single InAs/GaAs self-assembled quantum dots. The dots were embedded in an n-type, Schottky diode structure allowing for control of the charge state. We present here the exciton, singly charged exciton (positive and negative trions), and the twice negatively charged exciton. For non-resonant excitation below the wetting layer, we observed a large degree of polarization memory from the radiative recombination of both the positive and negative trions. In excitation spectra, through the p-shell, we have found several sharp resonances in the emission from the s-shell recombination of the dot in all charged states. Some of these excitation resonances exhibit strong coulomb shifts upon addition of charges into the quantum dot. One particular resonance of the negatively charged trion was found to exhibit a fine structure doublet under circular polarization. This observation is explained in terms of resonant absorption into the triplet states of the negative trion.

Photoinduced electron transfer in a ferrocene-distyryl BODIPY dyad and a ferrocene-distyryl BODIPY-C60 triad.

PubMed

Liu, Jian-Yong; El-Khouly, Mohamed E; Fukuzumi, Shunichi; Ng, Dennis K P

2012-06-04

A ferrocene-distyryl BODIPY dyad and a ferrocene-distyryl BODIPY-C(60) triad are synthesized and characterized. Upon photoexcitation at the distyryl BODIPY unit, these arrays undergo photoinduced electron transfer to form the corresponding charge-separated species. Based on their redox potentials, determined by cyclic voltammetry, the direction of the charge separation and the energies of these states are revealed. Femtosecond transient spectroscopic studies reveal that a fast charge separation (k(CS) =1.0×10(10) s(-1)) occurs for both the ferrocene-distyryl BODIPY dyad and the ferrocene-distyryl BODIPY-C(60) triad, but that a relatively slow charge recombination is observed only for the triad. The lifetime of the charge-separated state is 500 ps. Charge recombination of the dyad and triad leads to population of the triplet excited sate of ferrocene and the ground state, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of regioregularity on recombination dynamics in inverted bulk heterojunction organic solar cells

NASA Astrophysics Data System (ADS)

Chandrasekaran, Naresh; Liu, Amelia C. Y.; Kumar, Anil; McNeill, Christopher R.; Kabra, Dinesh

2018-01-01

The effect of polymer regioregularity on the charge transport properties and bimolecular recombination rates of polymer-based solar cells is studied in detail using transient photovoltaic techniques. We compare organic solar cells fabricated with an ITO/ZnO/PEIE/P3HT:PCBM/MoO3/Ag structure using either 100% regioregular poly(3-hexylthiophene) (DF-P3HT) yielding an average power conversion efficiency (PCE) of 3.8  ±  0.3% or 92% regioregular P3HT (rr-P3HT) that yields an average PCE of 3.28  ±  0.4%. Transient photocurrent measurements reveal the presence of less mobile photoinduced charges in rr-P3HT:PCBM cells when compared to DF-P3HT:PCBM solar cells. Transient photovoltage measurements are used to establish the relationship between regioregularity and bimolecular recombination rate constant (k) finding that under 1 Sun, devices with high regioregularity have a longer τ despite having a higher k. The high value of k for the DF-P3HT:PCBM system as compared to the rr-P3HT:PCBM system is attributed to enhanced mobility and better charge transport of mobile charges in the DF-P3HT:PCBM system, consistent with enhanced fibrillar order in DF-P3HT films observed with transmission electron microscopy. We also note a slight decrease in cell open circuit voltage with increase in polymer regioregularity, which is due to the increase in k. Other recombination mechanisms such as trap-assisted recombination are found to be important in the lower regioregular P3HT device compounded by the reduced mobility and poor inter-chain ordering.

Charge carrier dynamics in organic semiconductors and their donor-acceptor composites: Numerical modeling of time-resolved photocurrent

NASA Astrophysics Data System (ADS)

Johnson, Brian; Kendrick, Mark J.; Ostroverkhova, Oksana

2013-09-01

We present a model that describes nanosecond (ns) time-scale photocurrent dynamics in functionalized anthradithiophene (ADT) films and ADT-based donor-acceptor (D/A) composites. By fitting numerically simulated photocurrents to experimental data, we quantify contributions of multiple pathways of charge carrier photogeneration to the photocurrent, as well as extract parameters that characterize charge transport (CT) in organic films including charge carrier mobilities, trap densities, hole trap depth, and trapping and recombination rates. In pristine ADT films, simulations revealed two competing charge photogeneration pathways: fast, occurring on picosecond (ps) or sub-ps time scales with efficiencies below 10%, and slow, which proceeds at the time scale of tens of nanoseconds, with efficiencies of about 11%-12%, at the applied electric fields of 40-80 kV/cm. The relative contribution of these pathways to the photocurrent was electric field dependent, with the contribution of the fast process increasing with applied electric field. However, the total charge photogeneration efficiency was weakly electric field dependent exhibiting values of 14%-20% of the absorbed photons. The remaining 80%-86% of the photoexcitation did not contribute to charge carrier generation at these time scales. In ADT-based D/A composites with 2 wt.% acceptor concentration, an additional pathway of charge photogeneration that proceeds via CT exciton dissociation contributed to the total charge photogeneration. In the composite with the functionalized pentacene (Pn) acceptor, which exhibits strong exciplex emission from a tightly bound D/A CT exciton, the contribution of the CT state to charge generation was small, ˜8%-12% of the total number of photogenerated charge carriers, dependent on the electric field. In contrast, in the composite with PCBM acceptor, the CT state contributed about a half of all photogenerated charge carriers. In both D/A composites, the charge carrier mobilities were reduced and trap densities and average trap depths were increased, as compared to a pristine ADT donor film. A considerably slower recombination of free holes with trapped electrons was found in the composite with the PCBM acceptor, which led to slower decays of the transient photocurrent and considerably higher charge retention, as compared to a pristine ADT donor film and the composite with the functionalized Pn acceptor.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leonard, E.; Arzel, L.; Tomassini, M.

Thinning the absorber layer is one of the possibilities envisaged to further decrease the production costs of Cu(In,Ga)Se{sub 2} (CIGSe) thin films solar cell technology. In the present study, the electronic transport in submicron CIGSe-based devices has been investigated and compared to that of standard devices. It is observed that when the absorber is around 0.5 μm-thick, tunnelling enhanced interface recombination dominates, which harms cells energy conversion efficiency. It is also shown that by varying either the properties of the Mo back contact or the characteristics of 3-stage growth processing, one can shift the dominating recombination mechanism from interface to spacemore » charge region and thereby improve the cells efficiency. Discussions on these experimental facts led to the conclusions that 3-stage process implies the formation of a CIGSe/CIGSe homo-interface, whose location as well as properties rule the device operation; its influence is enhanced in submicron CIGSe based solar cells.« less

Potential-dependent recombination kinetics of photogenerated electrons in n- and p-type GaN photoelectrodes studied by time-resolved IR absorption spectroscopy.

PubMed

Yamakata, Akira; Yoshida, Masaaki; Kubota, Jun; Osawa, Masatoshi; Domen, Kazunari

2011-07-27

Recombination kinetics of photogenerated electrons in n-type and p-type GaN photoelectrodes active for H(2) and O(2) evolution, respectively, from water was examined by time-resolved IR absorption (TR-IR) spectroscopy. Illumination of a GaN film with UV pulse (355 nm and 6 ns in duration) gives transient interference spectra in both transmittance and reflection modes. Simulation shows that the interference spectra are caused by photogenerated electrons. We observed that recombination in the microsecond region is greatly affected by the applied potentials, the lifetime becoming longer at negative and positive potentials for n- and p-type GaN electrodes, respectively. There is a good correlation between potential dependence of the steady-state reaction efficiency and that of the number of surviving electrons in the millisecond region. We also performed potential jump measurement to examine the shift in Fermi level by photogenerated charge carriers. In the case of n-type GaN, the electrode potential jumps to the negative side by accumulation of electrons in the bulk. However, in the case of p-type GaN, the electrode potential first jumps to the negative side within 20 μs and gradually shifts to the positive side in a few milliseconds, while the number of charge carriers is constant at >0.2 ms. This two-step process is ascribed to electron transport from the bulk to the surface of GaN, because the electrode potential is sensitive to the number of electrons in the bulk. The results confirm that TR-IR combined with potential jump measurement provides useful information for understanding the behavior of charge carriers in photoelectrochemical systems.

Passivation of phosphorus diffused silicon surfaces with Al2O3: Influence of surface doping concentration and thermal activation treatments

NASA Astrophysics Data System (ADS)

Richter, Armin; Benick, Jan; Kimmerle, Achim; Hermle, Martin; Glunz, Stefan W.

2014-12-01

Thin layers of Al2O3 are well known for the excellent passivation of p-type c-Si surfaces including highly doped p+ emitters, due to a high density of fixed negative charges. Recent results indicate that Al2O3 can also provide a good passivation of certain phosphorus-diffused n+ c-Si surfaces. In this work, we studied the recombination at Al2O3 passivated n+ surfaces theoretically with device simulations and experimentally for Al2O3 deposited with atomic layer deposition. The simulation results indicate that there is a certain surface doping concentration, where the recombination is maximal due to depletion or weak inversion of the charge carriers at the c-Si/Al2O3 interface. This pronounced maximum was also observed experimentally for n+ surfaces passivated either with Al2O3 single layers or stacks of Al2O3 capped by SiNx, when activated with a low temperature anneal (425 °C). In contrast, for Al2O3/SiNx stacks activated with a short high-temperature firing process (800 °C) a significant lower surface recombination was observed for most n+ diffusion profiles without such a pronounced maximum. Based on experimentally determined interface properties and simulation results, we attribute this superior passivation quality after firing to a better chemical surface passivation, quantified by a lower interface defect density, in combination with a lower density of negative fixed charges. These experimental results reveal that Al2O3/SiNx stacks can provide not only excellent passivation on p+ surfaces but also on n+ surfaces for a wide range of surface doping concentrations when activated with short high-temperature treatments.

Controlling charge balance and exciton recombination by bipolar host in single-layer organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Qiao, Xianfeng; Tao, Youtian; Wang, Qiang; Ma, Dongge; Yang, Chuluo; Wang, Lixiang; Qin, Jingui; Wang, Fosong

2010-08-01

Highly efficient single-layer organic light-emitting diodes with reduced efficiency roll-off are demonstrated by using a bipolar host material of 2,5-bis(2-(9H-carbazol-9-yl)phenyl)-1,3,4-oxadiazole (o-CzOXD) doped with iridium complexes as the emissive layer. For example, the green single-layer device, employing fac-tris(2-phenylpyridine)iridium Ir(ppy)3 as dopant, shows a peak current efficiency of 45.57 cd A-1, corresponding to external quantum efficiency (EQE) of 12.42%, and still exhibits efficiencies of 45.26 cd A-1 and 40.42 cd A-1 at luminance of 1000 and 10 000 cd m-2, respectively. In addition, the yellow and red single-layer devices, with bis(2-(9,9- diethyl-9H-fluoren-2-yl)-1-phenyl-1H-benzoimidazol-N ,C3)iridium(acetylacetonate) (fbi)2Ir(acac) and bis(1-phenylisoquinolinolato-C2,N)iridium(acetylacetonate) (piq)2Ir(acac) as emitter, also show high EQE of 7.04% and 7.28%, respectively. The transport properties of o-CzOXD film are well investigated by current-voltage measurement, from which both hole and electron mobility are determined. It is found that the o-CzOXD shows appealing bipolar transport character, which is favor for the balanced charge distribution in the whole doped zone. More importantly, the multifunctional role of hole trapping and electron transporting of the iridium complex in o-CzOXD further balances the charge carriers and broadens the recombination zone. As a result, the recombination of electrons and holes is significantly improved and the triplet-triplet annihilation and triplet-polaron quenching processes are effectively suppressed, eventually leading to the high efficiency as well as the reduced efficiency roll-off.

Direct observation of sequential oxidations of a titania-bound molecular proxy catalyst generated through illumination of molecular sensitizers

NASA Astrophysics Data System (ADS)

Chen, Hsiang-Yun; Ardo, Shane

2018-01-01

Natural photosynthesis uses the energy in sunlight to oxidize or reduce reaction centres multiple times, therefore preparing each reaction centre for a multiple-electron-transfer reaction that will ultimately generate stable reaction products. This process relies on multiple chromophores per reaction centre to quickly generate the active state of the reaction centre and to outcompete deleterious charge recombination. Using a similar design principle, we report spectroscopic evidence for the generation of a twice-oxidized TiO2-bound molecular proxy catalyst after low-intensity visible-light excitation of co-anchored molecular Ru(II)-polypyridyl dyes. Electron transfer from an excited dye to TiO2 generated a Ru(III) state that subsequently and repeatedly reacted with neighbouring Ru(II) dyes via self-exchange electron transfer to ultimately oxidize a distant co-anchored proxy catalyst before charge recombination. The largest yield for twice-oxidized proxy catalysts occurred when they were present at low coverage, suggesting that large dye/electrocatalyst ratios are also desired in dye-sensitized photoelectrochemical cells.

Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells

DOE PAGES

Bi, Cheng; Wang, Qi; Shao, Yuchuan; ...

2015-07-20

Large-aspect-ratio grains are needed in polycrystalline thin-film solar cells for reduced charge recombination at grain boundaries; however, the grain size in organolead trihalide perovskite (OTP) films is generally limited by the film thickness. Here we report the growth of OTP grains with high average aspect ratio of 2.3–7.9 on a wide range of non-wetting hole transport layers (HTLs), which increase nucleus spacing by suppressing heterogeneous nucleation and facilitate grain boundary migration in grain growth by imposing less drag force. The reduced grain boundary area and improved crystallinity dramatically reduce the charge recombination in OTP thin films to the level inmore » OTP single crystals. Combining the high work function of several HTLs, a high stabilized device efficiency of 18.3% in low-temperature-processed planar-heterojunction OTP devices under 1 sun illumination is achieved. As a result, this simple method in enhancing OTP morphology paves the way for its application in other optoelectronic devices for enhanced performance.« less

Laboratory Studies in UV and EUV Solar Physics

NASA Technical Reports Server (NTRS)

Parkinson, W. H.; Wagner, William J. (Technical Monitor)

2002-01-01

The Ion Beam Experiment at the Center for Astrophysics is dedicated to the study of ion-electron collision processes of importance in solar physics. The analysis of measurements of Electron Impact Excitation (EIE) from the 3s3p(exp 3)P(exp o) metastable state to the 3s3p(exp 1)P state of Si(2+) was completed during the past year and a paper describing the results is available as a preprint. Our current program is directed at measuring absolute cross sections for dielectronic recombination (DR) and EIE in Si(3+), one of the primary ions used for probing the solar transition region. Our study of DR is particularly concerned with the effects of electric and magnetic fields on the recombination rates. Measurements of silicon ions with charge greater than n=2 have necessitated upgrading the experiment with a new ion source. The new source is also suitable for producing C(2+) beams to be used for measurements of EIE and DR for that system. The source is expected to be capable of producing beams of more highly charged systems as well.

Ferroelectric polarization effect on surface chemistry and photo-catalytic activity: A review

NASA Astrophysics Data System (ADS)

Khan, M. A.; Nadeem, M. A.; Idriss, H.

2016-03-01

The current efficiency of various photocatalytic processes is limited by the recombination of photogenerated electron-hole pairs in the photocatalyst as well as the back-reaction of intermediate species. This review concentrates on the use of ferroelectric polarization to mitigate electron-hole recombination and back-reactions and therefore improve photochemical reactivity. Ferroelectric materials are considered as wide band gap polarizable semiconductors. Depending on the surface polarization, different regions of the surface experience different extents of band bending and promote different carriers to move to spatially different locations. This can lead to some interesting interactions at the surface such as spatially selective adsorption and surface redox reactions. This introductory review covers the fundamental properties of ferroelectric materials, effect of an internal electric field/polarization on charge carrier separation, effect of the polarization on the surface photochemistry and reviews the work done on the use of these ferroelectric materials for photocatalytic applications such as dye degradation and water splitting. The manipulation of photogenerated charge carriers through an internal electric field/surface polarization is a promising strategy for the design of improved photocatalysts.

Bimodal exciton-plasmon light sources controlled by local charge carrier injection.

PubMed

Merino, Pablo; Rosławska, Anna; Große, Christoph; Leon, Christopher C; Kuhnke, Klaus; Kern, Klaus

2018-05-01

Electrical charges can generate photon emission in nanoscale quantum systems by two independent mechanisms. First, radiative recombination of pairs of oppositely charged carriers generates sharp excitonic lines. Second, coupling between currents and collective charge oscillations results in broad plasmonic bands. Both luminescence modes can be simultaneously generated upon charge carrier injection into thin C 60 crystallites placed in the plasmonic nanocavity of a scanning tunneling microscope (STM). Using the sharp tip of the STM as a subnanometer-precise local electrode, we show that the two types of electroluminescence are induced by two separate charge transport channels. Holes injected into the valence band promote exciton generation, whereas electrons extracted from the conduction band cause plasmonic luminescence. The different dynamics of the two mechanisms permit controlling their relative contribution in the combined bimodal emission. Exciton recombination prevails for low charge injection rates, whereas plasmon decay outshines for high tunneling currents. The continuous transition between both regimes is described by a rate model characterizing emission dynamics on the nanoscale. Our work provides the basis for developing blended exciton-plasmon light sources with advanced functionalities.

A multi-pathway model for photosynthetic reaction center

NASA Astrophysics Data System (ADS)

Qin, M.; Shen, H. Z.; Yi, X. X.

2016-03-01

Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

Role of the Charge-Transfer State in Reduced Langevin Recombination in Organic Solar Cells: A Theoretical Study

PubMed Central

2015-01-01

Reduced Langevin recombination has been observed in organic solar cells (OSCs) for many years, but its origin is still unclear. A recent work by Burke et al. (Adv. Energy Mater.2015, 5, 1500123-1) was inspired by this reduced Langevin recombination, and they proposed an equilibrium model of charge-transfer (CT) states that correlates the open-circuit voltage of OSCs with experimentally available device parameters. In this work, we extend Burke et al.’s CT model further and for the first time directly correlate the reduced Langevin recombination with the energetic and dynamic behavior of the CT state. Recombination through CT states leads in a straightforward manner to a decrease in the Langevin reduction factor with increasing temperature, without explicit consideration of the temperature dependence of the mobility. To verify the correlation between the CT states and reduced Langevin recombination, we incorporated this CT model and the reduced Langevin model into drift-diffusion simulations of a bilayer OSC. The simulations not only successfully reproduced realistic current–voltage (J–V) characteristics of the bilayer OSC, but also demonstrate that the two models consistently lead to same value of the apparent Langevin reduction factor. PMID:26640611

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

NASA Astrophysics Data System (ADS)

Miller, Richards; van Schooten, K. J.; Malissa, H.; Joshi, G.; Jamali, S.; Lupton, J. M.; Boehme, C.

2016-12-01

We have studied the role of spin-dependent processes on conductivity in polyfluorene (PFO) thin films by preforming continuous wave (cw) electrically detected magnetic resonance (EDMR) spectroscopy at temperatures between 10 K and room temperature using microwave frequencies between about 1 GHz and 20 GHz, as well as pulsed EDMR at the X band (10 GHz). Variable frequency EDMR allows us to establish the role of spin-orbit coupling in spin-dependent processes whereas pulsed EDMR allows for the observation of coherent spin motion effects. We used PFO for this study in order to allow for the investigation of the effects of microscopic morphological ordering since this material can adopt two distinct intrachain morphologies: an amorphous (glassy) phase, in which monomer units are twisted with respect to each other, and an ordered (β) phase, where all monomers lie within one plane. In thin films of organic light-emitting diodes, the appearance of a particular phase can be controlled by deposition parameters and solvent vapor annealing, and is verified by electroluminescence spectroscopy. Under bipolar charge-carrier injection conditions, we conducted multifrequency cw EDMR, electrically detected Rabi spin-beat experiments, and Hahn echo and inversion-recovery measurements. Coherent echo spectroscopy reveals electrically detected electron-spin-echo envelope modulation due to the coupling of the carrier spins to nearby nuclear spins. Our results demonstrate that, while conformational disorder can influence the observed EDMR signals, including the sign of the current changes on resonance as well as the magnitudes of local hyperfine fields and charge-carrier spin-orbit interactions, it does not qualitatively affect the nature of spin-dependent transitions in this material. In both morphologies, we observe the presence of at least two different spin-dependent recombination processes. At room temperature and 10 K, polaron-pair recombination through weakly spin-spin coupled intermediate charge-carrier pair states is dominant, while at low temperatures, additional signatures of spin-dependent charge transport through the interaction of polarons with triplet excitons are seen in the half-field resonance of a triplet spin-1 species. This additional contribution arises since triplet lifetimes are increased at lower temperatures. We tentatively conclude that spectral broadening induced by hyperfine coupling is slightly weaker in the more ordered β-phase than in the glassy phase since protons are more evenly spaced, whereas broadening effects due to spin-orbit coupling, which impacts the distribution of g -factors, appear to be somewhat more significant in the β-phase.

Strong higher-order resonant contributions to x-ray line polarization in hot plasmas

NASA Astrophysics Data System (ADS)

Shah, Chintan; Amaro, Pedro; Steinbrügge, Rene; Beilmann, Christian; Bernitt, Sven; Fritzsche, Stephan; Surzhykov, Andrey; Crespo López-Urrutia, José R.; Tashenov, Stanislav

2016-06-01

We studied angular distributions of x rays emitted in resonant recombination of highly charged iron and krypton ions, resolving dielectronic, trielectronic, and quadruelectronic channels. A tunable electron beam drove these processes, inducing x rays registered by two detectors mounted along and perpendicular to the beam axis. The measured emission asymmetries comprehensively benchmarked full-order atomic calculations. We conclude that accurate polarization diagnostics of hot plasmas can only be obtained under the premise of inclusion of higher-order processes that were neglected in earlier work.

Formation and ascent of nonisothermal ionospheric and chromospheric bubbles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genkin, L.G.; Erukhimov, L.M.; Myasnikov, E.N.

1987-11-01

The influences of nonisothermicity on the dynamics of ionospheric and chromospheric bubbles is discussed. The possibility of the existence in the ionosphere of a recombination-thermal instability, arising from the temperature dependence of the coefficient of charge exchange between molecules and atomic ions, is shown, and its influence on the formation and evolution of equatorial bubbles is analyzed. It is shown that the formation and dynamics of bubbles may depend on recombination processes and gravity, while plasma heating (predominantly by vertical electric fields) leads to the deepening and preservation of bubbles as they move to greater altitudes. The hypothesis is advancedmore » that the formation of bubbles may be connected with the ascent of clumps of molecules in ionospheric tornados.« less

Development of a Method for Local Electron Temperature and Density Measurements in the Divertor of the JET Tokamak

NASA Technical Reports Server (NTRS)

Jupen, C.; Meigs, A.; Bhatia, A. K.; Brezinsek, S.; OMullane, M.

2004-01-01

Plasma volume recombination in the divertor, a process in which charged particles recombine to neutral atoms, contributes to plasma detachment and hence cooling at the divertor target region. Detachment has been observed at JET and other tokamaks and is known to occur at low electron temperatures (T(sub e)<1 eV) and at high electron density (n(sub e)>10(exp 20)/m(exp 3)). The ability to measure such low temperatures is therefore of interest for modelling the divertor. In present work we report development of a new spectroscopic technique for investigation of local electron density (n(sub e)) and temperature (T,) in the outer divertor at JET.

Recombination dynamics of optically excited charge carriers in bulk MoS2

NASA Astrophysics Data System (ADS)

Völzer, Tim; Lütgens, Matthias; Fennel, Franziska; Lochbrunner, Stefan

2017-10-01

Transition metal dichalcogenides (TMDCs), such as MoS2, are promising candidates for optoelectronic or catalytic applications. On that account, a detailed characterization of the electronic dynamics in these materials is of pivotal importance. Here, we investigate the temporal evolution of an excited carrier population by all-optical pump-probe spectroscopy. On the sub-picosecond time scale we observe thermal relaxation of the excited carriers by electron-phonon coupling. The dynamics on the nanosecond time scale can be understood in terms of defect-assisted Auger recombination over a broad carrier density regime spanning more than one order of magnitude. Hence, our results emphasize the importance of defect states for electronic processes in TMDCs at room temperature.

Laser-Matter Interaction in Dielectrics: Insight from Picosecond-Pulsed Second-Harmonic Generation in Periodically Poled LiTaO3

NASA Astrophysics Data System (ADS)

Louchev, Oleg A.; Wada, Satoshi; Panchenko, Vladislav Ya.

2017-08-01

We develop a modified two-temperature (2T) model of laser-matter interaction in dielectrics based on experimental insight from picosecond-pulsed high-frequency temperature-controlled second-harmonic (515 nm) generation in periodically poled stoichiometric LiTaO3 crystal and required for computational treatment of short-pulsed nonlinear optics and materials processing applications. We show that the incorporation of an extended set of recombination-kinetics-related energy-release and heat-exchange processes following short-pulsed photoionization by two-photon absorption of the second harmonic allows accurate simulation of the electron-lattice relaxation dynamics and electron-lattice temperature evolution in LiTaO3 crystal in nonlinear laser-frequency conversion. Our experimentally confirmed model and detailed simulation study show that two-photon ionization with the recombination mechanism via ion-electron-lattice interaction followed by a direct transfer of the recombination energy to the lattice is the main laser-matter energy-transfer pathway responsible for the majority of the crystal lattice heating (approximately 90%) continuing for approximately 50 ps after laser-pulse termination and competing with effect of electron-phonon energy transfer from the free electrons. This time delay is due to a recombination bottleneck which hinders faster relaxation to thermal equilibrium in photoionized dielectric crystal. Generally, our study suggests that in dielectrics photoionized by short-pulsed radiation with intensity range used in nonlinear laser-frequency conversion, the electron-lattice relaxation period is defined by the recombination-stage bottleneck of a few tens of picoseconds and not by the time of the electron-phonon energy transfer. This modification of the 2T model can be applied to a broad range of processes involving laser-matter interactions in dielectrics and semiconductors for charge density reaching the range of 1021- 1022 cm-3 .

Atomic Data for Nebular Abundance Determinations: Photoionization and Recombination Properties of Xenon Ions

NASA Astrophysics Data System (ADS)

Sterling, Nicholas C.; Kerlin, Austin B.

2016-01-01

We present preliminary results of a study of the photoionization (PI) and recombination properties of low-charge Xe ions. The abundances of neutron(n)-capture elements (atomic number Z > 30) are of interest in planetary nebulae (PNe) since they can be enriched by slow n-capture nucleosynthesis (the ``s-process'') in the progenitor asymptotic giant branch (AGB) stars. Xe is particularly valuable, because it is the most widely-observed ``heavy-s'' species (Z > 40) in PNe. Its abundance relative to lighter n-capture elements can be used to determine s-process neutron exposures, and constrain s-process enrichment patterns as a function of progenitor metallicity. Using the atomic structure code AUTOSTRUCTURE (Badnell 2011, Comp. Phys. Comm., 182, 1528), we have computed multi-configuration Breit-Pauli distorted-wave PI cross sections and radiative recombination (RR) and dielectronic recombination (DR) rate coefficients for neutral through six-times ionized Xe, data which are critically needed for accurate Xe abundance determinations in ionized nebulae. We find good agreement between our computed direct PI cross sections and experimental measurements. Internal uncertainties are estimated for our calculations by using three different configuration interaction expansions for each ion, and by testing the sensitivity of our results to the radial orbital scaling parameters. As found for other n-capture elements (Sterling & Witthoeft 2011, A&A, 529, A147; Sterling 2011, A&A, 533, A62), DR is the dominant recombination mechanism for Xe ions at nebular temperatures (~104 K). Following Sterling et al. (2015, ApJS, 218, 25), these data will be added to nebular modeling codes to compute ionization correction factors for unobserved Xe ions in PNe, which will enable elemental Xe abundances to be determined with much higher accuracy than is currently possible. This work is supported by NSF award AST-1412928.

Microscopic dynamics research on the "mature" process of dye-sensitized solar cells after injection of highly concentrated electrolyte.

PubMed

Liang, Zhongguan; Liu, Weiqing; Chen, Jun; Hu, Linhua; Dai, Songyuan

2015-01-21

After injection of electrolyte, the internal three-dimensional solid-liquid penetration system of dye-sensitized solar cells (DSCs) can take a period of time to reach "mature" state. This paper studies the changes of microscopic processes of DSCs including TiO2 energy-level movement, localized state distribution, charge accumulation, electron transport, and recombination dynamics, from the beginning of electrolyte injection to the time of reached mature state. The results show that the microscopic dynamics process of DSCs exhibited a time-dependent behavior and achieved maturity ∼12 h after injecting the electrolyte into DSCs. Within 0-12 h, several results were observed: (1) the conduction band edge of TiO2 moved slightly toward negative potential direction; (2) the localized states in the band gap of TiO2 was reduced according to the same distribution law; (3) the transport resistance in TiO2 film increased, and electron transport time was prolonged as the time of maturity went on, which indicated that the electron transport process is impeded gradually; (4) the recombination resistance at the TiO2/electrolyte (EL) interface increases, and electron lifetime gradually extends, therefore, the recombination process is continuously suppressed. Furthermore, results suggest that the parameters of EL/Pt-transparent conductive oxide (TCO) interface including the interfacial capacitance, electron-transfer resistance, and transfer time constant would change with time of maturity, indicating that the EL/Pt-TCO interface is a potential factor affecting the mature process of DSCs.

Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

DOE PAGES

Hartnett, Patrick E.; Dyar, Scott M.; Margulies, Eric A.; ...

2015-07-31

The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ~6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, uponmore » CH₂Cl₂ vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ~4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.« less

Real-time dynamics of Auger wave packets and decays in ultrafast charge migration processes

NASA Astrophysics Data System (ADS)

Covito, F.; Perfetto, E.; Rubio, A.; Stefanucci, G.

2018-06-01

The Auger decay is a relevant recombination channel during the first few femtoseconds of molecular targets impinged by attosecond XUV or soft x-ray pulses. Including this mechanism in time-dependent simulations of charge-migration processes is a difficult task, and Auger scatterings are often ignored altogether. In this work we present an advance of the current state-of-the-art by putting forward a real-time approach based on nonequilibrium Green's functions suitable for first-principles calculations of molecules with tens of active electrons. To demonstrate the accuracy of the method we report comparisons against accurate grid simulations of one-dimensional systems. We also predict a highly asymmetric profile of the Auger wave packet, with a long tail exhibiting ripples temporally spaced by the inverse of the Auger energy.

Cation Recombination Energy/Coulomb Repulsion Effects in ETD/ECD as Revealed by Variation of Charge per Residue at Fixed Total Charge

PubMed Central

Mentinova, Marija; Crizer, David M.; Baba, Takashi; McGee, William M.; Glish, Gary L.; McLuckey, Scott A.

2013-01-01

Electron capture dissociation (ECD) and electron transfer dissociation (ETD) experiments in electrodynamic ion traps operated in the presence of a bath gas in the 1–10 mTorr range have been conducted on a common set of doubly protonated model peptides of the form X(AG)nX (X = lysine, arginine, or histidine, n=1, 2, or 4). The partitioning of reaction products was measured using thermal electrons, anions of azobenzene, and anions of 1,3-dinitrobenzene as reagents. Variation of n alters the charge per residue of the peptide cation, which affects recombination energy. The ECD experiments showed that H-atom loss is greatest for the n=1 peptides and decreases as n increases. Proton transfer in ETD, on the other hand, is expected to increase as charge per residue decreases (i.e., as n increases). These opposing tendencies were apparent in the data for the K(AG)nK peptides. H-atom loss appeared to be more prevalent in ECD than in ETD and is rationalized on the basis of either internal energy differences, differences in angular momentum transfer associated with the electron capture versus electron transfer processes, or a combination of the two. The histidine peptides showed the greatest extent of charge reduction without dissociation, the arginine peptides showed the greatest extent of side-chain cleavages, and the lysine peptides generally showed the greatest extent of partitioning into the c/z•-product ion channels. The fragmentation patterns for the complementary c- and z•-ions for ETD and ECD were found to be remarkably similar, particularly for the peptides with X = lysine. PMID:23568028

Increasing the efficiency of organic solar cells by photonic and electrostatic-field enhancements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nalwa, Kanwar

2011-01-01

Organic photovoltaic (OPV) technology is an attractive solar-electric conversion paradigm due to the promise of low cost roll-to-roll production and amenability to flexible substrates. Power conversion efficiency (PCE) exceeding 7% has recently been achieved. OPV cells suffer from low charge carrier mobilities of polymers, leading to recombination losses, higher series resistances and lower fill-factors. Thus, it is imperative to develop fabrication methodologies that can enable efficient optical absorption in films thinner than optical absorption length. Active layers conformally deposited on light-trapping, microscale textured, grating-type surfaces is one possible approach to achieve this objective. In this study, 40% theoretical increase inmore » photonic absorption over flat OPVs is shown for devices with textured geometry by the simulation results. For verifying this theoretical result and improving the efficiency of OPVs by light trapping, OPVs were fabricated on grating-type textured substrates possessing t pitch and -coat PV active-layer on these textured substrates led to over filling of the valleys and shunts at the crest, which severely affected the performance of the resultant PV devices. Thus, it is established that although the optical design is important for OPV performance but the potential of light trapping can only be effectively tapped if the textures are amenable for realizing a conformal active layer. It is discovered that if the height of the underlying topographical features is reduced to sub-micron regime (e.g. 300 nm) and the pitch is increased to more than a micron (e.g. 2 μm), the textured surface becomes amenable to coating a conformal PV active-layer. The resultant PV cells showed 100% increase in average light absorption near the band edge due to trapping of higher wavelength photons, and 20% improvement in power conversion efficiency as compared with the flat PV cell. Another factor that severely limits the performance of OPVs is recombination of charge carriers. Thus it becomes imperative to understand the effect of processing conditions such as spin coating speed and drying rate on defect density and hence induced carrier recombination mechanism. In this study, It is shown that slow growth (longer drying time) of the active-layer leads to reduction of sub-bandgap traps by an order of magnitude as compared to fast grown active-layer. By coupling the experimental results with simulations, it is demonstrated that at one sun condition, slow grown device has bimolecular recombination as the major loss mechanism while in the fast grown device with high trap density, the trap assisted recombination dominates. It has been estimated that non-radiative recombination accounts nearly 50% of efficiency loss in modern OPVs. Generally, an external bias (electric field) is required to collect all the photogenerated charges and thus prevent their recombination. The motivation is to induce additional electric field in otherwise low mobility conjugated polymer based active layer by incorporating ferroelectric dipoles. This is expected to facilitate singlet exciton dissociation in polymer matrix and impede charge transfer exciton (CTE) recombination at polymer:fullerene interface. For the first time, it is shown that the addition of ferroelectric dipoles to modern bulk heterojunction (BHJ) can significantly improve exciton dissociation, resulting in a ~50% enhancement of overall solar cell efficiency. The devices also exhibit the unique ferroelectric-photovoltaic effect with polarization-controlled power conversion efficiency.« less

Influence of an Inorganic Interlayer on Exciton Separation in Hybrid Solar Cells

PubMed Central

2015-01-01

It has been shown that in hybrid polymer–inorganic photovoltaic devices not all the photogenerated excitons dissociate at the interface immediately, but can instead exist temporarily as bound charge pairs (BCPs). Many of these BCPs do not contribute to the photocurrent, as their long lifetime as a bound species promotes various charge carrier recombination channels. Fast and efficient dissociation of BCPs is therefore considered a key challenge in improving the performance of polymer–inorganic cells. Here we investigate the influence of an inorganic energy cascading Nb2O5 interlayer on the charge carrier recombination channels in poly(3-hexylthiophene-2,5-diyl) (P3HT)–TiO2 and PbSe colloidal quantum dot–TiO2 photovoltaic devices. We demonstrate that the additional Nb2O5 film leads to a suppression of BCP formation at the heterojunction of the P3HT cells and also a reduction in the nongeminate recombination mechanisms in both types of cells. Furthermore, we provide evidence that the reduction in nongeminate recombination in the P3HT–TiO2 devices is due in part to the passivation of deep midgap trap states in the TiO2, which prevents trap-assisted Shockley–Read–Hall recombination. Consequently a significant increase in both the open-circuit voltage and the short-circuit current was achieved, in particular for P3HT-based solar cells, where the power conversion efficiency increased by 39%. PMID:26548399

Charge Transfer Processes in OPV Materials as Revealed by EPR Spectroscopy

DOE PAGES

Niklas, Jens; Poluektov, Oleg

2017-03-03

Understanding charge separation and charge transport at a molecular level is crucial for improving the efficiency of organic photovoltaic (OPV) cells. Under illumination of Bulk Heterojunction (BHJ) blends of polymers and fullerenes, various paramagnetic species are formed including polymer and fullerene radicals, radical pairs, and photoexcited triplet states. Light-induced Electron Paramagnetic Resonance (EPR) spectroscopy is ideally suited to study these states in BHJ due to its selectivity in probing the paramagnetic intermediates. Some advanced EPR techniques like light-induced ENDOR spectroscopy and pulsed techniques allow the determination of hyperfine coupling tensors, while high-frequency EPR allows the EPR signals of the individualmore » species to be resolved and their g-tensors to be determined. In these magnetic resonance parameters reveal details about the delocalization of the positive polaron on the various polymer donors which is important for the efficient charge separation in BHJ systems. Time-resolved EPR can contribute to the study of the dynamics of charge separation, charge transfer and recombination in BHJ by probing the unique spectral signatures of charge transfer and triplet states. Furthermore, the potential of the EPR also allows characterization of the intermediates and products of BHJ degradation.« less

Spatial variation in carrier dynamics along a single CdSSe nanowire

NASA Astrophysics Data System (ADS)

Blake, Jolie C.; Eldridge, Peter S.; Gundlach, Lars

2014-10-01

Ultrafast charge carrier dynamics along individual CdSxSe1-x nanowires has been measured. The use of an improved ultrafast Kerr-gated microscope allows for spatially resolved luminescence measurements along a single nanowire. Amplified spontaneous emission (ASE) was observed at high excitation fluences. Position dependent variations of ultrafast ASE dynamics were observed. SEM and colorimetric measurements showed that the difference in dynamics can be attributed to variations in non-radiative recombination rates along the wire. The dominant Shockley-Read recombination rate can be extracted from ASE dynamics and can be directly related to charge carrier mobility and defect density. Employing ASE as a probe for defect densities provides a new sub-micron spatially resolved, contactless method for measurements of charge carrier mobility.

Charge Exchange Recombination Spectroscopy Based on Diagnostic Neutral Beam in HT-7 Tokamak

NASA Astrophysics Data System (ADS)

Shi, Yuejiang; Fu, Jia; Li, Yingying; William, Rowan; Huang, He; Wang, Fudi; Gao, Huixian; Huang, Juann; Zhou, Qian; Liu, Sheng; Zhang, Jian; Li, Jun; Xie, Yuanlai; Liu, Zhimin; Huang, Yiyun; Hu, Chundong; Wan, Baonian

2010-02-01

Charge exchange recombination spectroscopy (CXRS) based on a diagnostic neutral beam (DNB) installed in the HT-7 tokamak is introduced. DNB can provide a 6 A extracted current at 50 kV for 0.1 s in hydrogen. It can penetrate into the core plasma in HT-7. The CXRS system is designed to observe charge exchange (CX) transitions in the visible spectrum. CX light from the beam is focused onto 10 optical fibers, which view the plasma from -5 cm to 20 cm. The CXRS system can measure the ion temperature as low as 0.1 keV. With CXRS, the local ion temperature profile in HT-7 was obtained for the first time.

Properties of the surface generation-recombination noise in 1.94 μm GaSb-based laser diodes

NASA Astrophysics Data System (ADS)

Glemža, Justinas; Palenskis, Vilius; Pralgauskaitė, Sandra; Vyšniauskas, Juozas; Matukas, Jonas

2018-06-01

A detail investigation of generation-recombination (g-r) noise in 1.94 μm GaSb-based type-I ridge waveguide laser diodes (LDs) has been performed in a temperature range (230-295) K. Lorentzian-type noise spectra have been observed in the current range below the threshold at the forward and reverse biases of the LDs with the same characteristic time (3.7 μs) and activation energy (≈0.37 eV) of charge carriers transitions associated with the g-r processes. An equivalent electrical circuit possessing the voltage noise source is presented, which allows the description of both the current-voltage characteristic and the voltage fluctuation spectral density of the laser diode. Results indicate that the origin of the g-r noise in the investigated samples is the surface recombination caused by the surface leakage current channel between n+GaSb and p+GaSb contacts, which is practically independent from the applied bias polarity.

Tailoring recombinant protein quality by rational media design.

PubMed

Brühlmann, David; Jordan, Martin; Hemberger, Jürgen; Sauer, Markus; Stettler, Matthieu; Broly, Hervé

2015-01-01

Clinical efficacy and safety of recombinant proteins are closely associated with their structural characteristics. The major quality attributes comprise glycosylation, charge variants (oxidation, deamidation, and C- & N-terminal modifications), aggregates, low-molecular-weight species (LMW), and misincorporation of amino acids in the protein backbone. Cell culture media design has a great potential to modulate these quality attributes due to the vital role of medium in mammalian cell culture. The purpose of this review is to provide an overview of the way both classical cell culture medium components and novel supplements affect the quality attributes of recombinant therapeutic proteins expressed in mammalian hosts, allowing rational and high-throughput optimization of mammalian cell culture media. A selection of specific and/or potent inhibitors and activators of oligosaccharide processing as well as components affecting multiple quality attributes are presented. Extensive research efforts in this field show the feasibility of quality engineering through media design, allowing to significantly modulate the protein function. © 2015 American Institute of Chemical Engineers.

Unraveling Charge Carriers Generation, Diffusion, and Recombination in Formamidinium Lead Triiodide Perovskite Polycrystalline Thin Film.

PubMed

Piatkowski, Piotr; Cohen, Boiko; Ponseca, Carlito S; Salado, Manuel; Kazim, Samrana; Ahmad, Shahzada; Sundström, Villy; Douhal, Abderrazzak

2016-01-07

We report on studies of the formamidinium lead triiodide (FAPbI3) perovskite film using time-resolved terahertz (THz) spectroscopy (TRTS) and flash photolysis to explore charge carriers generation, migration, and recombination. The TRTS results show that upon femtosecond excitation above the absorption edge, the initial high photoconductivity (∼75 cm(2) V(-1) s(-1)) remains constant at least up to 8 ns, which corresponds to a diffusion length of 25 μm. Pumping below the absorption edge results in a mobility of 40 cm(2) V(-1) s(-1) suggesting lower mobility of charge carriers located at the bottom of the conduction band or shallow sub-bandgap states. Furthermore, analysis of the THz kinetics reveals rising components of <1 and 20 ps, reflecting dissociation of excitons having different binding energies. Flash photolysis experiments indicate that trapped charge carriers persist for milliseconds.

Novel Flexible Plastic-Based Solar Cells

DTIC Science & Technology

2009-11-30

the high mobility of charge carriers in pentacene probably due to conducting domains provided by it. 2. Multi-Exciton Generation (MEG) in Devices...with simulating the model including recombination rate, trap density and trapped charge induced electric field. £ < £ O 0.2 0.3 0.4...to charge extraction and transport in hybrid nanoparticle:polymer photovoltaic devices. In particular, we demonstrated (i) enhancement of charge

Recent Livermore Excitation and Dielectronic Recombination Measurements for Laboratory and Astrophysical Spectral Modeling

NASA Technical Reports Server (NTRS)

Beiersdorfer, P.; Brown, G. V.; Gu, M.-F.; Harris, C. L.; Kahn, S. M.; Kim, S.-H.; Neill, P. A.; Savin, D. W.; Smith, A. J.; Utter, S. B.

2000-01-01

Using the EBIT facility in Livermore we produce definitive atomic data for input into spectral synthesis codes. Recent measurements of line excitation and dielectronic recombination of highly charged K-shell and L-shell ions are presented to illustrate this point.

Polarization of K-shell Dielectronic Recombination Satellite Lines of Fe XIX–XXV and Its Application for Diagnostics of Anisotropies of Hot Plasmas

NASA Astrophysics Data System (ADS)

Shah, Chintan; Amaro, Pedro; Steinbrügge, René; Bernitt, Sven; Crespo López-Urrutia, José R.; Tashenov, Stanislav

2018-02-01

We present a systematic measurement of the X-ray emission asymmetries in the K-shell dielectronic, trielectronic, and quadruelectronic recombination of free electrons into highly charged ions. Iron ions in He-like through O-like charge states were produced in an electron beam ion trap, and the electron–ion collision energy was scanned over the recombination resonances. Two identical X-ray detectors mounted head-on and side-on with respect to the electron beam propagation recorded X-rays emitted in the decay of resonantly populated states. The degrees of linear polarization of X-rays inferred from observed emission asymmetries benchmark distorted-wave predictions of the Flexible Atomic Code for several dielectronic recombination satellite lines. The present method also demonstrates its applicability for diagnostics of energy and direction of electron beams inside hot anisotropic plasmas. Both experimental and theoretical data can be used for modeling of hot astrophysical and fusion plasmas.

Kinetic Evidence of Two Pathways for Charge Recombination in NiO-Based Dye-Sensitized Solar Cells.

PubMed

D'Amario, Luca; Antila, Liisa J; Pettersson Rimgard, Belinda; Boschloo, Gerrit; Hammarström, Leif

2015-03-05

Mesoporous nickel oxide has been used as electrode material for p-type dye-sensitized solar cells (DSCs) for many years but no high efficiency cells have yet been obtained. One of the main issues that lowers the efficiency is the poor fill factor, for which a clear reason is still missing. In this paper we present the first evidence for a relation between applied potential and the charge recombination rate of the NiO electrode. In particular, we find biphasic recombination kinetics: a fast (15 ns) pathway attributed to the reaction with the holes in the valence band and a slow (1 ms) pathway assigned to the holes in the trap states. The fast component is the most relevant at positive potentials, while the slow component becomes more important at negative potentials. This means that at the working condition of the cell, the fast recombination is the most important. This could explain the low fill factor of NiO-based DSCs.

Separating grain-boundary and bulk recombination with time-resolved photoluminescence microscopy

DOE PAGES

Kuciauskas, Darius; Lu, Dingyuan; Grover, Sachit; ...

2017-12-04

Two-photon excitation (2PE) microscopy allows contactless and non-destructive cross-sectional analysis of grain-boundary (GB) and grain-interior (GI) properties in polycrystalline solar cells, with measurements of doping uniformity, space-charge field distribution, and carrier dynamics in different regions of the device. Using 2PE time-resolved microscopy, we analyzed charge-carrier lifetimes near the GBs and in the GI of polycrystalline thin-film CdTe solar cells doped with As. When the grain radius is larger than the minority-carrier diffusion length, GI lifetimes are interpreted as the bulk lifetimes ..tau..B, and GB recombination velocity SGB is extracted by comparing recombination rates in the GI and near GBs. Inmore » As-doped CdTe solar cells, we find ..tau..B = 1.0-2.4 ns and S GB = (1-4) x 10 5 cm/s. The results imply the potential to improve solar cell voltage via GB passivation and reduced recombination center concentration in the GI.« less

Separating grain-boundary and bulk recombination with time-resolved photoluminescence microscopy

NASA Astrophysics Data System (ADS)

Kuciauskas, Darius; Lu, Dingyuan; Grover, Sachit; Xiong, Gang; Gloeckler, Markus

2017-12-01

Two-photon excitation (2PE) microscopy allows contactless and non-destructive cross-sectional analysis of grain-boundary (GB) and grain-interior (GI) properties in polycrystalline solar cells, with measurements of doping uniformity, space-charge field distribution, and carrier dynamics in different regions of the device. Using 2PE time-resolved microscopy, we analyzed charge-carrier lifetimes near the GBs and in the GI of polycrystalline thin-film CdTe solar cells doped with As. When the grain radius is larger than the minority-carrier diffusion length, GI lifetimes are interpreted as the bulk lifetimes τB, and GB recombination velocity SGB is extracted by comparing recombination rates in the GI and near GBs. In As-doped CdTe solar cells, we find τB = 1.0-2.4 ns and SGB = (1-4) × 105 cm/s. The results imply the potential to improve solar cell voltage via GB passivation and reduced recombination center concentration in the GI.

Separating grain-boundary and bulk recombination with time-resolved photoluminescence microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuciauskas, Darius; Lu, Dingyuan; Grover, Sachit

Two-photon excitation (2PE) microscopy allows contactless and non-destructive cross-sectional analysis of grain-boundary (GB) and grain-interior (GI) properties in polycrystalline solar cells, with measurements of doping uniformity, space-charge field distribution, and carrier dynamics in different regions of the device. Using 2PE time-resolved microscopy, we analyzed charge-carrier lifetimes near the GBs and in the GI of polycrystalline thin-film CdTe solar cells doped with As. When the grain radius is larger than the minority-carrier diffusion length, GI lifetimes are interpreted as the bulk lifetimes ..tau..B, and GB recombination velocity SGB is extracted by comparing recombination rates in the GI and near GBs. Inmore » As-doped CdTe solar cells, we find ..tau..B = 1.0-2.4 ns and S GB = (1-4) x 10 5 cm/s. The results imply the potential to improve solar cell voltage via GB passivation and reduced recombination center concentration in the GI.« less

Electron transport limitation in P3HT:CdSe nanorods hybrid solar cells.

PubMed

Lek, Jun Yan; Xing, Guichuan; Sum, Tze Chien; Lam, Yeng Ming

2014-01-22

Hybrid solar cells have the potential to be efficient solar-energy-harvesting devices that can combine the benefits of solution-processable organic materials and the extended absorption offered by inorganic materials. In this work, an understanding of the factors limiting the performance of hybrid solar cells is explored. Through photovoltaic-device characterization correlated with transient absorption spectroscopy measurements, it was found that the interfacial charge transfer between the organic (P3HT) and inorganic (CdSe nanorods) components is not the factor limiting the performance of these solar cells. The insulating original ligands retard the charge recombination between the charge-transfer states across the CdSe-P3HT interface, and this is actually beneficial for charge collection. These cells are, in fact, limited by the subsequent electron collection via CdSe nanoparticles to the electrodes. Hence, the design of a more continuous electron-transport pathway should greatly improve the performance of hybrid solar cells in the future.

Comparative experimental study of gas evolution and gas consumption reactions in sealed Ni-Cd and Ni-MH cells

NASA Astrophysics Data System (ADS)

Cha, Chuansin; Yu, Jingxian; Zhang, Jixiao

The behavior of the sealed Ni-Cd and Ni-MH systems are compared experimentally with regard to their ability to consume gaseous products generated during the overcharge stage of these systems. It was found that the Ni-Cd system could only consume oxygen, while the Ni-MH system possesses the additional ability to adsorb hydrogen and to catalyze the recombination reaction of hydrogen and oxygen. The internal pressure within both sealed Ni-Cd cells and sealed Ni-MH cells can be kept well under control during the charge/overcharge processes if the rate of overcharge is not too high and if there is sufficient surplus of charging capacity at the negative electrodes. However, the internal pressure can rise to dangerously high levels if the rate of overcharge is too high or there is a deficiency of the charging capacity at the negative electrodes. The various factors that may affect the surplus of charging capacity of the negative electrodes are also discussed.

Exciton dynamics of C60-based single-photon emitters explored by Hanbury Brown-Twiss scanning tunnelling microscopy.

PubMed

Merino, P; Große, C; Rosławska, A; Kuhnke, K; Kern, K

2015-09-29

Exciton creation and annihilation by charges are crucial processes for technologies relying on charge-exciton-photon conversion. Improvement of organic light sources or dye-sensitized solar cells requires methods to address exciton dynamics at the molecular scale. Near-field techniques have been instrumental for this purpose; however, characterizing exciton recombination with molecular resolution remained a challenge. Here, we study exciton dynamics by using scanning tunnelling microscopy to inject current with sub-molecular precision and Hanbury Brown-Twiss interferometry to measure photon correlations in the far-field electroluminescence. Controlled injection allows us to generate excitons in solid C60 and let them interact with charges during their lifetime. We demonstrate electrically driven single-photon emission from localized structural defects and determine exciton lifetimes in the picosecond range. Monitoring lifetime shortening and luminescence saturation for increasing carrier injection rates provides access to charge-exciton annihilation dynamics. Our approach introduces a unique way to study single quasi-particle dynamics on the ultimate molecular scale.

Experimental verification of gain drop due to general ion recombination for a carbon-ion pencil beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tansho, Ryohei, E-mail: r-tansho@nirs.go.jp; Furukawa, Takuji; Hara, Yousuke

Purpose: Accurate dose measurement in radiotherapy is critically dependent on correction for gain drop, which is the difference of the measured current from the ideal saturation current due to general ion recombination. Although a correction method based on the Boag theory has been employed, the theory assumes that ionized charge density in an ionization chamber (IC) is spatially uniform throughout the irradiation volume. For particle pencil beam scanning, however, the charge density is not uniform, because the fluence distribution of a pencil beam is not uniform. The aim of this study was to verify the effect of the nonuniformity ofmore » ionized charge density on the gain drop due to general ion recombination. Methods: The authors measured the saturation curve, namely, the applied voltage versus measured current, using a large plane-parallel IC and 24-channel parallel-plate IC with concentric electrodes. To verify the effect of the nonuniform ionized charge density on the measured saturation curve, the authors calculated the saturation curve using a method which takes into account the nonuniform ionized charge density and compared it with the measured saturation curves. Results: Measurement values of the different saturation curves in the different channels of the concentric electrodes differed and were consistent with the calculated values. The saturation curves measured by the large plane-parallel IC were also consistent with the calculation results, including the estimation error of beam size and of setup misalignment. Although the impact of the nonuniform ionized charge density on the gain drop was clinically negligible with the conventional beam intensity, it was expected that the impact would increase with higher ionized charge density. Conclusions: For pencil beam scanning, the assumption of the conventional Boag theory is not valid. Furthermore, the nonuniform ionized charge density affects the prediction accuracy of gain drop when the ionized charge density is increased by a higher dose rate and/or lower beam size.« less

Calculation of the thermoneutral potential of NiCd and NiH2 cells

NASA Technical Reports Server (NTRS)

Zimmerman, Albert H.

1994-01-01

The thermoneutral potential of a nickel cadmium or nickel hydrogen cell is the potential at which the cell charge or discharge process puts out zero heat, and thus is the potential corresponding to the enthalpy change of the charge/discharge reaction, delta H. A relatively straightforward method for obtaining the thermoneutral potential E(sub tn), is based on the measured potential and temperature derivative of the cell reactions, which are related to the free energy change delta G, and entropy change delta S, respectively. Particularly in the nickel hydrogen cell, the pressure of hydrogen can often vary over an order of magnitude or more during the course of a charge or discharge. In a nickel cadmium cell, although significant changes in oxygen pressure can occur during charge or discharge, since oxygen does not enter into the charge/discharge reaction, these pressure changes are related to the heat generated from oxygen evolution and recombination. However, the entropy changes due to changes in hydrogen pressure relative to the 1 atm standard state must be included to apply this method to the nickel hydrogen cell.

Surface/Interface Carrier-Transport Modulation for Constructing Photon-Alternative Ultraviolet Detectors Based on Self-Bending-Assembled ZnO Nanowires.

PubMed

Guo, Zhen; Zhou, Lianqun; Tang, Yuguo; Li, Lin; Zhang, Zhiqi; Yang, Hongbo; Ma, Hanbin; Nathan, Arokia; Zhao, Dongxu

2017-09-13

Surface/interface charge-carrier generation, diffusion, and recombination/transport modulation are especially important in the construction of photodetectors with high efficiency in the field of nanoscience. In the paper, a kind of ultraviolet (UV) detector is designed based on ZnO nanostructures considering photon-trapping, surface plasmonic resonance (SPR), piezophototronic effects, interface carrier-trapping/transport control, and collection. Through carefully optimized surface/interface carrier-transport modulation, a designed device with detectivity as high as 1.69 × 10 16 /1.71 × 10 16 cm·Hz 1/2 /W irradiating with 380 nm photons under ultralow bias of 0.2 V is realized by alternating nanoparticle/nanowire active layers, respectively, and the designed UV photodetectors show fast and slow recovery processes of 0.27 and 4.52 ms, respectively, which well-satisfy practical needs. Further, it is observed that UV photodetection could be performed within an alternative response by varying correlated key parameters, through efficient surface/interface carrier-transport modulation, spectrally resolved photoresponse of the detector revealing controlled detection in the UV region based on the ZnO nanomaterial, photodetection allowed or limited by varying the active layers, irradiation distance from one of the electrodes, standing states, or electric field. The detailed carrier generation, diffusion, and recombination/transport processes are well illustrated to explain charge-carrier dynamics contributing to the photoresponse behavior.

Exciton recombination dynamics in CdSe nanowires: bimolecular to three-carrier Auger kinetics.

PubMed

Robel, István; Bunker, Bruce A; Kamat, Prashant V; Kuno, Masaru

2006-07-01

Ultrafast relaxation dynamics of charge carriers in CdSe quantum wires with diameters between 6 and 8 nm are studied as a function of carrier density. At high electron-hole pair densities above 10(19) cm(-3) the dominant process for carrier cooling is the "bimolecular" Auger recombination of one-dimensional (1D) excitons. However, below this excitation level an unexpected transition from a bimolecular (exciton-exciton) to a three-carrier Auger relaxation mechanism occurs. Thus, depending on excitation intensity, electron-hole pair relaxation dynamics in the nanowires exhibit either 1D or 0D (quantum dot) character. This dual nature of the recovery kinetics defines an optimal intensity for achieving optical gain in solution-grown nanowires given the different carrier-density-dependent scaling of relaxation rates in either regime.

Role of the inversion layer on the charge injection in silicon nanocrystal multilayered light emitting devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tondini, S.; Dipartimento di Fisica, Informatica e Matematica, Università di Modena e Reggio Emilia, Via Campi 213/a, 41125 Modena; Pucker, G.

2016-09-07

The role of the inversion layer on injection and recombination phenomena in light emitting diodes (LEDs) is here studied on a multilayer (ML) structure of silicon nanocrystals (Si-NCs) embedded in SiO{sub 2}. Two Si-NC LEDs, which are similar for the active material but different in the fabrication process, elucidate the role of the non-radiative recombination rates at the ML/substrate interface. By studying current- and capacitance-voltage characteristics as well as electroluminescence spectra and time-resolved electroluminescence under pulsed and alternating bias pumping scheme in both the devices, we are able to ascribe the different experimental results to an efficient or inefficient minoritymore » carrier (electron) supply by the p-type substrate in the metal oxide semiconductor LEDs.« less

A high etendue spectrometer suitable for core charge eXchange recombination spectroscopy on ITER.

PubMed

Jaspers, R J E; Scheffer, M; Kappatou, A; van der Valk, N C J; Durkut, M; Snijders, B; Marchuk, O; Biel, W; Pokol, G I; Erdei, G; Zoletnik, S; Dunai, D

2012-10-01

A feasibility study for the use of core charge exchange recombination spectroscopy on ITER has shown that accurate measurements on the helium ash require a spectrometer with a high etendue of 1mm(2)sr to comply with the measurement requirements [S. Tugarinov et al., Rev. Sci. Instrum. 74, 2075 (2003)]. To this purpose such an instrument has been developed consisting of three separate wavelength channels (to measure simultaneously He/Be, C/Ne, and H/D/T together with the Doppler shifted direct emission of the diagnostic neutral beam, the beam emission (BES) signal), combining high dispersion (0.02 nm/pixel), sufficient resolution (0.2 nm), high efficiency (55%), and extended wavelength range (14 nm) at high etendue. The combined measurement of the BES along the same sightline within a third wavelength range provides the possibility for in situ calibration of the charge eXchange recombination spectroscopy signals. In addition, the option is included to use the same instrument for measurements of the fast fluctuations of the beam emission intensity up to 2 MHz, with the aim to study MHD activity.

Interplay between Interfacial Structures and Device Performance in Organic Solar Cells: A Case Study with the Low Work Function Metal, Calcium.

PubMed

Ju, Huanxin; Knesting, Kristina M; Zhang, Wei; Pan, Xiao; Wang, Chia-Hsin; Yang, Yaw-Wen; Ginger, David S; Zhu, Junfa

2016-01-27

A better understanding of how interfacial structure affects charge carrier recombination would benefit the development of highly efficient organic photovoltaic (OPV) devices. In this paper, transient photovoltage (TPV) and charge extraction (CE) measurements are used in combination with synchrotron radiation photoemission spectroscopy (SRPES) to gain insight into the correlation between interfacial properties and device performance. OPV devices based on PCDTBT/PC71BM with a Ca interlayer were studied as a reference system to investigate the interfacial effects on device performance. Devices with a Ca interlayer exhibit a lower recombination than devices with only an Al cathode at a given charge carrier density (n). In addition, the interfacial band structures indicate that the strong dipole moment produced by the Ca interlayer can facilitate the extraction of electrons and drive holes away from the cathode/polymer interface, resulting in beneficial reduction in interfacial recombination losses. These results help explain the higher efficiencies of devices made with Ca interlayers compared to that without the Ca interlayer.

Encapsulating Bi2Ti2O7 (BTO) with reduced graphene oxide (RGO): an effective strategy to enhance photocatalytic and photoelectrocatalytic activity of BTO.

PubMed

Gupta, Satyajit; Subramanian, Vaidyanathan Ravi

2014-11-12

Multimetal oxides (AxByOz) offer a higher degree of freedom compared to single metal oxides (AOx) in that these oxides facilitate (i) designing nanomaterials with greater stability, (ii) tuning of the optical bandgap, and (iii) promoting visible light absorption. However, all AxByOz materials such as pyrochlores (A2B2O7)--referred to here as band-gap engineered composite oxide nanomaterials or BECONs--are traditionally prone to severe charge recombination at their surface. To alleviate the charge recombination, an effective strategy is to employ reduced graphene oxide (RGO) as a charge separator. The BECON and the RGO with oppositely charged functional groups attached to them can be integrated at the interface by employing a simple electrostatic self-assembly approach. As a case study, the approach is demonstrated using the Pt-free pyrochlore bismuth titanate (BTO) with RGO, and the application of the composite is investigated for the first time. When tested as a photocatalyst toward hydrogen production, an increase of ∼ 250% using BTO in the presence of RGO was observed. Further, photoelectrochemical measurements indicate an enhancement of ∼ 130% in the photocurrent with RGO inclusion. These two results firmly establish the viability of the electrostatic approach and the inclusion of RGO. The merits of the RGO addition is identified as (i) the RGO-assisted improvement in the separation of the photogenerated charges of BTO, (ii) the enhanced utilization of the charges in a photocatalytic process, and (iii) the maintenance of the BTO/RGO structural integrity after repeated use (established through reusability analysis). The success of the self-assembly strategy presented here lays the foundation for developing other forms of BECONs, belonging to perovskites (ABO3), sillenite (A12BO20), or delafossite (ABO2) groups, hitherto written off due to limited or no photoelectrochemicalactivity.

Evidence for strong Breit interaction in dielectronic recombination of highly charged heavy ions.

PubMed

Nakamura, Nobuyuki; Kavanagh, Anthony P; Watanabe, Hirofumi; Sakaue, Hiroyuki A; Li, Yueming; Kato, Daiji; Currell, Fred J; Ohtani, Shunsuke

2008-02-22

Resonant strengths have been measured for dielectronic recombination of Li-like iodine, holmium, and bismuth using an electron beam ion trap. By observing the atomic number dependence of the state-resolved resonant strength, clear experimental evidence has been obtained that the importance of the generalized Breit interaction (GBI) effect on dielectronic recombination increases as the atomic number increases. In particular, it has been shown that the GBI effect is exceptionally strong for the recombination through the resonant state [1s2s(2)2p(1/2)](1).

Enhanced Solar Cell Conversion Efficiency of InGaN/GaN Multiple Quantum Wells by Piezo-Phototronic Effect.

PubMed

Jiang, Chunyan; Jing, Liang; Huang, Xin; Liu, Mengmeng; Du, Chunhua; Liu, Ting; Pu, Xiong; Hu, Weiguo; Wang, Zhong Lin

2017-09-26

The piezo-phototronic effect is the tuning of piezoelectric polarization charges at the interface to largely enhance the efficiency of optoelectronic processes related to carrier separation or recombination. Here, we demonstrated the enhanced short-circuit current density and the conversion efficiency of InGaN/GaN multiple quantum well solar cells with an external stress applied on the device. The external-stress-induced piezoelectric charges generated at the interfaces of InGaN and GaN compensate the piezoelectric charges induced by lattice mismatch stress in the InGaN wells. The energy band realignment is calculated with a self-consistent numerical model to clarify the enhancement mechanism of optical-generated carriers. This research not only theoretically and experimentally proves the piezo-phototronic effect modulated the quantum photovoltaic device but also provides a great promise to maximize the use of solar energy in the current energy revolution.

Multiple exciton dissociation in CdSe quantum dots by ultrafast electron transfer to adsorbed methylene blue.

PubMed

Huang, Jier; Huang, Zhuangqun; Yang, Ye; Zhu, Haiming; Lian, Tianquan

2010-04-07

Multiexciton generation in quantum dots (QDs) may provide a new approach for improving the solar-to-electric power conversion efficiency in QD-based solar cells. However, it remains unclear how to extract these excitons before the ultrafast exciton-exciton annihilation process. In this study we investigate multiexciton dissociation dynamics in CdSe QDs adsorbed with methylene blue (MB(+)) molecules by transient absorption spectroscopy. We show that excitons in QDs dissociate by ultrafast electron transfer to MB(+) with an average time constant of approximately 2 ps. The charge separated state is long-lived (>1 ns), and the charge recombination rate increases with the number of dissociated excitons. Up to three MB(+) molecules per QD can be reduced by exciton dissociation. Our result demonstrates that ultrafast interfacial charge separation can effectively compete with exciton-exciton annihilation, providing a viable approach for utilizing short-lived multiple excitons in QDs.

Realizing 11.3% efficiency in PffBT4T-2OD fullerene organic solar cells via superior charge extraction at interfaces

NASA Astrophysics Data System (ADS)

Xu, Cheng; Wright, Matthew; Elumalai, Naveen Kumar; Mahmud, Md Arafat; Wang, Dian; Gonçales, Vinicius R.; Upama, Mushfika Baishakhi; Haque, Faiazul; Gooding, J. Justin; Uddin, Ashraf

2018-06-01

The influence of interface engineering on the performance and photovoltaic properties of the PffBT4T-2OD poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-di(2-octyldodecyl)-2,2';5',2″;5″,2'''-quaterthiophen-5,5'''-diy)] based polymer solar cells (PSCs) are investigated. Owing to the high crystallinity and processing parameter dependent morphology distribution of the PffBT4T-2OD polymer, the performance of the devices can vary significantly with power conversion efficiency (PCE) of around 10% has been reported via such morphology modification. In this work, we demonstrate the effect of trap state passivation at the electron transport layer (ETL)/Polymer interface on the performance of PffBT4T-2OD based PSCs. Aluminium doped ZnO (AZO) and pristine Zinc Oxide (ZnO) are employed as ETLs, which modified the polymer wettability and blend morphology. The interface engineered devices exhibited high PCE of over 11% with high J sc of about 22.5 mA/cm2 which is about 19% higher than that of the conventional ZnO based devices. The reason behind such distinct enhancements is investigated using several material and device characterization methods including electrochemical impedance spectroscopy (EIS). The recombination resistance ( R rec) of the AZO based device is found to be 4.5 times higher than that of the ZnO devices. The enhanced photovoltaic parameters of the AZO based device are attributed to the superior charge transport characteristics in the ETL as well as at the ETL/polymer interface, enabling effective charge extraction at the respective electrodes with much lesser recombination. The mechanism and the processes behind such enhancements are also elaborated in detail.

A solution-processed binary cathode interfacial layer facilitates electron extraction for inverted polymer solar cells.

PubMed

Zhang, Xinyuan; Li, Zhiqi; Liu, Chunyu; Guo, Jiaxin; Shen, Liang; Guo, Wenbin

2018-03-15

The charge transfer and separation are significantly affected by the electron properties of the interface between the electron-donor layer and the carrier-transporting layer in polymer solar cells (PSCs). In this study, we investigate the electron extraction mechanism of PSCs with a low temperature solution-processed ZnO/PEI as electron transport layer. The incorporation of PEI layer can decrease the work function of ZnO and reduce interfacial barrier, which facilitates electron extraction and suppresses bimolecular recombination, leading to a significant performance enhancement. Furthermore, PEI layer can induce phase separation and passivite inorganic surface trap states as well as shift the interfacial energy offset between metal oxide and organic materials. This work offers a simple and effective way to improve the charge transporting property of organic photovoltaic devices. Copyright © 2017 Elsevier Inc. All rights reserved.

Spectrum-enhanced Au@ZnO plasmonic nanoparticles for boosting dye-sensitized solar cell performance

NASA Astrophysics Data System (ADS)

Liu, Qisheng; Wei, Yunwei; Shahid, Malik Zeeshan; Yao, Mingming; Xu, Bo; Liu, Guangning; Jiang, Kejian; Li, Cuncheng

2018-03-01

Spectrum-enhanced Au@ZnO plasmonic nanoparticles (NPs) are developed for fabrication of the dye-sensitized solar cells (DSSCs), and their remarkable enhanced performances are achieved due to Surface Plasmon Resonance (SPR) effects. When being doped different blended amounts of the Au@ZnO NPs within the photoanode layers, various enhanced effects in the SPR-based DSSCs are exhibited. Compared with the power conversion efficiency (PCE, 7.50%) achieved for bare DSSC, device with doped Au@ZnO NPs of 1.93% delivers the top PCE of 8.91%, exhibiting about 20% enhancement. To elaborate the charge transfer process in the Au@ZnO NPs blended DSSCs, the photoluminescence (PL), electrochemical impedance spectra (EIS), etc are performed. We find that both the enhanced SPR absorption properties and the suppressed recombination process of charges contribute much to the improved performance of Au@ZnO-incorporated DSSCs.

A series connection architecture for large-area organic photovoltaic modules with a 7.5% module efficiency.

PubMed

Hong, Soonil; Kang, Hongkyu; Kim, Geunjin; Lee, Seongyu; Kim, Seok; Lee, Jong-Hoon; Lee, Jinho; Yi, Minjin; Kim, Junghwan; Back, Hyungcheol; Kim, Jae-Ryoung; Lee, Kwanghee

2016-01-05

The fabrication of organic photovoltaic modules via printing techniques has been the greatest challenge for their commercial manufacture. Current module architecture, which is based on a monolithic geometry consisting of serially interconnecting stripe-patterned subcells with finite widths, requires highly sophisticated patterning processes that significantly increase the complexity of printing production lines and cause serious reductions in module efficiency due to so-called aperture loss in series connection regions. Herein we demonstrate an innovative module structure that can simultaneously reduce both patterning processes and aperture loss. By using a charge recombination feature that occurs at contacts between electron- and hole-transport layers, we devise a series connection method that facilitates module fabrication without patterning the charge transport layers. With the successive deposition of component layers using slot-die and doctor-blade printing techniques, we achieve a high module efficiency reaching 7.5% with area of 4.15 cm(2).

Optoelectronic Properties of Conjugated Block Copolymer with Flexible Linking Group

NASA Astrophysics Data System (ADS)

Hu, Zhiqi; Verduzco, Rafael

State-of-the-art organic photovoltaics (OPVs) are prepared by depositing a disordered, co-continuous donor and acceptor blend. While optimization of material processing has produced significant improvements in performance, a fundamental understanding of charge separation and recombination at the donor/acceptor interface is lacking. Block copolymers with donor and acceptor polymer blocks provide an opportunity for controlling the donor-accepter interfacial structure and understanding its relationship to charge separation and photovoltaic performance. Here, we report the synthesis and characterization of donor-linker-acceptor block copolymers for use in OPVs. A series of poly(3-hexylthiophene)-block- poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (P3HT-linkerPFTBT) are synthesized with flexible oligo-ethylene glycol (PEG) linkers. Photoluminescence measurements demonstrate that the insertion of a non-conjugated linker has a significant impact on energy transfer between the two blocks, and the block copolymers are used as additives for bulk heterojunction OPVs. This work provides insight into the charge separation process and demonstrates a technique for tailoring the donor-accepter interface in OPVs.

Charge carrier transport and photogeneration in P3HT:PCBM photovoltaic blends.

PubMed

Laquai, Frédéric; Andrienko, Denis; Mauer, Ralf; Blom, Paul W M

2015-06-01

This article reviews the charge transport and photogeneration in bulk-heterojunction solar cells made from blend films of regioregular poly(3-hexylthiophene) (RR-P3HT) and methano-fullerene (PCBM). The charge transport, specifically the hole mobility in the RR-P3HT phase of the polymer:fullerene photovoltaic blend, is dramatically affected by thermal annealing. The hole mobility increases more than three orders of magnitude and reaches a value of up to 2 × 10(-4) cm(2) V(-1) s(-1) after the thermal annealing process as a result of an improved semi-crystallinity of the film. This significant increase of the hole mobility balances the electron and hole mobilities in a photovoltaic blend in turn reducing space-charge formation, and this is the most important factor for the strong enhancement of the photovoltaic efficiency compared to an as cast, that is, non-annealed device. In fact, the balanced charge carrier mobility in RR-P3HT:PCBM blends in combination with a field- and temperature-independent charge carrier generation and greatly reduced non-geminate recombination explains the large quantum efficiencies mea-sured in P3HT:PCBM photovoltaic devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of emission layer doping on the spatial distribution of charge and host recombination rate density in organic light emitting devices: A numerical study

NASA Astrophysics Data System (ADS)

Li, Yanli; Zhou, Maoqing; Zheng, Tingcai; Yao, Bo; Peng, Yingquan

2013-12-01

Based on drift-diffusion theory, a numerical model of the doping of a single energy level trap in the emission layer of an organic light emitting device (OLED) was developed, and the effects of doping of this single energy level trap on the distribution of the charge density, the recombination rate density, and the electric field in single- and double-layer OLEDs were studied numerically. The results show that by doping the n-type (p-type) emission layer with single energy electron (hole) traps, the distribution of the recombination rate density can be tuned and shifted, which is useful for improvement of the device performance by reduced electrode quenching or for realization of desirable special functions, e.g., emission spectrum tuning in multiple dye-doped white OLEDs.

The effect of N2/+/ recombination on the aeronomic determination of the charge exchange rate coefficient of O/+//2D/ with N2

NASA Technical Reports Server (NTRS)

Torr, D. G.; Orsini, N.

1978-01-01

The Atmosphere Explorer (AE) data are reexamined in the light of new laboratory measurements of the N2(+) recombination rate coefficient alpha. The new measurements support earlier measurements which yielded values of alpha significantly lower than the AE values. It is found that the values for alpha determined from the satellite data can be reconciled with the laboratory measurements, if the charge exchange rate coefficient for O(+)(2D) with N2 is less than one-quarter of that derived in the laboratory by Rutherford and Vroom (1971).

Use of low-energy hydrogen ion implants in high-efficiency crystalline-silicon solar cells

NASA Technical Reports Server (NTRS)

Fonash, S. J.; Sigh, R.; Mu, H. C.

1986-01-01

The use of low-energy hydrogen implants in the fabrication of high-efficiency crystalline silicon solar cells was investigated. Low-energy hydrogen implants result in hydrogen-caused effects in all three regions of a solar cell: emitter, space charge region, and base. In web, Czochralski (Cz), and floating zone (Fz) material, low-energy hydrogen implants reduced surface recombination velocity. In all three, the implants passivated the space charge region recombination centers. It was established that hydrogen implants can alter the diffusion properties of ion-implanted boron in silicon, but not ion-implated arsenic.

Diphenylphenoxy-Thiophene-PDI Dimers as Acceptors for OPV Applications with Open Circuit Voltage Approaching 1 Volt.

PubMed

Stenta, Caterina; Molina, Desiré; Viterisi, Aurélien; Montero-Rama, María Pilar; Pla, Sara; Cambarau, Werther; Fernández-Lázaro, Fernando; Palomares, Emilio; Marsal, Lluis F; Sastre-Santos, Ángela

2018-03-30

Two new perylenediimides (PDIs) have been developed for use as electron acceptors in solution-processed bulk heterojunction solar cells. The compounds were designed to exhibit maximal solubility in organic solvents, and reduced aggregation in the solid state. In order to achieve this, diphenylphenoxy groups were used to functionalize a monomeric PDI core, and two PDI dimers were bridged with either one or two thiophene units. In photovoltaic devices prepared using PDI dimers and a monomer in conjunction with PTB7, it was found that the formation of crystalline domains in either the acceptor or donor was completely suppressed. Atomic force microscopy, X-ray diffraction, charge carrier mobility measurements and recombination kinetics studies all suggest that the lack of crystallinity in the active layer induces a significant drop in electron mobility. Significant surface recombination losses associated with a lack of segregation in the material were also identified as a significant loss mechanism. Finally, the monomeric PDI was found to have sub-optimum LUMO energy matching the cathode contact, thus limiting charge carrier extraction. Despite these setbacks, all PDIs produced high open circuit voltages, reaching almost 1 V in one particular case.

High-Potential Porphyrins Supported on SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications

DOE PAGES

Jiang, Jianbing; Swierk, John R.; Materna, Kelly L.; ...

2016-12-03

Here, we report CF 3-substituted porphyrins and evaluate their use as photosensitizers in water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) by characterizing interfacial electron transfer on metal oxide surfaces. Furthermore, by using (CF 3) 2C 6H 3 instead of C 6F 5 substituents at the meso positions, we obtain the desired high potentials while avoiding the sensitivity of C 6F 5 substituents to nucleophilic substitution, a process that limits the types of synthetic reactions that can be used. Both the number of CF 3 groups and the central metal tune the ground and excited-state potentials. A pair of porphyrins bearing carboxylic acidsmore » as anchoring groups were deposited on SnO 2 and TiO 2 surfaces and the interfacial charge-injection and charge-recombination kinetics were characterized by using a combination of computational modeling, terahertz measurements, and transient absorption spectroscopy. We also found that both free-base and metallated porphyrins inject into SnO 2, and that recombination is slower for the latter case. Our findings demonstrate that (CF 3) 2C 6H 3-substituted porphyrins are promising photosensitizers for use in WS-DSPECs.« less

Large-scale atomistic calculations of clusters in intense x-ray pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Phay J.; Knight, Chris

Here, we present the methodology of our recently developed Monte-Carlo/ Molecular-Dynamics method for studying the fundamental ultrafast dynamics induced by high-fluence, high-intensity x-ray free electron laser (XFEL) pulses in clusters. The quantum nature of the initiating ionization process is accounted for by a Monte Carlo method to calculate probabilities of electronic transitions, including photo absorption, inner-shell relaxation, photon scattering, electron collision and recombination dynamics, and thus track the transient electronic configurations explicitly. The freed electrons and ions are followed by classical particle trajectories using a molecular dynamics algorithm. These calculations reveal the surprising role of electron-ion recombination processes that leadmore » to the development of nonuniform spatial charge density profiles in x-ray excited clusters over femtosecond timescales. In the high-intensity limit, it is important to include the recombination dynamics in the calculated scattering response even for a 2- fs pulse. We also demonstrate that our numerical codes and algorithms can make e!cient use of the computational power of massively parallel supercomputers to investigate the intense-field dynamics in systems with increasing complexity and size at the ultrafast timescale and in non-linear x-ray interaction regimes. In particular, picosecond trajectories of XFEL clusters with attosecond time resolution containing millions of particles can be e!ciently computed on upwards of 262,144 processes.« less

Large-scale atomistic calculations of clusters in intense x-ray pulses

DOE PAGES

Ho, Phay J.; Knight, Chris

2017-04-28

Here, we present the methodology of our recently developed Monte-Carlo/ Molecular-Dynamics method for studying the fundamental ultrafast dynamics induced by high-fluence, high-intensity x-ray free electron laser (XFEL) pulses in clusters. The quantum nature of the initiating ionization process is accounted for by a Monte Carlo method to calculate probabilities of electronic transitions, including photo absorption, inner-shell relaxation, photon scattering, electron collision and recombination dynamics, and thus track the transient electronic configurations explicitly. The freed electrons and ions are followed by classical particle trajectories using a molecular dynamics algorithm. These calculations reveal the surprising role of electron-ion recombination processes that leadmore » to the development of nonuniform spatial charge density profiles in x-ray excited clusters over femtosecond timescales. In the high-intensity limit, it is important to include the recombination dynamics in the calculated scattering response even for a 2- fs pulse. We also demonstrate that our numerical codes and algorithms can make e!cient use of the computational power of massively parallel supercomputers to investigate the intense-field dynamics in systems with increasing complexity and size at the ultrafast timescale and in non-linear x-ray interaction regimes. In particular, picosecond trajectories of XFEL clusters with attosecond time resolution containing millions of particles can be e!ciently computed on upwards of 262,144 processes.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Kaifeng; Lim, Jaehoon; Klimov, Victor I.

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdSmore » QDs with two distinct core/shell interfacial profiles (“sharp” versus “smooth”). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. Furthermore, by comparing the measurements on the QDs with the “sharp” versus “smooth” interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. Our findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states, suggesting its generality to quantum-confined nanocrystals of arbitrary compositions and complexities.« less

Transport-related triplet states and hyperfine couplings in organic tandem solar cells probed by pulsed electrically detected magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Bahro, Daniel; Meier, Christoph; Denne, Maximilian; Colsmann, Alexander; Behrends, Jan

2017-09-01

Tandem solar cells constitute the most successful organic photovoltaic devices with power conversion efficiencies comparable to thin-film silicon solar cells. Especially their high open-circuit voltage - only achievable by a well-adjusted layer stacking - leads to their high efficiencies. Nevertheless, the microscopic processes causing the lossless recombination of charge carriers within the recombination zone are not well understood yet. We show that advanced pulsed electrically detected magnetic resonance techniques such as electrically detected (ED)-Rabi nutation measurements and electrically detected hyperfine sublevel correlation (ED-HYSCORE) spectroscopy help to understand the role of triplet excitons in these microscopic processes. We investigate fully working miniaturised organic tandem solar cells and detect current-influencing doublet states in different layers as well as triplet excitons located on the fullerene-based acceptor. We apply ED-HYSCORE in order to study the nuclear spin environment of the relevant electron/hole spins and detect a significant amount of the low abundant 13C nuclei coupled to the observer spins.

Probing Photoexcited Carriers in a Few-Layer MoS2 Laminate by Time-Resolved Optical Pump-Terahertz Probe Spectroscopy.

PubMed

Kar, Srabani; Su, Y; Nair, R R; Sood, A K

2015-12-22

We report the dynamics of photoinduced carriers in a free-standing MoS2 laminate consisting of a few layers (1-6 layers) using time-resolved optical pump-terahertz probe spectroscopy. Upon photoexcitation with the 800 nm pump pulse, the terahertz conductivity increases due to absorption by the photoinduced charge carriers. The relaxation of the non-equilibrium carriers shows fast as well as slow decay channels, analyzed using a rate equation model incorporating defect-assisted Auger scattering of photoexcited electrons, holes, and excitons. The fast relaxation time occurs due to the capture of electrons and holes by defects via Auger processes, resulting in nonradiative recombination. The slower relaxation arises since the excitons are bound to the defects, preventing the defect-assisted Auger recombination of the electrons and the holes. Our results provide a comprehensive understanding of the non-equilibrium carrier kinetics in a system of unscreened Coulomb interactions, where defect-assisted Auger processes dominate and should be applicable to other 2D systems.

Spectroscopy of Photovoltaic Materials: Charge-Transfer Complexes and Titanium Dioxide

NASA Astrophysics Data System (ADS)

Dillon, Robert John

The successful function of photovoltaic (PV) and photocatalytic (PC) systems centers primarily on the creation and photophysics of charge separated electron-hole pairs. The pathway leading to separate carriers varies by material; organic materials typically require multiple events to charge separate, whereas inorganic semiconductors can directly produce free carriers. In this study, time-resolved spectroscopy is used to provide insight into two such systems: 1) organic charge-transfer (CT) complexes, where electrons and holes are tightly bound to each other, and 2) Au-TiO2 core-shell nanostructures, where free carriers are directly generated. 1) CT complexes are structurally well defined systems consisting of donor molecules, characterized by having low ionization potentials, and acceptor molecules, characterized by having high electron affinities. Charge-transfer is the excitation of an electron from the HOMO of a donor material directly into the LUMO of the acceptor material, leading to an electron and hole separated across the donor:acceptor interface. The energy of the CT transition is often less than that of the bandgaps of donor and acceptor materials individually, sparking much interest if PV systems can utilize the CT band to generate free carriers from low energy photons. In this work we examine the complexes formed between acceptors tetracyanobenzene (TCNB) and tetracyanoquinodimethane (TCNQ) with several aromatic donors. We find excitation of the charge-transfer band of these systems leads to strongly bound electron-hole pairs that exclusively undergo recombination to the ground state. In the case of the TCNB complexes, our initial studies were flummoxed by the samples' generally low threshold for photo and mechanical damage. As our results conflicted with previous literature, a significant portion of this study was spent quantifying the photodegradation process. 2) Unlike the previous system, free carriers are directly photogenerated in TiO2, and the prime consideration is avoiding loss due to recombination of the electron and hole. In this study, four samples of core-shell Au-TiO 2 nanostructures are analyzed for their photocatalytic activity and spectroscopic properties. The samples were made with increasingly crystalline TiO2 shells. The more crystalline samples had higher photocatalytic activities, attributed to longer carrier lifetimes. The observed photophysics of these samples vary with excitation wavelength and detection method used. We find the time-resolved photoluminescence correlates with the samples' photocatalytic activities only when high energy, excitation wavelength less than or equal to 300 nm is used, while transient absorption experiments show no correlation regardless of excitation source. The results imply that photoexcitation with high energy photons can generate both reactive surface sites and photoluminescent surface sites in parallel. Both types of sites then undergo similar electron-hole recombination processes that depend on the crystallinity of the TiO2 shell. Surface sites created by low energy photons, as well as bulk TiO2 carrier dynamics that are probed by transient absorption, do not appear to be sensitive to the same dynamics that determine chemical reactivity.

Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene-MoS2 van der Waals Heterojunction.

PubMed

Bettis Homan, Stephanie; Sangwan, Vinod K; Balla, Itamar; Bergeron, Hadallia; Weiss, Emily A; Hersam, Mark C

2017-01-11

van der Waals heterojunctions between two-dimensional (2D) layered materials and nanomaterials of different dimensions present unique opportunities for gate-tunable optoelectronic devices. Mixed-dimensional p-n heterojunction diodes, such as p-type pentacene (0D) and n-type monolayer MoS 2 (2D), are especially interesting for photovoltaic applications where the absorption cross-section and charge transfer processes can be tailored by rational selection from the vast library of organic molecules and 2D materials. Here, we study the kinetics of excited carriers in pentacene-MoS 2 p-n type-II heterojunctions by transient absorption spectroscopy. These measurements show that the dissociation of MoS 2 excitons occurs by hole transfer to pentacene on the time scale of 6.7 ps. In addition, the charge-separated state lives for 5.1 ns, up to an order of magnitude longer than the recombination lifetimes from previously reported 2D material heterojunctions. By studying the fractional amplitudes of the MoS 2 decay processes, the hole transfer yield from MoS 2 to pentacene is found to be ∼50%, with the remaining holes undergoing trapping due to surface defects. Overall, the ultrafast charge transfer and long-lived charge-separated state in pentacene-MoS 2 p-n heterojunctions suggest significant promise for mixed-dimensional van der Waals heterostructures in photovoltaics, photodetectors, and related optoelectronic technologies.

Lifetime of excess electrons in Cu–Zn–Sn–Se powders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Novikov, G. F., E-mail: ngf@icp.ac.ru; Gapanovich, M. V.; Gremenok, V. F.

2017-01-15

The method of time-resolved microwave photoconductivity at a frequency of 36 GHz in the range of temperatures of 200–300 K is used to study the kinetics of the annihilation of charge carriers in Cu–Zn–Sn–Se powders obtained by the solid-phase method of synthesis in cells. The lifetime of excess electrons at room temperature is found to be shorter than 5 ns. The activation energy for the process of recombination amounted to E{sub a} ~ 0.054 eV.

Instantaneous charge state of uranium projectiles in fully ionized plasmas from energy loss experiments

NASA Astrophysics Data System (ADS)

Morales, Roberto; Barriga-Carrasco, Manuel D.; Casas, David

2017-04-01

The instantaneous charge state of uranium ions traveling through a fully ionized hydrogen plasma has been theoretically studied and compared with one of the first energy loss experiments in plasmas, carried out at GSI-Darmstadt by Hoffmann et al. in the 1990s. For this purpose, two different methods to estimate the instantaneous charge state of the projectile have been employed: (1) rate equations using ionization and recombination cross sections and (2) equilibrium charge state formulas for plasmas. Also, the equilibrium charge state has been obtained using these ionization and recombination cross sections and compared with the former equilibrium formulas. The equilibrium charge state of projectiles in plasmas is not always reached, and it depends mainly on the projectile velocity and the plasma density. Therefore, a non-equilibrium or an instantaneous description of the projectile charge is necessary. The charge state of projectile ions cannot be measured, except after exiting the target, and experimental data remain very scarce. Thus, the validity of our charge state model is checked by comparing the theoretical predictions with an energy loss experiment, as the energy loss has a generally quadratic dependence on the projectile charge state. The dielectric formalism has been used to calculate the plasma stopping power including the Brandt-Kitagawa (BK) model to describe the charge distribution of the projectile. In this charge distribution, the instantaneous number of bound electrons instead of the equilibrium number has been taken into account. Comparing our theoretical predictions with experiments, it is shown the necessity of including the instantaneous charge state and the BK charge distribution for a correct energy loss estimation. The results also show that the initial charge state has a strong influence in order to estimate the energy loss of the uranium ions.

Bimolecular recombination quenching in Langmuir Blodgett multilayers

NASA Astrophysics Data System (ADS)

Elliott, J. E.; Jeong, I. S.; Scott, K.; Donovan, K. J.; Wilson, E. G.

2000-11-01

A model is developed that describes bimolecular recombination of photogenerated carriers in two dimensional systems. Carriers are free to diffuse in two dimensions and undergo bimolecular recombination, while drifting under the influence of an electric field in the third dimension. The model describes a competition between carrier loss due to transiting and loss due to bimolecular recombination. This model of recombination quenching is then used to obtain information on microscopic parameters associated with photogeneration efficiency and charge transport in organic quantum wells formed from Langmuir Blodgett films of conjugated molecules. The ratio of the intralayer to interlayer tunneling rates is found along with the quantum efficiency for photocarrier generation for two bis-phthalocyanine amphiphilic molecules.

Energy gap law of electron transfer in nonpolar solvents.

PubMed

Tachiya, M; Seki, Kazuhiko

2007-09-27

We investigate the energy gap law of electron transfer in nonpolar solvents for charge separation and charge recombination reactions. In polar solvents, the reaction coordinate is given in terms of the electrostatic potentials from solvent permanent dipoles at solutes. In nonpolar solvents, the energy fluctuation due to solvent polarization is absent, but the energy of the ion pair state changes significantly with the distance between the ions as a result of the unscreened strong Coulomb potential. The electron transfer occurs when the final state energy coincides with the initial state energy. For charge separation reactions, the initial state is a neutral pair state, and its energy changes little with the distance between the reactants, whereas the final state is an ion pair state and its energy changes significantly with the mutual distance; for charge recombination reactions, vice versa. We show that the energy gap law of electron-transfer rates in nonpolar solvents significantly depends on the type of electron transfer.

Evidence for ion migration in hybrid perovskite solar cells with minimal hysteresis

PubMed Central

Calado, Philip; Telford, Andrew M.; Bryant, Daniel; Li, Xiaoe; Nelson, Jenny; O'Regan, Brian C.; Barnes, Piers R.F.

2016-01-01

Ion migration has been proposed as a possible cause of photovoltaic current–voltage hysteresis in hybrid perovskite solar cells. A major objection to this hypothesis is that hysteresis can be reduced by changing the interfacial contact materials; however, this is unlikely to significantly influence the behaviour of mobile ionic charge within the perovskite phase. Here, we show that the primary effects of ion migration can be observed regardless of whether the contacts were changed to give devices with or without significant hysteresis. Transient optoelectronic measurements combined with device simulations indicate that electric-field screening, consistent with ion migration, is similar in both high and low hysteresis CH3NH3PbI3 cells. Simulation of the photovoltage and photocurrent transients shows that hysteresis requires the combination of both mobile ionic charge and recombination near the perovskite-contact interfaces. Passivating contact recombination results in higher photogenerated charge concentrations at forward bias which screen the ionic charge, reducing hysteresis. PMID:28004653

Can ferroelectric polarization explain the high performance of hybrid halide perovskite solar cells?

PubMed

Sherkar, Tejas S; Koster, L Jan Anton

2016-01-07

The power conversion efficiency of photovoltaic cells based on the use of hybrid halide perovskites, CH3NH3PbX3 (X = Cl, Br, I), now exceeds 20%. Recently, it was suggested that this high performance originates from the presence of ferroelectricity in the perovskite, which is hypothesized to lower charge recombination in the device. Here, we investigate and quantify the influence of mesoscale ferroelectric polarization on the device performance of perovskite solar cells. We implement a 3D drift diffusion model to describe the solar cell operation. To account for the mesoscale ferroelectricity, we incorporate domains defined by polarization strength, P, in 3D space, forming different polarization landscapes or microstructures. Study of microstructures with highly-ordered polarized domains shows that charge transport and recombination in the solar cell depends significantly on the polarization landscape viz. the orientation of domain boundaries and the size of domains. In the case of the microstructure with random correlated polarization, a realistic scenario, we find indication of the existence of channels for efficient charge transport in the device which leads to lowering of charge recombination, as evidenced by the high fill factor (FF). However, the high open-circuit voltage (VOC), which is typical of high performance perovskite solar cells, is unlikely to be explained by the presence of ferroelectric polarization in the perovskite.

Effect of carbon nano tube working electrode thickness on charge transport kinetics and photo-electrochemical characteristics of dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Gacemi, Yahia; Cheknane, Ali; Hilal, Hikmat S.

2018-02-01

Physiochemical processes at the photo-electrode and the counter electrode of dye sensitized solar cells (DSSCs) involving having carbon nanotubes (CNTs) instead of the TiO2 layer, within the working electrode, are simulated in this work. Attention is paid to find the effect of CNT layer thickness on photo-electrochemical (PEC) characteristics of the CNT-DSSCs. Comparison with other conventional TiO2-DSSC systems, taking into account the working electrode film thickness, is also described here. To achieve these goals, a model is presented to explain charge transport and electron recombination which involve electron photo-excitation in dye molecules, injection of electrons from the excited dye to CNT working electrode conduction band, diffusion of electrons inside the CNT electrode, charge transfer between oxidized dye and (I-) and recombination of electrons. The simulation is based on solving non-linear equations using the Newton-Raphson numerical method. This concept is proposed for modelling numerical Faradaic impedance at the photo-electrode and the platinum counter electrode. It then simulates the cell impedance spectrum describing the locus of the three semicircles in the Nyquist diagram. The transient equivalent circuit model is also presented based on optimizing current-voltage curves of CNT-DSSCs so as to optimize the fill factor (FF) and conversion efficiency (η). The results show that the simulated characteristics of CNT-DSSCs, with different active CNT layer thicknesses, are superior to conventional TiO2-DSSCs.

Passivation of phosphorus diffused silicon surfaces with Al{sub 2}O{sub 3}: Influence of surface doping concentration and thermal activation treatments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richter, Armin, E-mail: armin.richter@ise.fraunhofer.de; Benick, Jan; Kimmerle, Achim

2014-12-28

Thin layers of Al{sub 2}O{sub 3} are well known for the excellent passivation of p-type c-Si surfaces including highly doped p{sup +} emitters, due to a high density of fixed negative charges. Recent results indicate that Al{sub 2}O{sub 3} can also provide a good passivation of certain phosphorus-diffused n{sup +} c-Si surfaces. In this work, we studied the recombination at Al{sub 2}O{sub 3} passivated n{sup +} surfaces theoretically with device simulations and experimentally for Al{sub 2}O{sub 3} deposited with atomic layer deposition. The simulation results indicate that there is a certain surface doping concentration, where the recombination is maximal duemore » to depletion or weak inversion of the charge carriers at the c-Si/Al{sub 2}O{sub 3} interface. This pronounced maximum was also observed experimentally for n{sup +} surfaces passivated either with Al{sub 2}O{sub 3} single layers or stacks of Al{sub 2}O{sub 3} capped by SiN{sub x}, when activated with a low temperature anneal (425 °C). In contrast, for Al{sub 2}O{sub 3}/SiN{sub x} stacks activated with a short high-temperature firing process (800 °C) a significant lower surface recombination was observed for most n{sup +} diffusion profiles without such a pronounced maximum. Based on experimentally determined interface properties and simulation results, we attribute this superior passivation quality after firing to a better chemical surface passivation, quantified by a lower interface defect density, in combination with a lower density of negative fixed charges. These experimental results reveal that Al{sub 2}O{sub 3}/SiN{sub x} stacks can provide not only excellent passivation on p{sup +} surfaces but also on n{sup +} surfaces for a wide range of surface doping concentrations when activated with short high-temperature treatments.« less

Tunneling modulation of a quantum-well transistor laser

NASA Astrophysics Data System (ADS)

Feng, M.; Qiu, J.; Wang, C. Y.; Holonyak, N.

2016-11-01

Different than the Bardeen and Brattain transistor (1947) with the current gain depending on the ratio of the base carrier spontaneous recombination lifetime to the emitter-collector transit time, the Feng and Holonyak transistor laser current gain depends upon the base electron-hole (e-h) stimulated recombination, the base dielectric relaxation transport, and the collector stimulated tunneling. For the n-p-n transistor laser tunneling operation, the electron-hole pairs are generated at the collector junction under the influence of intra-cavity photon-assisted tunneling, with electrons drifting to the collector and holes drifting to the base. The excess charge in the base lowers the emitter junction energy barrier, allowing emitter electron injection into the base and satisfying charge neutrality via base dielectric relaxation transport (˜femtoseconds). The excess electrons near the collector junction undergo stimulated recombination at the base quantum-well or transport to the collector, thus supporting tunneling current amplification and optical modulation of the transistor laser.

Diffusion length measurements in bulk and epitaxially grown 3-5 semiconductors using charge collection microscopy

NASA Technical Reports Server (NTRS)

Leon, R. P.

1987-01-01

Diffusion lengths and surface recombination velocities were measured in GaAs diodes and InP finished solar cells. The basic techniques used was charge collection microscopy also known as electron beam induced current (EBIC). The normalized currents and distances from the pn junction were read directly from the calibrated curves obtained while using the line scan mode in an SEM. These values were then equated to integral and infinite series expressions resulting from the solution of the diffusion equation with both extended generation and point generation functions. This expands previous work by examining both thin and thick samples. The surface recombination velocity was either treated as an unknown in a system of two equations, or measured directly using low e(-) beam accelerating voltages. These techniques give accurate results by accounting for the effects of surface recombination and the finite size of the generation volume.

Peripheral Hole Acceptor Moieties on an Organic Dye Improve Dye‐Sensitized Solar Cell Performance

PubMed Central

Hao, Yan; Gabrielsson, Erik; Lohse, Peter William; Yang, Wenxing; Johansson, Erik M. J.; Hagfeldt, Anders

2015-01-01

Investigation of charge transfer dynamics in dye‐sensitized solar cells is of fundamental interest and the control of these dynamics is a key factor for developing more efficient solar cell devices. One possibility for attenuating losses through recombination between injected electrons and oxidized dye molecules is to move the positive charge further away from the metal oxide surface. For this purpose, a metal‐free dye named E6 is developed, in which the chromophore core is tethered to two external triphenylamine (TPA) units. After photoinduced electron injection into TiO2, the remaining hole is rapidly transferred to a peripheral TPA unit. Electron–hole recombination is slowed down by 30% compared to a reference dye without peripheral TPA units. Furthermore, it is found that the added TPA moieties improve the electron blocking effect of the dye, retarding recombination of electrons from TiO2 to the cobalt‐based electrolyte. PMID:27722076

Direct evidence of void passivation in Cu(InGa)(SSe){sub 2} absorber layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Dongho; Kim, Young-Su; Mo, Chan B.

We have investigated the charge collection condition around voids in copper indium gallium sulfur selenide (CIGSSe) solar cells fabricated by sputter and a sequential process of selenization/sulfurization. In this study, we found direct evidence of void passivation by using the junction electron beam induced current method, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The high sulfur concentration at the void surface plays an important role in the performance enhancement of the device. The recombination around voids is effectively suppressed by field-assisted void passivation. Hence, the generated carriers are easily collected by the electrodes. Therefore, when the S/(S + Se)more » ratio at the void surface is over 8% at room temperature, the device performance degradation caused by the recombination at the voids is negligible at the CIGSSe layer.« less

Simulation of bipolar charge transport in nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Lean, Meng H.; Chu, Wei-Ping L.

2015-03-01

This paper describes 3D particle-in-cell simulation of bipolar charge injection and transport through nanocomposite film comprised of ferroelectric ceramic nanofillers in an amorphous polymer matrix. The classical electrical double layer (EDL) model for a monopolar core is extended (eEDL) to represent the nanofiller by replacing it with a dipolar core. Charge injection at the electrodes assumes metal-polymer Schottky emission at low to moderate fields and Fowler-Nordheim tunneling at high fields. Injected particles migrate via field-dependent Poole-Frenkel mobility and recombine with Monte Carlo selection. The simulation algorithm uses a boundary integral equation method for solution of the Poisson equation coupled with a second-order predictor-corrector scheme for robust time integration of the equations of motion. The stability criterion of the explicit algorithm conforms to the Courant-Friedrichs-Levy limit assuring robust and rapid convergence. The model is capable of simulating a wide dynamic range spanning leakage current to pre-breakdown. Simulation results for BaTiO3 nanofiller in amorphous polymer matrix indicate that charge transport behavior depend on nanoparticle polarization with anti-parallel orientation showing the highest leakage conduction and therefore lowest level of charge trapping in the interaction zone. Charge recombination is also highest, at the cost of reduced leakage conduction charge. The eEDL model predicts the meandering pathways of charge particle trajectories.

A new model for volume recombination in plane-parallel chambers in pulsed fields of high dose-per-pulse

NASA Astrophysics Data System (ADS)

Gotz, M.; Karsch, L.; Pawelke, J.

2017-11-01

In order to describe the volume recombination in a pulsed radiation field of high dose-per-pulse this study presents a numerical solution of a 1D transport model of the liberated charges in a plane-parallel ionization chamber. In addition, measurements were performed on an Advanced Markus ionization chamber in a pulsed electron beam to obtain suitable data to test the calculation. The experiment used radiation pulses of 4 μs duration and variable dose-per-pulse values up to about 1 Gy, as well as pulses of variable duration up to 308 μs at constant dose-per-pulse values between 85 mGy and 400 mGy. Those experimental data were compared to the developed numerical model and existing descriptions of volume recombination. At low collection voltages the observed dose-per-pulse dependence of volume recombination can be approximated by the existing theory using effective parameters. However, at high collection voltages large discrepancies are observed. The developed numerical model shows much better agreement with the observations and is able to replicate the observed behavior over the entire range of dose-per-pulse values and collection voltages. Using the developed numerical model, the differences between observation and existing theory are shown to be the result of a large fraction of the charge being collected as free electrons and the resultant distortion of the electric field inside the chamber. Furthermore, the numerical solution is able to calculate recombination losses for arbitrary pulse durations in good agreement with the experimental data, an aspect not covered by current theory. Overall, the presented numerical solution of the charge transport model should provide a more flexible tool to describe volume recombination for high dose-per-pulse values as well as for arbitrary pulse durations and repetition rates.

Ultrafast and slow charge recombination dynamics of diketopyrrolopyrrole-NiO dye sensitized solar cells.

PubMed

Zhang, Lei; Favereau, Ludovic; Farré, Yoann; Mijangos, Edgar; Pellegrin, Yann; Blart, Errol; Odobel, Fabrice; Hammarström, Leif

2016-07-21

In a photophysical study, two diketopyrrolopyrrole (DPP)-based sensitizers functionalized with 4-thiophenecarboxylic acid as an anchoring group and a bromo (DPPBr) or dicyanovinyl (DPPCN2) group, and a dyad consisting of a DPP unit linked to a naphthalenediimide group (DPP-NDI), were investigated both in solution and grafted on mesoporous NiO films. Femtosecond transient absorption measurements indicate that ultrafast hole injection occurred predominantly on a timescale of ∼200 fs, whereas the subsequent charge recombination occurred on a surprisingly wide range of timescales, from tens of ps to tens of μs; this kinetic heterogeneity is much greater than is typically observed for dye-sensitized TiO2 or ZnO. Also, in contrast to what is typically observed for dye-sensitized TiO2, there was no significant dependence on the excitation power of the recombination kinetics, which can be explained by the hole density being comparatively higher near the valence band of NiO before excitation. The additional acceptor group in DPP-NDI provided a rapid electron shift and stabilized charge separation up to the μs timescale. This enabled efficient (∼95%) regeneration of NDI by a Co(III)(dtb)3 electrolyte (dtb = 4,4'-di-tert-butyl-2,2'-bipyridine), according to transient absorption measurements. The regeneration of DPPBr and DPPCN2 by Co(III)(dtb)3 was instead inefficient, as most recombination for these dyes occurred on the sub-ns timescale. The transient spectroscopy data thus corroborated the trend of the published photovoltaic properties of dye-sensitized solar cells (DSSCs) based on these dyes on mesoporous NiO, and show the potential of a design strategy with a secondary acceptor bound to the dye. The study identifies rapid initial recombination between the dye and NiO as the main obstacle to obtaining high efficiencies in NiO-based DSSCs; these recombination components may be overlooked when studies are conducted using only methods with ns resolution or slower.

A new model for volume recombination in plane-parallel chambers in pulsed fields of high dose-per-pulse.

PubMed

Gotz, M; Karsch, L; Pawelke, J

2017-11-01

In order to describe the volume recombination in a pulsed radiation field of high dose-per-pulse this study presents a numerical solution of a 1D transport model of the liberated charges in a plane-parallel ionization chamber. In addition, measurements were performed on an Advanced Markus ionization chamber in a pulsed electron beam to obtain suitable data to test the calculation. The experiment used radiation pulses of 4 μs duration and variable dose-per-pulse values up to about 1 Gy, as well as pulses of variable duration up to 308 [Formula: see text] at constant dose-per-pulse values between 85 mGy and 400 mGy. Those experimental data were compared to the developed numerical model and existing descriptions of volume recombination. At low collection voltages the observed dose-per-pulse dependence of volume recombination can be approximated by the existing theory using effective parameters. However, at high collection voltages large discrepancies are observed. The developed numerical model shows much better agreement with the observations and is able to replicate the observed behavior over the entire range of dose-per-pulse values and collection voltages. Using the developed numerical model, the differences between observation and existing theory are shown to be the result of a large fraction of the charge being collected as free electrons and the resultant distortion of the electric field inside the chamber. Furthermore, the numerical solution is able to calculate recombination losses for arbitrary pulse durations in good agreement with the experimental data, an aspect not covered by current theory. Overall, the presented numerical solution of the charge transport model should provide a more flexible tool to describe volume recombination for high dose-per-pulse values as well as for arbitrary pulse durations and repetition rates.

Quantum dot sensitized solar cells: Light harvesting versus charge recombination, a film thickness consideration

NASA Astrophysics Data System (ADS)

Wang, Xiu Wei; Wang, Ye Feng; Zeng, Jing Hui; Shi, Feng; Chen, Yu; Jiang, Jiaxing

2017-08-01

Sensitizer loading level is one of the key factors determined the performance of sensitized solar cells. In this work, we systemically studied the influence of photo-anode thicknesses on the performance of the quantum-dot sensitized solar cells. It is found that the photo-to-current conversion efficiency enhances with increased film thickness and peaks at around 20 μm. The optimal value is about twice as large as the dye counterparts. Here, we also uncover the underlying mechanism about the influence of film thickness over the photovoltaic performance of QDSSCs from the light harvesting and charge recombination viewpoint.

An integrated charge exchange recombination spectroscopy/beam emission spectroscopy diagnostic for Alcator C-Mod tokamak.

PubMed

Bespamyatnov, I O; Rowan, W L; Liao, K T; Granetz, R S

2010-10-01

A novel integrated charge exchange recombination spectroscopy (CXRS)/beam emission spectroscopy (BES) system is proposed for C-Mod, in which both measurements are taken from a shared viewing geometry. The supplementary BES system serves to quantify local beam densities and supplants the common calculation of beam attenuation. The new system employs two optical viewing arrays, 20 poloidal and 22 toroidal channels. A dichroic filter splits the light between two spectrometers operating at different wavelengths for impurity ion and beam neutrals emission. In this arrangement, the impurity density is inferred from the electron density, measured BES and CXRS spectral radiances, and atomic emission rates.

Generation Dependent Ultrafast Charge Separation and Recombination in a Pyrene-Viologen Family of Dendrons.

PubMed

Gong, Zheng; Bao, Jianhua; Nagai, Keiji; Iyoda, Tomokazu; Kawauchi, Takehiro; Piotrowiak, Piotr

2016-05-12

The ability of a dendritic network to intercept electrons and extend the lifetime of a short-lived photoinduced charge separated (CS) state was investigated in a homologous family of methyl viologen (MV(2+)) dendrons spanning four generations, G0 through G3. The CS state in the parent pyrene-methylene-viologen G0 system with a single acceptor exhibits an extremely short lifetime of τ = 0.72 ps. The expansion of the viologen network introduces slower components to the recombination kinetics by allowing the injected electron to migrate further away from the donor. The long-lived fraction of the population increases monotonically in the order G3 > G2 > G1 > G0, while the respective recombination rates decrease. In the highest generation of the dendron ∼14% of the CS state population experiences a 10-fold or greater lifetime extension. Long range tunneling across multiple viologen units and sequential site-to-site hopping both contribute to the overall effect. The large excess energy deposited in the apical viologen upon charge separation and the presence of an extended network of low lying π-orbitals likely facilitate shuttling the electron further down the dendron.

The binding of quinone to the photosynthetic reaction centers: kinetics and thermodynamics of reactions occurring at the QB-site in zwitterionic and anionic liposomes.

PubMed

Mavelli, Fabio; Trotta, Massimo; Ciriaco, Fulvio; Agostiano, Angela; Giotta, Livia; Italiano, Francesca; Milano, Francesco

2014-07-01

Liposomes represent a versatile biomimetic environment for studying the interaction between integral membrane proteins and hydrophobic ligands. In this paper, the quinone binding to the QB-site of the photosynthetic reaction centers (RC) from Rhodobacter sphaeroides has been investigated in liposomes prepared with either the zwitterionic phosphatidylcholine (PC) or the negatively charged phosphatidylglycerol (PG) to highlight the role of the different phospholipid polar heads. Quinone binding (K Q) and interquinone electron transfer (L AB) equilibrium constants in the two type of liposomes were obtained by charge recombination reaction of QB-depleted RC in the presence of increasing amounts of ubiquinone-10 over the temperature interval 6-35 °C. The kinetic of the charge recombination reactions has been fitted by numerically solving the ordinary differential equations set associated with a detailed kinetic scheme involving electron transfer reactions coupled with quinone release and uptake. The entire set of traces at each temperature was accurately fitted using the sole quinone release constants (both in a neutral and a charge separated state) as adjustable parameters. The temperature dependence of the quinone exchange rate at the QB-site was, hence, obtained. It was found that the quinone exchange regime was always fast for PC while it switched from slow to fast in PG as the temperature rose above 20 °C. A new method was introduced in this paper for the evaluation of constant K Q using the area underneath the charge recombination traces as the indicator of the amount of quinone bound to the QB-site.

Effect of the energy of bombarding electrons on the conductivity of n-4H-SiC (CVD) epitaxial layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kozlovski, V. V., E-mail: kozlovski@physics.spbstu.ru; Lebedev, A. A.; Strel’chuk, A. M.

The electrical characteristics of epitaxial layers of n-4H-SiC (CVD) irradiated with 0.9 and 3.5MeV electrons are studied. It is shown that the donor removal rate becomes nearly four times higher as the energy of impinging electrons increases by a factor of 4, although the formation cross section of primary radiation defects (Frenkel pairs in the carbon sublattice) responsible for conductivity compensation of the material is almost energy independent in this range. It is assumed that the reason for the observed differences is the influence exerted by primary knocked-out atoms. First, cascade processes start to manifest themselves with increasing energy ofmore » primary knocked-out atoms. Second, the average distance between genetically related Frenkel pairs grows, and, as a consequence, the fraction of defects that do not recombine under irradiation becomes larger. The recombination radius of Frenkel pairs in the carbon sublattice is estimated and the possible charge state of the recombining components is assessed.« less

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex.

PubMed

Aly, Shawkat M; Goswami, Subhadip; Alsulami, Qana A; Schanze, Kirk S; Mohammed, Omar F

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Probing interfacial energetics and charge transfer kinetics in semiconductor nanocomposites: New insights into heterostructured TiO 2/BiVO 4 photoanodes

DOE PAGES

Hess, Lucas H.; Cooper, Jason K.; Loiudice, Anna; ...

2017-02-28

Heterostructured nanocomposites offer promise for creating systems exhibiting functional properties that exceed those of the isolated components. For solar energy conversion, such combinations of semiconducting nanomaterials can be used to direct charge transfer along pathways that reduce recombination and promote efficient charge extraction. However, interfacial energetics and associated kinetic pathways often differ significantly from predictions derived from the characteristics of pure component materials, particularly at the nanoscale. Here, the emergent properties of TiO 2/BiVO 4 nanocomposite photoanodes are explored using a combination of X-ray and optical spectroscopies, together with photoelectrochemical (PEC) characterization. Application of these methods to both the puremore » components and the fully assembled nanocomposites reveals unpredicted interfacial energetic alignment, which promotes ultrafast injection of electrons from BiVO 4 into TiO 2. Physical charge separation yields extremely long-lived photoexcited states and correspondingly enhanced photoelectrochemical functionality. This work highlights the importance of probing emergent interfacial energetic alignment and kinetic processes for understanding mechanisms of solar energy conversion in complex nanocomposites.« less

Exciton shelves for charge and energy transport in third-generation quantum-dot devices

NASA Astrophysics Data System (ADS)

Goodman, Samuel; Singh, Vivek; Noh, Hyunwoo; Casamada, Josep; Chatterjee, Anushree; Cha, Jennifer; Nagpal, Prashant

2014-03-01

Quantum dots are semiconductor nanocrystallites with size-dependent quantum-confined energy levels. While they have been intensively investigated to utilize hot-carriers for photovoltaic applications, to bridge the mismatch between incident solar photons and finite bandgap of semiconductor photocells, efficient charge or exciton transport in quantum-dot films has proven challenging. Here we show development of new coupled conjugated molecular wires with ``exciton shelves'', or different energy levels, matched with the multiple energy levels of quantum dots. Using single nanoparticle and ensemble device measurements we show successful extraction and transport of both bandedge and high-energy charge carriers, and energy transport of excitons. We demonstrate using measurements of electronic density of states, that careful matching of energy states of quantum-dot with molecular wires is important, and any mismatch can generate midgap states leading to charge recombination and reduced efficiency. Therefore, these exciton-shelves and quantum dots can lead to development of next-generation photovoltaic and photodetection devices using simultaneous transport of bandedge and hot-carriers or energy transport of excitons in these nanostructured solution-processed films.

Luminescence in Conjugated Molecular Materials under Sub-bandgap Excitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

So, Franky

2014-05-08

Light emission in semiconductors occurs when they are under optical and electrical excitation with energy larger than the bandgap energy. In some low-dimensional semiconductor heterostructure systems, this thermodynamic limit can be violated due to radiative Auger recombination (AR), a process in which the sub-bandgap energy released from a recombined electron-hole pair is transferred to a third particle leading to radiative band-to-band recombination.1 Thus far, photoluminescence up-conversion phenomenon has been observed in some low dimensional semiconductor systems, and the effect is very weak and it can only be observed at low temperatures. Recently, we discovered that efficient electroluminescence in poly[2-methoxy-5-(2’-ethylhexyloxy)-1, phenylenevinylene]more » (MEH-PPV) polymer light-emitting devices (PLEDs) at drive voltages below its bandgap voltage could be observed when a ZnO nanoparticles (NPs) electron injection layer was inserted between the polymer and the aluminum electrode. Specifically, emitted photons with energy of 2.13 eV can be detected at operating voltages as low as 1.2 V at room temperature. Based on these data, we propose that the sub-bandgap turn-on in the MEH-PPV device is due to an Auger-assisted energy up-conversion process. The significance of this discovery is three-fold. First, radiative recombination occurs at operating voltages below the thermodynamic bandgap voltage. This process can significantly reduce the device operating voltage. For example, the current density of the device with the ZnO NC layer is almost two orders of magnitude higher than that of the device without the NC layer. Second, a reactive metal is no longer needed for the cathode. Third, this electroluminescence up-conversion process can be applied to inorganic semiconductors systems as well and their operation voltages of inorganic LEDs can be reduced to about half of the bandgap energy. Based on our initial data, we propose that the sub-bandgap turn-on in MEH-PPV devices is due to Auger-assisted energy up-conversion process. Specifically, we propose that the up-conversion process is due to charge accumulation at the polymer/NPs interface. This model requires that holes should be the dominant carriers in the polymer and the polymer/ZnO NCs heterojunction should be a type II alignment. In order to determine the mechanism of the up-conversion process, we will characterize devices fabricated using polymers with different carrier transporting properties to determine whether hole accumulation at the polymer/nanocrystals is required. Likewise, we will also use NPs with different electronic structures to fabricate devices to determine how electron accumulation affects the up-conversion process. Finally, we will measure quantitatively the interface charge accumulation by electroabsorption and correlate the results with the up-conversion photoluminescence efficiency measurements under an applied electric field.« less

Spatiotemporal Monte Carlo transport methods in x-ray semiconductor detectors: application to pulse-height spectroscopy in a-Se.

PubMed

Fang, Yuan; Badal, Andreu; Allec, Nicholas; Karim, Karim S; Badano, Aldo

2012-01-01

The authors describe a detailed Monte Carlo (MC) method for the coupled transport of ionizing particles and charge carriers in amorphous selenium (a-Se) semiconductor x-ray detectors, and model the effect of statistical variations on the detected signal. A detailed transport code was developed for modeling the signal formation process in semiconductor x-ray detectors. The charge transport routines include three-dimensional spatial and temporal models of electron-hole pair transport taking into account recombination and trapping. Many electron-hole pairs are created simultaneously in bursts from energy deposition events. Carrier transport processes include drift due to external field and Coulombic interactions, and diffusion due to Brownian motion. Pulse-height spectra (PHS) have been simulated with different transport conditions for a range of monoenergetic incident x-ray energies and mammography radiation beam qualities. Two methods for calculating Swank factors from simulated PHS are shown, one using the entire PHS distribution, and the other using the photopeak. The latter ignores contributions from Compton scattering and K-fluorescence. Comparisons differ by approximately 2% between experimental measurements and simulations. The a-Se x-ray detector PHS responses simulated in this work include three-dimensional spatial and temporal transport of electron-hole pairs. These PHS were used to calculate the Swank factor and compare it with experimental measurements. The Swank factor was shown to be a function of x-ray energy and applied electric field. Trapping and recombination models are all shown to affect the Swank factor.

Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons.

PubMed

Rivas, N; Moriena, G; Domenianni, L; Hodak, J H; Marceca, E

2017-12-06

We performed femtosecond transient absorption (TA) experiments to monitor the solvation dynamics of charge-transfer-to-solvent (CTTS) electrons originating from UV photoexcitation of ammoniated iodide in close proximity to the counterions. Solutions of KI were prepared in liquid ammonia and TA experiments were carried out at different temperatures and densities, along the liquid-gas coexistence curve of the fluid. The results complement previous femtosecond TA work by P. Vöhringer's group in neat ammonia via multiphoton ionization. The dynamics of CTTS-detached electrons in ammonia was found to be strongly affected by ion pairing. Geminate recombination time constants as well as escape probabilities were determined from the measured temporal profiles and analysed as a function of the medium density. A fast unresolved (τ < 250 fs) increase of absorption related to the creation/thermalization of solvated electron species was followed by two decay components: one with a characteristic time around 10 ps, and a slower one that remains active for hundreds of picoseconds. While the first process is attributed to an early recombination of (I, e - ) pairs, the second decay and its asymptote reflects the effect of the K + counterion on the geminate recombination dynamics, rate and yield. The cation basically acts as an electron anchor that restricts the ejection distance, leading to solvent-separated counterion-electron species. The formation of (K + , NH 3 , e - ) pairs close to the parent iodine atom brings the electron escape probability to very low values. Transient spectra of the electron species have also been estimated as a function of time by probing the temporal profiles at different wavelengths.

Upgrading a high-throughput spectrometer for high-frequency (<400 kHz) measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishizawa, T., E-mail: nishizawa@wisc.edu; Nornberg, M. D.; Den Hartog, D. J.

2016-11-15

The upgraded spectrometer used for charge exchange recombination spectroscopy on the Madison Symmetric Torus resolves emission fluctuations up to 400 kHz. The transimpedance amplifier’s cutoff frequency was increased based upon simulations comparing the change in the measured photon counts for time-dynamic signals. We modeled each signal-processing stage of the diagnostic and scanned the filtering frequency to quantify the uncertainty in the photon counting rate. This modeling showed that uncertainties can be calculated based on assuming each amplification stage is a Poisson process and by calibrating the photon counting rate with a DC light source to address additional variation.

Upgrading a high-throughput spectrometer for high-frequency (<400 kHz) measurements

NASA Astrophysics Data System (ADS)

Nishizawa, T.; Nornberg, M. D.; Den Hartog, D. J.; Craig, D.

2016-11-01

The upgraded spectrometer used for charge exchange recombination spectroscopy on the Madison Symmetric Torus resolves emission fluctuations up to 400 kHz. The transimpedance amplifier's cutoff frequency was increased based upon simulations comparing the change in the measured photon counts for time-dynamic signals. We modeled each signal-processing stage of the diagnostic and scanned the filtering frequency to quantify the uncertainty in the photon counting rate. This modeling showed that uncertainties can be calculated based on assuming each amplification stage is a Poisson process and by calibrating the photon counting rate with a DC light source to address additional variation.

Stimulated electronic transition concept for an erasable optical memory

NASA Technical Reports Server (NTRS)

Albin, Sacharia; Satira, James D.; Livingston, David L.; Shull, Thomas A.

1992-01-01

A new concept for an erasable optical memory is demonstrated using stimulated electronic transition (SET). Large bandgap semiconductors are suitable materials for the SET medium. The properties of MgS:Eu,Sm and SrS:Eu,Sm as possible media for the SET process are investigated. Quantum storage is achieved in the form of charges in deep levels in the medium and stimulated radiative recombination is used as the reading process. Unlike magneto-optic (M-O) and phase change (PC) processes, optical writing, reading and erasing are achieved without localized heating. The SET process will have an inherently faster data transfer rate and a higher storage density, and the medium will be more durable than the M-O and PC media. A possible application of the SET process in neural networks is also discussed.

Band structure engineering of TiO2 nanowires by n-p codoping for enhanced visible-light photoelectrochemical water-splitting.

PubMed

Zhang, Daoyu; Yang, Minnan

2013-11-14

The advantages of one-dimensional nanostructures, such as excellent charge separation and charge transport, low charge carrier recombination losses and so on, render them the photocatalysts of choice for many applications that exploit solar energy. In this work, based on very recently synthesized ultrathin anatase TiO2 nanowires, we explore the possibility of these wires as photocatalysts for photoelectrochemical water-splitting via the mono-doping (C, N, V, and Cr) and n-p codoping (C&V, C&Cr, N&V, and N&Cr) schemes. Our first-principles calculations predict that the C&Cr and C&V codoped ANWs may be strong candidates for photoelectrochemical water-splitting, because they have a substantially reduced band gap of 2.49 eV, appropriate band edge positions, no carrier recombination centers, and enhanced optical absorption in the visible light region.

High Mobility Conjugated Polymers

DTIC Science & Technology

2007-10-20

will act as a trap for opposite charge carriers; the electron affinities were 4.0 eV (BBL) and 2.7 eV (PTHQx) and ionization potentials were 6.0 eV...transistors (OFETs), photovoltaic cells, and photodetectors, is limited primarily by the low charge carrier mobilities of current materials. To address this...showing a maximum mobility with hexyl. Fundamental insights into the structural factors that govern high mobility charge transport and recombination in

Poly(4-Vinylpyridine)-Based Interfacial Passivation to Enhance Voltage and Moisture Stability of Lead Halide Perovskite Solar Cells.

PubMed

Chaudhary, Bhumika; Kulkarni, Ashish; Jena, Ajay Kumar; Ikegami, Masashi; Udagawa, Yosuke; Kunugita, Hideyuki; Ema, Kazuhiro; Miyasaka, Tsutomu

2017-06-09

It is well known that the surface trap states and electronic disorders in the solution-processed CH 3 NH 3 PbI 3 perovskite film affect the solar cell performance significantly and moisture sensitivity of photoactive perovskite material limits its practical applications. Herein, we show the surface modification of a perovskite film with a solution-processable hydrophobic polymer (poly(4-vinylpyridine), PVP), which passivates the undercoordinated lead (Pb) atoms (on the surface of perovskite) by its pyridine Lewis base side chains and thereby eliminates surface-trap states and non-radiative recombination. Moreover, it acts as an electron barrier between the perovskite and hole-transport layer (HTL) to reduce interfacial charge recombination, which led to improvement in open-circuit voltage (V oc ) by 120 to 160 mV whereas the standard cell fabricated in same conditions showed V oc as low as 0.9 V owing to dominating interfacial recombination processes. Consequently, the power conversion efficiency (PCE) increased by 3 to 5 % in the polymer-modified devices (PCE=15 %) with V oc more than 1.05 V and hysteresis-less J-V curves. Advantageously, hydrophobicity of the polymer chain was found to protect the perovskite surface from moisture and improved stability of the non-encapsulated cells, which retained their device performance up to 30 days of exposure to open atmosphere (50 % humidity). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mass spectrometry of acoustically levitated droplets.

PubMed

Westphall, Michael S; Jorabchi, Kaveh; Smith, Lloyd M

2008-08-01

Containerless sample handling techniques such as acoustic levitation offer potential advantages for mass spectrometry, by eliminating surfaces where undesired adsorption/desorption processes can occur. In addition, they provide a unique opportunity to study fundamental aspects of the ionization process as well as phenomena occurring at the air-droplet interface. Realizing these advantages is contingent, however, upon being able to effectively interface levitated droplets with a mass spectrometer, a challenging task that is addressed in this report. We have employed a newly developed charge and matrix-assisted laser desorption/ionization (CALDI) technique to obtain mass spectra from a 5-microL acoustically levitated droplet containing peptides and an ionic matrix. A four-ring electrostatic lens is used in conjunction with a corona needle to produce bursts of corona ions and to direct those ions toward the droplet, resulting in droplet charging. Analyte ions are produced from the droplet by a 337-nm laser pulse and detected by an atmospheric sampling mass spectrometer. The ion generation and extraction cycle is repeated at 20 Hz, the maximum operating frequency of the laser employed. It is shown in delayed ion extraction experiments that both positive and negative ions are produced, behavior similar to that observed for atmospheric pressure matrix-assisted laser absorption/ionization. No ion signal is observed in the absence of droplet charging. It is likely, although not yet proven, that the role of the droplet charging is to increase the strength of the electric field at the surface of the droplet, reducing charge recombination after ion desorption.

Photocatalytic degradation of H2S aqueous media using sulfide nanostructured solid-solution solar-energy-materials to produce hydrogen fuel.

PubMed

Lashgari, Mohsen; Ghanimati, Majid

2018-03-05

H 2 S is a corrosive, flammable and noxious gas, which can be neutralized by dissolving in alkaline media and employed as H 2 -source by utilizing inside semiconductor-assisted/photochemical reactors. Herein, through a facile hydrothermal route, a ternary nanostructured solid-solution of iron, zinc and sulfur was synthesized in the absence and presence of Ag-dopant, and applied as efficient photocatalyst of hydrogen fuel production from H 2 S media. The effect of pH on the photocatalyst performance was scrutinized and the maximum activity was attained at pH=11, where HS - concentration is high. BET, diffuse reflectance and photoluminescence studies indicated that the ternary solid-solution photocatalyst, in comparison to its solid-solvent (ZnS), has a greater surface area, stronger photon absorption and less charge recombination, which justify its superiority. Moreover, the effect of silver-dopant on the photocatalyst performance was examined. The investigations revealed that although silver could boost the absorption of photons and increase the surface area, it could not appreciably enhance the photocatalyst performance due to its weak influence on retarding the charge-recombination process. Finally, the phenomenon was discussed in detail from mechanistic viewpoint. Copyright © 2017 Elsevier B.V. All rights reserved.

Ultrafast photoinduced charge transport in Pt(II) donor-acceptor assembly bearing naphthalimide electron acceptor and phenothiazine electron donor.

PubMed

Sazanovich, Igor V; Best, Jonathan; Scattergood, Paul A; Towrie, Michael; Tikhomirov, Sergei A; Bouganov, Oleg V; Meijer, Anthony J H M; Weinstein, Julia A

2014-12-21

Visible light-induced charge transfer dynamics were investigated in a novel transition metal triad acceptor-chromophore-donor, (NDI-phen)Pt(II)(-C≡C-Ph-CH2-PTZ)2 (1), designed for photoinduced charge separation using a combination of time-resolved infrared (TRIR) and femtosecond electronic transient absorption (TA) spectroscopy. In 1, the electron acceptor is 1,4,5,8-naphthalene diimide (NDI), and the electron donor is phenothiazine (PTZ), and [(phen)Pt(-C≡C-Ph-)], where phen is 1,10-phenanthroline, represents the chromophoric core. The first excited state observed in 1 is a (3)MLCT/LL'CT, with {Pt(II)-acetylide}-to-phen character. Following that, charge transfer from the phen-anion onto the NDI subunit to form NDI(-)-phen-[Pt-(C≡C)2](+)-PTZ2 occurs with a time constant of 2.3 ps. This transition is characterised by appearance of the prominent NDI-anion features in both TRIR and TA spectra. The final step of the charge separation in 1 proceeds with a time constant of ∼15 ps during which the hole migrates from the [Pt-(C≡C)2] subunit to one of the PTZ groups. Charge recombination in 1 then occurs with two distinct time constants of 36 ns and 107 ns, corresponding to the back electron transfer to each of the two donor groups; a rather rare occurrence which manifests that the hole in the final charge-separated state is localised on one of the two donor PTZ groups. The assignment of the nature of the excited states and dynamics in 1 was assisted by TRIR investigations of the analogous previously reported ((COOEt)2bpy)Pt(C≡C-Ph-CH2-PTZ)2 (2), (J. E. McGarrah and R. Eisenberg, Inorg. Chem., 2003, 42, 4355; J. E. McGarrah, J. T. Hupp and S. N. Smirnov, J. Phys. Chem. A, 2009, 113, 6430) as well as (bpy)Pt(C≡C-Ph-C7H15)2, which represent the acceptor-free dyad, and the chromophoric core, respectively. Thus, the step-wise formation of the full charge-separated state on the picosecond time scale and charge recombination via tunnelling have been established; and the presence of two distinct charge recombination pathways has been observed.

Non-equilibrium character of resistive switching and negative differential resistance in Ga-doped Cr2O3 system

NASA Astrophysics Data System (ADS)

Bhowmik, R. N.; Siva, K. Venkata

2018-07-01

The samples of Ga-doped Cr2O3 system in rhombohedral crystal structure with space group R 3 bar C were prepared by chemical co-precipitation route and annealing at 800 °C. The current-voltage (I-V) curves exhibited many unique non-linear properties, e.g., hysteresis loop, resistive switching, and negative differential resistance (NDR). In this work, we report non-equilibrium properties of resistive switching and NDR phenomena. The non-equilibrium I-V characteristics were confirmed by repetiting measurement and time relaxation of current. The charge conduction process was understood by analysing the I-V curves using electrode-limited and bulk-limited charge conduction mechanisms, which were proposed for metal electrode/metal oxide/metal electrode structure. The I-V curves in the NDR regime and at higher bias voltage regime in our samples did not obey Fowler-Nordheim equation, which was proposed for charge tunneling mechanism in many thin film junctions. The non-equilibrium I-V phenomena were explained by considering the competitions between the injection of charge carriers from metal electrode to metal oxide, the charge flow through bulk material mediated by trapping/de-trapping and recombination of charge carriers at the defect sites of ions, the space charge effects at the junctions of electrodes and metal oxides, and finally, the out flow of electrons from metal oxide to metal electrode.

Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Bailey, S. G.; McNatt, J. S.; Chandrashekhar, M. V. S.; Harris, J. D.; Rusch, A. W.; Nogales, K. A.; Goettsche, K.V.; Hanson, W.; Amos, D.;

Novel Materials, Processing, and Device Technologies for Space Exploration with Potential Dual-Use Applications

NASA Technical Reports Server (NTRS)

Hepp, A. F.; Bailey, S. G.; McNatt, J. S.; Chandrashekhar, M. V. S.; Harris, J. D.; Rusch, A. W.; Nogales, K. A.; Goettsche, K. V.; Hanson, W.; Amos, D.;

Energy relaxation of intense laser pulse-produced plasmas

NASA Astrophysics Data System (ADS)

Shihab, M.; Abou-Koura, G. H.; El-Siragy, N. M.

2016-05-01

We describe a collisional radiative model (CRE) of homogeneously expanded nickel plasmas in vacuum. The CRE model is coupled with two separate electron and ion temperature magneto-hydrodynamic equations. On the output, the model provides the temporal variation of the electron temperature, ion temperature, and average charge state. We demonstrate the effect of three-body recombination ({∝}N_e T^{-9/2}_e) on plasma parameters, as it changes the time dependence of electron temperature from t^{-2} to t^{-1} and exhibits a pronounced effect leading to a freezing feature in the average charge state. In addition, the effect of the three-body recombination on the warm up of ions and delaying the equilibration is addressed.

Luminescence evolution from alumina ceramic surface before flashover under direct and alternating current voltage in vacuum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Guo-Qiang; Wang, Yi-Bo; Song, Bai-Peng

2016-06-15

The luminescence evolution phenomena from alumina ceramic surface in vacuum under high voltage of direct and alternating current are reported, with the voltage covering a large range from far below to close to the flashover voltage. Its time resolved and spatial distributed behaviors are examined by a photon counting system and an electron-multiplying charge-coupled device (EMCCD) together with a digital camera, respectively. The luminescence before flashover exhibits two stages as voltage increasing, i.e., under a relative low voltage (Stage A), the luminescence is ascribed to radiative recombination of hetero-charges injected into the sample surface layer by Schottky effect; under amore » higher voltage (Stage B), a stable secondary electron emission process, resulting from the Fowler-Nordheim emission at the cathode triple junction (CTJ), is responsible for the luminescence. Spectrum analysis implies that inner secondary electrons within the surface layer of alumina generated during the SSEE process also participate in the luminescence of Stage B. A comprehensive interpretation of the flashover process is formulated, which might promote a better understanding of flashover issue in vacuum.« less

Luminescence evolution from alumina ceramic surface before flashover under direct and alternating current voltage in vacuum

NASA Astrophysics Data System (ADS)

Su, Guo-Qiang; Wang, Yi-Bo; Song, Bai-Peng; Mu, Hai-Bao; Zhang, Guan-Jun; Li, Feng; Wang, Meng

2016-06-01

The luminescence evolution phenomena from alumina ceramic surface in vacuum under high voltage of direct and alternating current are reported, with the voltage covering a large range from far below to close to the flashover voltage. Its time resolved and spatial distributed behaviors are examined by a photon counting system and an electron-multiplying charge-coupled device (EMCCD) together with a digital camera, respectively. The luminescence before flashover exhibits two stages as voltage increasing, i.e., under a relative low voltage (Stage A), the luminescence is ascribed to radiative recombination of hetero-charges injected into the sample surface layer by Schottky effect; under a higher voltage (Stage B), a stable secondary electron emission process, resulting from the Fowler-Nordheim emission at the cathode triple junction (CTJ), is responsible for the luminescence. Spectrum analysis implies that inner secondary electrons within the surface layer of alumina generated during the SSEE process also participate in the luminescence of Stage B. A comprehensive interpretation of the flashover process is formulated, which might promote a better understanding of flashover issue in vacuum.

Operating Mechanisms of Mesoscopic Perovskite Solar Cells through Impedance Spectroscopy and J-V Modeling.

PubMed

Zarazúa, Isaac; Sidhik, Siraj; Lopéz-Luke, Tzarara; Esparza, Diego; De la Rosa, Elder; Reyes-Gomez, Juan; Mora-Seró, Iván; Garcia-Belmonte, Germà

2017-12-21

The performance of perovskite solar cell (PSC) is highly sensitive to deposition conditions, the substrate, humidity, and the efficiency of solvent extraction. However, the physical mechanism involved in the observed changes of efficiency with different deposition conditions has not been elucidated yet. In this work, PSCs were fabricated by the antisolvent deposition (AD) and recently proposed air-extraction antisolvent (AAD) process. Impedance analysis and J-V curve fitting were used to analyze the photogeneration, charge transportation, recombination, and leakage properties of PSCs. It can be elucidated that the improvement in morphology of perovskite film promoted by AAD method leads to increase in light absorption, reduction in recombination sites, and interstitial defects, thus enhancing the short-circuit current density, open-circuit voltage, and fill factor. This study will open up doors for further improvement of device and help in understanding its physical mechanism and its relation to the deposition methods.

Derivation of the open-circuit voltage of organic solar cells

NASA Astrophysics Data System (ADS)

Staple, Douglas B.; Oliver, Patricia A. K.; Hill, Ian G.

2014-05-01

Organic photovoltaic cells have improved in efficiency from 1% two decades ago to over 10% today. Continued improvement necessitates a theoretical understanding of the factors determining efficiency. Organic photovoltaic efficiency can be parameterized in terms of open-circuit voltage, short-circuit current, and fill factor. Here we present a theory that explains the dependencies of open-circuit voltage on semiconductor energy levels, light intensity, solar cell and light-source temperatures, charge-carrier recombination, and external fluorescence efficiency. The present theory also explains why recombination at the donor-acceptor heterointerface is a dominant process in heterojunction-based cells. Furthermore, the Carnot efficiency appears, highlighting the connection to basic thermodynamics. The theory presented here is consistent with and builds on the experimental and theoretical observations already in the literature. Crucially, the present theory can be straightforwardly derived in a line-by-line fashion using standard tools from statistical physics.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

NASA Astrophysics Data System (ADS)

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; Chalupský, J.; Chung, H.-K.; Ciricosta, O.; Dakovski, G. L.; Hájková, V.; Hollebon, P.; Juha, L.; Krzywinski, J.; Lee, R. W.; Minitti, M. P.; Preston, T. R.; de la Varga, A. G.; Vozda, V.; Zastrau, U.; Wark, J. S.; Velarde, P.; Vinko, S. M.

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1 s →2 p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We present a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.

Using resonant x-ray scattering to determine how structure controls the charge generation process in PCPDTBT:PC70BM solar cells

NASA Astrophysics Data System (ADS)

Pope, Michael; Waldrip, Matthew; Ferron, Thomas; Collins, Brian

Increased solar power conversion efficiencies to 12% in bulk heterojunction organic photovoltaics (OPVs) continue to brighten their prospects as an economically viable source of solar energy. It is known that OPV performance can be enhanced through processing additives that change the nanostructure. We track these critical structure-property relationships in the OPV system PCPDTBT:PC70BM while varying the amount of DIO additive. Resonant Soft X-ray Scattering reveals domain purity, domain size, and molecular orientation to highlight the system's complex dependence on DIO concentration. We will show the effect the resulting structure has on charge generation and recombination via in-situ transient and steady state optoelectronic measurements. By measuring structure, excited state dynamics and device performance all on the same sample enables direct relationships to be measured. We show that the appropriate balance of crystallinity, domain size and domain purity are important for optimized excited state dynamics and device performance.

Clocking Femtosecond Collisional Dynamics via Resonant X-Ray Spectroscopy

DOE PAGES

van den Berg, Q. Y.; Fernandez-Tello, E. V.; Burian, T.; ...

2018-02-01

Electron-ion collisional dynamics is of fundamental importance in determining plasma transport properties, nonequilibrium plasma evolution, and electron damage in diffraction imaging applications using bright x-ray free-electron lasers (FELs). Here in this paper, we describe the first experimental measurements of ultrafast electron impact collisional ionization dynamics using resonant core-hole spectroscopy in a solid-density magnesium plasma, created and diagnosed with the Linac Coherent Light Source x-ray FEL. By resonantly pumping the 1s → 2p transition in highly charged ions within an optically thin plasma, we have measured how off-resonance charge states are populated via collisional processes on femtosecond time scales. We presentmore » a collisional cross section model that matches our results and demonstrates how the cross sections are enhanced by dense-plasma effects including continuum lowering. Nonlocal thermodynamic equilibrium collisional radiative simulations show excellent agreement with the experimental results and provide new insight on collisional ionization and three-body-recombination processes in the dense-plasma regime.« less

Ionothermal Synthesis of Triazine-Heptazine Based Co-frameworks with Apparent Quantum Yields of 60 % at 420 nm for Solar Hydrogen Production from "Sea Water".

PubMed

Zhang, Guigang; Lin, Lihua; Li, Guosheng; Zhang, Yongfan; Savateev, Aleksandr; Wang, Xinchen; Antonietti, Markus

2018-05-31

Polymeric carbon nitride (PCN), either in triazine or heptazine forms, has been regarded as promising metal-free, environmental benign and sustainable photocatalysts for solar hydrogen production. However, PCN in most cases only exhibits moderate activities due to the inherent properties such as rapid charge carrier recombination. Here we present a triazine-heptazine copolymer synthesized from simple post-calcination of PCN in eutectic salts, i.e. NaCl/KCl, to modulate the polymerization process and optimize the structure. The construction of internal triazine-heptazine donor-acceptor (D-A) heterostructures is affirmed to significantly accelerate the charge transfer (CT) and thus corporately boost the photocatalytic activity (AQY= 60 % at 420 nm). This study highlights the construction of intermolecular D-A copolymers in NaCl/KCl molten salts with higher melting points but absence of lithium to modulate the polymerization process and chemical structure of PCN. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A series connection architecture for large-area organic photovoltaic modules with a 7.5% module efficiency

PubMed Central

Hong, Soonil; Kang, Hongkyu; Kim, Geunjin; Lee, Seongyu; Kim, Seok; Lee, Jong-Hoon; Lee, Jinho; Yi, Minjin; Kim, Junghwan; Back, Hyungcheol; Kim, Jae-Ryoung; Lee, Kwanghee

2016-01-01

The fabrication of organic photovoltaic modules via printing techniques has been the greatest challenge for their commercial manufacture. Current module architecture, which is based on a monolithic geometry consisting of serially interconnecting stripe-patterned subcells with finite widths, requires highly sophisticated patterning processes that significantly increase the complexity of printing production lines and cause serious reductions in module efficiency due to so-called aperture loss in series connection regions. Herein we demonstrate an innovative module structure that can simultaneously reduce both patterning processes and aperture loss. By using a charge recombination feature that occurs at contacts between electron- and hole-transport layers, we devise a series connection method that facilitates module fabrication without patterning the charge transport layers. With the successive deposition of component layers using slot-die and doctor-blade printing techniques, we achieve a high module efficiency reaching 7.5% with area of 4.15 cm2. PMID:26728507

Exploring what prompts ITIC to become a superior acceptor in organic solar cell by combining molecular dynamics simulation with quantum chemistry calculation.

PubMed

Pan, Qing-Qing; Li, Shuang-Bao; Duan, Ying-Chen; Wu, Yong; Zhang, Ji; Geng, Yun; Zhao, Liang; Su, Zhong-Min

2017-11-29

The interface characteristic is a crucial factor determining the power conversion efficiency of organic solar cells (OSCs). In this work, our aim is to conduct a comparative study on the interface characteristics between the very famous non-fullerene acceptor, ITIC, and a fullerene acceptor, PC71BM by combining molecular dynamics simulations with density functional theory. Based on some typical interface models of the acceptor ITIC or PC71BM and the donor PBDB-T selected from MD simulation, besides the evaluation of charge separation/recombination rates, the relative positions of Frenkel exciton (FE) states and the charge transfer states along with their oscillator strengths are also employed to estimate the charge separation abilities. The results show that, when compared with those for the PBDB-T/PC71BM interface, the CT states are more easily formed for the PBDB-T/ITIC interface by either the electron transfer from the FE state or direct excitation, indicating the better charge separation ability of the former. Moreover, the estimation of the charge separation efficiency manifests that although these two types of interfaces have similar charge recombination rates, the PBDB-T/ITIC interface possesses the larger charge separation rates than those of the PBDB-T/PC71BM interface. Therefore, the better match between PBDB-T and ITIC together with a larger charge separation efficiency at the interface are considered to be the reasons for the prominent performance of ITIC in OSCs.

Bimolecular crystals with an intercalated structure improve poly(p-phenylenevinylene)-based organic photovoltaic cells.

PubMed

Lim, Kyung-Geun; Park, Jun-Mo; Mangold, Hannah; Laquai, Frédéric; Choi, Tae-Lim; Lee, Tae-Woo

2015-01-01

The exciton dissociation, recombination, and charge transport of bulk heterojunction organic photovoltaic cells (OPVs) is influenced strongly by the nanomorphology of the blend, such as the grain size and the molecular packing. Although it is well known that polymers based on amorphous poly(p-phenylenevinylene) (PPV) have a fundamental limit to their efficiency because of low carrier mobility, which leads to increased recombination and unbalanced charge extraction, herein, we demonstrate that the issue can be overcome by forming bimolecular crystals of an amorphous PPV-based polymer:phenyl-C61 -butyric acid methyl ester (PCBM) intercalated structure. We used amorphous poly(2,5-dioctyloxy-p-phenylene vinylene-alt-2',5'-thienylene vinylene) (PPVTV), which has a simple chemical structure. A reasonably high power conversion efficiency (∼3.5 %) was obtained, although the material has an intrinsically amorphous structure and a relatively large band gap (2.0 eV). We demonstrate a correlation between a well-ordered bimolecular crystal of PPVTV:PCBM and an improved hole mobility of a PPVTV:PCBM film compared to a pristine PPVTV film by using 2 D grazing incidence XRD and space-charge-limited current measurements. Furthermore, we show that the bimolecular crystal structure in high-performance OPVs is related to an optimum molecular packing, which is influenced by the PPVTV:PCBM blending ratio, side-chain length, and molecular weight of the PPVTV polymer. Improved charge transport in PPVTV:PCBM bimolecular crystals leads to a fast sweep out of charges and thus suppression of nongeminate recombination under the operating conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonradiative recombination centers and electrical aging of organic light-emitting diodes: Direct connection between accumulation of trapped charge and luminance loss

NASA Astrophysics Data System (ADS)

Kondakov, D. Y.; Sandifer, J. R.; Tang, C. W.; Young, R. H.

2003-01-01

Organic light-emitting diodes (OLEDs) are attractive for display applications because of their high brightness, low driving voltage, and tunable color. Their operating lifetimes, hundreds or thousands of hours, are sufficient for only a limited range of applications. The luminance efficiency decreases gradually as the device is operated (electrically aged), for reasons that are poorly understood. A prototypical OLED has the structure anode|HTL|ETL|cathode, where the HTL and ETL are hole- and electron-transporting layers, and the recombination and emission occur at or near the HTL|ETL interface. We find that the decreasing luminance efficiency is linearly correlated with an accumulation of immobile positive charge at the HTL|ETL interface, and the magnitude of the charge is comparable to the total charge at that interface when an unaged device is operated. A natural explanation of the connection between the two phenomena is that electrical aging either generates hole traps (and trapped holes) or drives metal ions into the device, and that either species act as nonradiative recombination centers. To estimate the accumulating immobile charge and determine its location, we use a variant of a recently introduced capacitance versus voltage technique. In the prototypical OLEDs described here, the HTL is a ca. 1000 Å layer of NPB, and the ETL is a 300-1800 Å layer of Alq3. A device with an additional "emission layer" (EML) of an anthracene derivative between the HTL and ETL, in which the electroluminescence spectrum is characteristic of the EML, behaved similarly. We surmise that the phenomena reported here may be common to a wider variety of OLED structures and compositions.

Enhanced excitonic photoconductivity due to built-in internal electric field in TlGaSe{sub 2} layered semiconductor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seyidov, MirHasan Yu., E-mail: smirhasan@gyte.edu.tr; Suleymanov, Rauf A.; Institute of Physics Azerbaijan National Academy of Sciences, AZ-1143 Baku

2014-12-07

The strong enhancement, by several orders of magnitude, of the excitonic peak within the photoconductivity spectrum of TlGaSe{sub 2} semiconductor was observed. The samples were polarized in external dc electric field, which was applied prior to the measurements. Due to the accumulation of charges near the surface, an internal electric field was formed. Electron-hole pairs that were created after the absorption of light are fallen in and then separated by the built-in electric field, which prevents radiative recombination process.

Lewis Base Passivation of Hybrid Halide Perovskites Slows Electron-Hole Recombination: Time-Domain Ab Initio Analysis.

PubMed

Liu, Lihong; Fang, Wei-Hai; Long, Run; Prezhdo, Oleg V

2018-03-01

Nonradiative electron-hole recombination plays a key role in determining photon conversion efficiencies in solar cells. Experiments demonstrate significant reduction in the recombination rate upon passivation of methylammonium lead iodide perovskite with Lewis base molecules. Using nonadiabatic molecular dynamics combined with time-domain density functional theory, we find that the nonradiative charge recombination is decelerated by an order of magnitude upon adsorption of the molecules. Thiophene acts by the traditional passivation mechanism, forcing electron density away from the surface. In contrast, pyridine localizes the electron at the surface while leaving it energetically near the conduction band edge. This is because pyridine creates a stronger coordinative bond with a lead atom of the perovskite and has a lower energy unoccupied orbital compared with thiophene due to the more electronegative nitrogen atom relative to thiophene's sulfur. Both molecules reduce two-fold the nonadiabatic coupling and electronic coherence time. A broad range of vibrational modes couple to the electronic subsystem, arising from inorganic and organic components. The simulations reveal the atomistic mechanisms underlying the enhancement of the excited-state lifetime achieved by the perovskite passivation, rationalize the experimental results, and advance our understanding of charge-phonon dynamics in perovskite solar cells.

Multimodal Kelvin Probe Force Microscopy Investigations of a Photovoltaic WSe2/MoS2 Type-II Interface.

PubMed

Almadori, Yann; Bendiab, Nedjma; Grévin, Benjamin

2018-01-10

Atomically thin transition-metal dichalcogenides (TMDC) have become a new platform for the development of next-generation optoelectronic and light-harvesting devices. Here, we report a Kelvin probe force microscopy (KPFM) investigation carried out on a type-II photovoltaic heterojunction based on WSe 2 monolayer flakes and a bilayer MoS 2 film stacked in vertical configuration on a Si/SiO 2 substrate. Band offset characterized by a significant interfacial dipole is pointed out at the WSe 2 /MoS 2 vertical junction. The photocarrier generation process and phototransport are studied by applying a differential technique allowing to map directly two-dimensional images of the surface photovoltage (SPV) over the vertical heterojunctions (vHJ) and in its immediate vicinity. Differential SPV reveals the impact of chemical defects on the photocarrier generation and that negative charges diffuse in the MoS 2 a few hundreds of nanometers away from the vHJ. The analysis of the SPV data confirms unambiguously that light absorption results in the generation of free charge carriers that do not remain coulomb-bound at the type-II interface. A truly quantitative determination of the electron-hole (e-h) quasi-Fermi levels splitting (i.e., the open-circuit voltage) is achieved by measuring the differential vacuum-level shift over the WSe 2 flakes and the MoS 2 layer. The dependence of the energy-level splitting as a function of the optical power reveals that Shockley-Read-Hall processes significantly contribute to the interlayer recombination dynamics. Finally, a newly developed time-resolved mode of the KPFM is applied to map the SPV decay time constants. The time-resolved SPV images reveal the dynamics of delayed recombination processes originating from photocarriers trapping at the SiO 2 /TMDC interfaces.

[Study on the discharge properties of xeon flash lamp and experimental measurement].

PubMed

Zhao, You-Quan; Miao, Pei-Liang; He, Feng; Gu, Jian; Zhai, Rui-Wei

2014-07-01

The Xenon flash lamp is a new type of light source for analytical instrument. The present paper analyzed the discharge process of xenon flash lamp, presented the discharge test system, and conducted experimental measurement of the voltage, current and optical pulse signal in the process of discharge. The results show that in the preliminary discharge, the free electron concentration was at a low level, so the energy was at a low level, then following the gas discharge, numerous free electrons formed in the lamp, resultin in the increase in the concentration of free electrons, therefore discharge current rised rapidly and voltage reduced. The lamp released photons to generate light pulse in the moment of ionic recombination, The pulse xenon lamp light energy output and spectral characteristic is related to electron energy in recombination and combination level of xenon, if the input energy and the energy consumption of the xenon lamp is inconsistent, it will lead to repeated capacitor charging and discharging and produce oscillation waveform. This paper is very useful for understanding the process of xenon lamp discharge, optimizing the driver circuit and the production of xenon flash lamp.

An enhanced surface passivation effect in InGaN/GaN disk-in-nanowire light emitting diodes for mitigating Shockley-Read-Hall recombination.

PubMed

Zhao, Chao; Ng, Tien Khee; Prabaswara, Aditya; Conroy, Michele; Jahangir, Shafat; Frost, Thomas; O'Connell, John; Holmes, Justin D; Parbrook, Peter J; Bhattacharya, Pallab; Ooi, Boon S

2015-10-28

We present a detailed study of the effects of dangling bond passivation and the comparison of different sulfide passivation processes on the properties of InGaN/GaN quantum-disk (Qdisk)-in-nanowire based light emitting diodes (NW-LEDs). Our results demonstrated the first organic sulfide passivation process for nitride nanowires (NWs). The results from Raman spectroscopy, photoluminescence (PL) measurements, and X-ray photoelectron spectroscopy (XPS) showed that octadecylthiol (ODT) effectively passivated the surface states, and altered the surface dynamic charge, and thereby recovered the band-edge emission. The effectiveness of the process with passivation duration was also studied. Moreover, we also compared the electro-optical performance of NW-LEDs emitting at green wavelength before and after ODT passivation. We have shown that the Shockley-Read-Hall (SRH) non-radiative recombination of NW-LEDs can be greatly reduced after passivation by ODT, which led to a much faster increasing trend of quantum efficiency and higher peak efficiency. Our results highlighted the possibility of employing this technique to further design and produce high performance NW-LEDs and NW-lasers.

Monitoring Ultrafast Chemical Dynamics by Time-Domain X-ray Photo- and Auger-Electron Spectroscopy.

PubMed

Gessner, Oliver; Gühr, Markus

2016-01-19

The directed flow of charge and energy is at the heart of all chemical processes. Extraordinary efforts are underway to monitor and understand the concerted motion of electrons and nuclei with ever increasing spatial and temporal sensitivity. The element specificity, chemical sensitivity, and temporal resolution of ultrafast X-ray spectroscopy techniques hold great promise to provide new insight into the fundamental interactions underlying chemical dynamics in systems ranging from isolated molecules to application-like devices. Here, we focus on the potential of ultrafast X-ray spectroscopy techniques based on the detection of photo- and Auger electrons to provide new fundamental insight into photochemical processes of systems with various degrees of complexity. Isolated nucleobases provide an excellent testing ground for our most fundamental understanding of intramolecular coupling between electrons and nuclei beyond the traditionally applied Born-Oppenheimer approximation. Ultrafast electronic relaxation dynamics enabled by the breakdown of this approximation is the major component of the nucleobase photoprotection mechanisms. Transient X-ray induced Auger electron spectroscopy on photoexcited thymine molecules provides atomic-site specific details of the extremely efficient coupling that converts potentially bond changing ultraviolet photon energy into benign heat. In particular, the time-dependent spectral shift of a specific Auger band is sensitive to the length of a single bond within the molecule. The X-ray induced Auger transients show evidence for an electronic transition out of the initially excited state within only ∼200 fs in contrast to theoretically predicted picosecond population trapping behind a reaction barrier. Photoinduced charge transfer dynamics between transition metal complexes and semiconductor nanostructures are of central importance for many emerging energy and climate relevant technologies. Numerous demonstrations of photovoltaic and photocatalytic activity have been performed based on the combination of strong light absorption in dye molecules with charge separation and transport in adjacent semiconductor nanostructures. However, a fundamental understanding of the enabling and limiting dynamics on critical atomic length- and time scales is often still lacking. Femtosecond time-resolved X-ray photoelectron spectroscopy is employed to gain a better understanding of a short-lived intermediate that may be linked to the unexpectedly limited performance of ZnO based dye-sensitized solar cells by delaying the generation of free charge carriers. The transient spectra strongly suggest that photoexcited dye molecules attached to ZnO nanocrystals inject their charges into the substrate within less than 1 ps but the electrons are then temporarily trapped at the surface of the semiconductor in direct vicinity of the injecting molecules. The experiments are extended to monitor the electronic response of the semiconductor substrate to the collective injection from a monolayer of dye molecules and the subsequent electron-ion recombination dynamics. The results indicate some qualitative similarities but quantitative differences between the recombination dynamics at molecule-semiconductor interfaces and previously studied bulk-surface electron-hole recombination dynamics in photoexcited semiconductors.

Elucidation of reaction mechanisms of Ni2SnP in Li-ion and Na-ion systems

NASA Astrophysics Data System (ADS)

Marino, C.; Dupré, N.; Villevieille, C.

2017-10-01

Electrochemical performance of Ni2SnP was assessed in Li-ion and Na-ion battery systems. When cycled versus Li, Ni2SnP exhibited a reversible specific charge of 700 mAh.g-1 (theoretical specific charge: 742 mAh.g-1). In the Na system, the specific observed charge was ca. 200 mAh.g-1 (theoretical specific charge: 676 mAh.g-1). X-ray diffraction, Ni K-edge X-ray absorption spectroscopy, and 31P and 7Li/23Na nuclear magnetic resonance spectroscopy were used to elucidate the electrochemical mechanisms in both systems. Versus Li, Ni2SnP undergoes a conversion reaction resulting in the extrusion of Ni and the alloying of Li-Sn and Li-P. On delithiation, the material partially recombines into a Sn- and Ni-deficient form. In the Na system, Ni2SnP reacts through the conversion of P into Na3P. These results indicate that the recombination of the pristine material (even partially) increases cycling stability.

Impact of extended defects on recombination in CdTe heterostructures grown by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Zaunbrecher, Katherine N.; Kuciauskas, Darius; Swartz, Craig H.; Dippo, Pat; Edirisooriya, Madhavie; Ogedengbe, Olanrewaju S.; Sohal, Sandeep; Hancock, Bobby L.; LeBlanc, Elizabeth G.; Jayathilaka, Pathiraja A. R. D.; Barnes, Teresa M.; Myers, Thomas H.

2016-08-01

Heterostructures with CdTe and CdTe1-xSex (x ˜ 0.01) absorbers between two wider-band-gap Cd1-xMgxTe barriers (x ˜ 0.25-0.3) were grown by molecular beam epitaxy to study carrier generation and recombination in bulk materials with passivated interfaces. Using a combination of confocal photoluminescence (PL), time-resolved PL, and low-temperature PL emission spectroscopy, two extended defect types were identified and the impact of these defects on charge-carrier recombination was analyzed. The dominant defects identified by confocal PL were dislocations in samples grown on (211)B CdTe substrates and crystallographic twinning-related defects in samples on (100)-oriented InSb substrates. Low-temperature PL shows that twin-related defects have a zero-phonon energy of 1.460 eV and a Huang-Rhys factor of 1.50, while dislocation-dominated samples have a 1.473-eV zero-phonon energy and a Huang-Rhys factor of 1.22. The charge carrier diffusion length near both types of defects is ˜6 μm, suggesting that recombination is limited by diffusion dynamics. For heterostructures with a low concentration of extended defects, the bulk lifetime was determined to be 2.2 μs with an interface recombination velocity of 160 cm/s and an estimated radiative lifetime of 91 μs.

Impact of extended defects on recombination in CdTe heterostructures grown by molecular beam epitaxy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaunbrecher, Katherine N.; Kuciauskas, Darius; Swartz, Craig H.

Heterostructures with CdTe and CdTe 1-xSex (x ~ 0.01) absorbers between two wider-band-gap Cd1-xMgxTe barriers (x ~ 0.25-0.3) were grown by molecular beam epitaxy to study carrier generation and recombination in bulk materials with passivated interfaces. Using a combination of confocal photoluminescence (PL), time-resolved PL, and low-temperature PL emission spectroscopy, two extended defect types were identified and the impact of these defects on charge-carrier recombination was analyzed. The dominant defects identified by confocal PL were dislocations in samples grown on (211)B CdTe substrates and crystallographic twinning-related defects in samples on (100)-oriented InSb substrates. Low-temperature PL shows that twin-related defects havemore » a zero-phonon energy of 1.460 eV and a Huang-Rhys factor of 1.50, while dislocation-dominated samples have a 1.473-eV zero-phonon energy and a Huang-Rhys factor of 1.22. The charge carrier diffusion length near both types of defects is ~6 um, suggesting that recombination is limited by diffusion dynamics. For heterostructures with a low concentration of extended defects, the bulk lifetime was determined to be 2.2 us with an interface recombination velocity of 160 cm/s and an estimated radiative lifetime of 91 us.« less

Abnormal crystal growth in CH 3NH 3PbI 3-xCl x using a multi-cycle solution coating process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Qingfeng; Yuan, Yongbo; Shao, Yuchuan

2015-06-23

Recently, the efficiency of organolead trihalide perovskite solar cells has improved greatly because of improved material qualities with longer carrier diffusion lengths. Mixing chlorine in the precursor for mixed halide films has been reported to dramatically enhance the diffusion lengths of mixed halide perovskite films, mainly as a result of a much longer carrier recombination lifetime. Here we report that adding Cl containing precursor for mixed halide perovskite formation can induce the abnormal grain growth behavior that yields well-oriented grains accompanied by the appearance of some very large size grains. The abnormal grain growth becomes prominent only after multi-cycle coatingmore » of MAI : MACl blend precursor. The large grain size is found mainly to contribute to a longer carrier charge recombination lifetime, and thus increases the device efficiency to 18.9%, but without significantly impacting the carrier transport property. As a result, the strong correlation identified between material process and morphology provides guidelines for future material optimization and device efficiency enhancement.« less

Rational Design of Solution-Processed Ti-Fe-O Ternary Oxides for Efficient Planar CH3NH3PbI3 Perovskite Solar Cells with Suppressed Hysteresis.

PubMed

Li, Xin; Hao, Feng; Zhao, Xingyue; Yin, Xuewen; Yao, Zhibo; Guo, Ying; Shen, Heping; Lin, Hong

2017-10-11

Electron-extraction layer (EEL) plays a critical role in determining the charge extraction and the power conversion efficiencies of the organometal-halide perovskite solar cells (PSCs). In this work, Ti-Fe-O ternary oxides were first developed to work as an efficient EEL in planar PSC. Compared with the widely used TiO x and the pure FeO x , the ternary composites show superior properties in multiple aspects including the excellent stability of the precursor solution, good coverage on the substrates, outstanding electrical properties, and suitable energy levels. By varying the Fe content from 0 to 100% in the Ti-Fe-O composites, the conductivity of the resultant compact layer was markedly improved, confirmed by consistent results from the conductive atomic force microscopy and the linear sweep voltammetry measurements. Meanwhile, the compositional engineering tunes the energy level alignment of the Ti-Fe-O EEL/CH 3 NH 3 PbI 3 interface to a region that is favorable for obtaining excellent charge-extraction property. The combinational advantages of the Ti-Fe-O composites significantly improved the photovoltaic performance of the as-prepared solar cells. An increase of over 20% in the short-circuit current (J SC ) density has been achieved due to a modified EEL conductivity and energy alignment with the perovskite layer. The reduction in the surface recombination and enhancement of the charge collection efficiency also result in about 15% increase in the fill factor. Notably, the device also showed remarkably alleviated hysteresis behavior, revealing a prominently inhibited surface recombination.

Photophysical Properties of Novel Organic, Inorganic, and Hybrid Semiconductor Materials

NASA Astrophysics Data System (ADS)

Chang, Angela Yenchi

For the past 200 years, novel materials have driven technological progress, and going forward these advanced materials will continue to deeply impact virtually all major industrial sectors. Therefore, it is vital to perform basic and applied research on novel materials in order to develop new technologies for the future. This dissertation describes the results of photophysical studies on three novel materials with electronic and optoelectronic applications, namely organic small molecules DTDCTB with C60 and C70, colloidal indium antimonide (InSb) nanocrystals, and an organic-inorganic hybrid perovskite with the composition CH3NH3PbI 3-xClx, using transient absorption (TA) and photoluminescence (PL) spectroscopy. In chapter 2, we characterize the timescale and efficiency of charge separation and recombination in thin film blends comprising DTDCTB, a narrow-band gap electron donor, and either C60 or C70 as an electron acceptor. TA and time-resolved PL studies show correlated, sub-picosecond charge separation times and multiple timescales of charge recombination. Our results indicate that some donors fail to charge separate in donor-acceptor mixed films, which suggests material manipulations may improve device efficiency. Chapter 3 describes electron-hole pair dynamics in strongly quantum-confined, colloidal InSb nanocrystal quantum dots. For all samples, TA shows a bleach feature that, for several picoseconds, dramatically red-shifts prior to reaching a time-independent position. We suggest this unusual red-shift relates transient population flow through two energetically comparable conduction band states. From pump-power-dependent measurements, we also determine biexciton lifetimes. In chapter 4, we examine carrier dynamics in polycrystalline methylammonium lead mixed halide perovskite (CH3NH3PbI3-xCl x) thin films as functions of temperature and photoexcitation wavelength. At room temperature, the long-lived TA signals stand in contrast to PL dynamics, where the latter present a fast decay process prior to slower recombination. We show that this PL feature persists with similar decay amplitude and timescale for temperatures down to the phase transition temperature, and that it depends on pump photon energy at room temperature. Together with high-level electronic structure and dynamics calculations, we suggest the fast PL decay relates a characteristic organic-to-inorganic sub-lattice equilibration timescale at optoelectronic-relevant excitation energies.

High efficiency ZnO-based dye-sensitized solar cells with a 1H,1H,2H,2H-perfluorodecyltriethoxysilane chain barrier for cutting on interfacial recombination

NASA Astrophysics Data System (ADS)

Xie, Yahong; Zhou, Xiaofeng; Mi, Hongyu; Ma, Junhong; Yang, Jianya; Cheng, Jian

2018-03-01

Charge recombination at the ZnO photoanode/electrolyte interface is one of the major limitations for high performance dye-sensitized solar cells (DSSCs) toward their theoretical power conversion efficiency (PCE). Here, we proposed an efficient approach for reducing this interfacial losses and consequently facilitating charge transfer by decorating a hydrophobic thin-film on the surface of the dye-coated zinc oxide photoanode via 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) hexane solution immersing. As a result, a high PCE of 8.22% was obtained, which far exceeded the efficiency of 5.40% in a conventional DSSC without PFDTES treatment. Furthermore, PFDTES treatment also largely elongated the lifetime of photogenerated electrons, and maintained a good photo-response at the photoelectrode. This work provides a comprehensive explanation of electron injection, transfer and recombination at the ZnO photoanode/electrolyte interface, and a promising strategy to explore high efficiency ZnO-based DSSCs.

The effect of PbS nanocrystal additives on the charge transfer state recombination in a bulk heterojunction blend

NASA Astrophysics Data System (ADS)

Abdu-Aguye, Mustapha; Protesescu, Loredana; Dirin, Dmitry N.; Kovalenko, Maksym V.; Loi, Maria Antonietta

2018-05-01

A persistent limitation of organic semiconductors is their low dielectric constant єr, which limits the performance of bulk heterojunction (BHJ) solar cells. One way to increase єr is to employ high-єr additives, such as PbS nanocrystals (QDs) to BHJ blends. In this work, we use the recombination of the interfacial charge transfer (CT) state as a means to study the effects of PbS nanocrystals on blends of a narrow bandgap copolymer: poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1- b;3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), and phenyl-C61-butyric acid methyl ester (PCBM). We show that at low dilution levels (0.25% - 0.75% by weight), there is a decrease in the relative weight of the CT recombination lifetime (longer decay component); suggesting that there is an increase in the local єr of the ternary blend.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Y.; Yi, H. T.; Wu, X.

Impressive performance of hybrid perovskite solar cells reported in recent years still awaits a comprehensive understanding of its microscopic origins. In this work, the intrinsic Hall mobility and photocarrier recombination coefficient are directly measured in these materials in steady-state transport studies. The results show that electron-hole recombination and carrier trapping rates in hybrid perovskites are very low. The bimolecular recombination coefficient (10 –11 to 10 –10 cm 3 s –1) is found to be on par with that in the best direct-band inorganic semiconductors, even though the intrinsic Hall mobility in hybrid perovskites is considerably lower (up to 60 cmmore » 2 V –1 s –1). Measured here, steady-state carrier lifetimes (of up to 3 ms) and diffusion lengths (as long as 650 μm) are significantly longer than those in high-purity crystalline inorganic semiconductors. As a result, we suggest that these experimental findings are consistent with the polaronic nature of charge carriers, resulting from an interaction of charges with methylammonium dipoles.« less

Robust nonfullerene solar cells approaching unity external quantum efficiency enabled by suppression of geminate recombination.

PubMed

Baran, Derya; Gasparini, Nicola; Wadsworth, Andrew; Tan, Ching Hong; Wehbe, Nimer; Song, Xin; Hamid, Zeinab; Zhang, Weimin; Neophytou, Marios; Kirchartz, Thomas; Brabec, Christoph J; Durrant, James R; McCulloch, Iain

2018-05-25

Nonfullerene solar cells have increased their efficiencies up to 13%, yet quantum efficiencies are still limited to 80%. Here we report efficient nonfullerene solar cells with quantum efficiencies approaching unity. This is achieved with overlapping absorption bands of donor and acceptor that increases the photon absorption strength in the range from about 570 to 700 nm, thus, almost all incident photons are absorbed in the active layer. The charges generated are found to dissociate with negligible geminate recombination losses resulting in a short-circuit current density of 20 mA cm -2 along with open-circuit voltages >1 V, which is remarkable for a 1.6 eV bandgap system. Most importantly, the unique nano-morphology of the donor:acceptor blend results in a substantially improved stability under illumination. Understanding the efficient charge separation in nonfullerene acceptors can pave the way to robust and recombination-free organic solar cells.

Why Chemical Vapor Deposition Grown MoS2 Samples Outperform Physical Vapor Deposition Samples: Time-Domain ab Initio Analysis.

PubMed

Li, Linqiu; Long, Run; Prezhdo, Oleg V

2018-06-13

Two-dimensional transition metal dichalcogenides (TMDs) have drawn strong attention due to their unique properties and diverse applications. However, TMD performance depends strongly on material quality and defect morphology. Experiments show that samples grown by chemical vapor deposition (CVD) outperform those obtained by physical vapor deposition (PVD). Experiments also show that CVD samples exhibit vacancy defects, while antisite defects are frequently observed in PVD samples. Our time-domain ab initio study demonstrates that both antisites and vacancies accelerate trapping and nonradiative recombination of charge carriers, but antisites are much more detrimental than vacancies. Antisites create deep traps for both electrons and holes, reducing energy gaps for recombination, while vacancies trap primarily holes. Antisites also perturb band-edge states, creating significant overlap with the trap states. In comparison, vacancy defects overlap much less with the band-edge states. Finally, antisites can create pairs of electron and hole traps close to the Fermi energy, allowing trapping by thermal activation from the ground state and strongly contributing to charge scattering. As a result, antisites accelerate charge recombination by more than a factor of 8, while vacancies enhance the recombination by less than a factor of 2. Our simulations demonstrate a general principle that missing atoms are significantly more benign than misplaced atoms, such as antisites and adatoms. The study rationalizes the existing experimental data, provides theoretical insights into the diverse behavior of different classes of defects, and generates guidelines for defect engineering to achieve high-performance electronic, optoelectronic, and solar-cell devices.

Charge Shielding of PIP2 by Cations Regulates Enzyme Activity of Phospholipase C

PubMed Central

Seo, Jong Bae; Jung, Seung-Ryoung; Huang, Weigang; Zhang, Qisheng; Koh, Duk-Su

2015-01-01

Hydrolysis of phosphatidylinositol 4,5-bisphosphate (PIP2) of the plasma membrane by phospholipase C (PLC) generates two critical second messengers, inositol-1,4,5-trisphosphate and diacylglycerol. For the enzymatic reaction, PIP2 binds to positively charged amino acids in the pleckstrin homology domain of PLC. Here we tested the hypothesis that positively charged divalent and multivalent cations accumulate around the negatively charged PIP2, a process called electrostatic charge shielding, and therefore inhibit electrostatic PIP2-PLC interaction. This charge shielding of PIP2 was measured quantitatively with an in vitro enzyme assay using WH-15, a PIP2 analog, and various recombinant PLC proteins (β1, γ1, and δ1). Reduction of PLC activity by divalent cations, polyamines, and neomycin was well described by a theoretical model considering accumulation of cations around PIP2 via their electrostatic interaction and chemical binding. Finally, the charge shielding of PIP2 was also observed in live cells. Perfusion of the cations into cells via patch clamp pipette reduced PIP2 hydrolysis by PLC as triggered by M1 muscarinic receptors with a potency order of Mg2+ < spermine4+ < neomycin6+. Accumulation of divalent cations into cells through divalent-permeable TRPM7 channel had the same effect. Altogether our results suggest that Mg2+ and polyamines modulate the activity of PLCs by controlling the amount of free PIP2 available for the enzymes and that highly charged biomolecules can be inactivated by counterions electrostatically. PMID:26658739

Charge Shielding of PIP2 by Cations Regulates Enzyme Activity of Phospholipase C.

PubMed

Seo, Jong Bae; Jung, Seung-Ryoung; Huang, Weigang; Zhang, Qisheng; Koh, Duk-Su

2015-01-01

Hydrolysis of phosphatidylinositol 4,5-bisphosphate (PIP2) of the plasma membrane by phospholipase C (PLC) generates two critical second messengers, inositol-1,4,5-trisphosphate and diacylglycerol. For the enzymatic reaction, PIP2 binds to positively charged amino acids in the pleckstrin homology domain of PLC. Here we tested the hypothesis that positively charged divalent and multivalent cations accumulate around the negatively charged PIP2, a process called electrostatic charge shielding, and therefore inhibit electrostatic PIP2-PLC interaction. This charge shielding of PIP2 was measured quantitatively with an in vitro enzyme assay using WH-15, a PIP2 analog, and various recombinant PLC proteins (β1, γ1, and δ1). Reduction of PLC activity by divalent cations, polyamines, and neomycin was well described by a theoretical model considering accumulation of cations around PIP2 via their electrostatic interaction and chemical binding. Finally, the charge shielding of PIP2 was also observed in live cells. Perfusion of the cations into cells via patch clamp pipette reduced PIP2 hydrolysis by PLC as triggered by M1 muscarinic receptors with a potency order of Mg2+ < spermine4+ < neomycin6+. Accumulation of divalent cations into cells through divalent-permeable TRPM7 channel had the same effect. Altogether our results suggest that Mg2+ and polyamines modulate the activity of PLCs by controlling the amount of free PIP2 available for the enzymes and that highly charged biomolecules can be inactivated by counterions electrostatically.

Hydrodynamic flow of ions and atoms in partially ionized plasmas.

PubMed

Nemirovsky, R A; Fredkin, D R; Ron, A

2002-12-01

We have derived the hydrodynamic equations of motion for a partially ionized plasma, when the ionized component and the neutral components have different flow velocities and kinetic temperatures. Starting from the kinetic equations for a gas of ions and a gas of atoms we have considered various processes of encounters between the two species: self-collisions, interspecies collisions, ionization, recombination, and charge exchange. Our results were obtained by developing a general approach for the hydrodynamics of a gas in a binary mixture, in particular when the components drift with respect to each other. This was applied to a partially ionized plasma, when the neutral-species gas and the charged-species gas have separate velocities. We have further suggested a generalized version of the relaxation time approximation and obtained the contributions of the interspecies encounters to the transport equations.

Tuning Light Emission of a Pressure-Sensitive Silicon/ZnO Nanowires Heterostructure Matrix through Piezo-phototronic Effects.

PubMed

Chen, Mengxiao; Pan, Caofeng; Zhang, Taiping; Li, Xiaoyi; Liang, Renrong; Wang, Zhong Lin

2016-06-28

Based on white light emission at silicon (Si)/ZnO hetrerojunction, a pressure-sensitive Si/ZnO nanowires heterostructure matrix light emitting diode (LED) array is developed. The light emission intensity of a single heterostructure LED is tuned by external strain: when the applied stress keeps increasing, the emission intensity first increases and then decreases with a maximum value at a compressive strain of 0.15-0.2%. This result is attributed to the piezo-phototronic effect, which can efficiently modulate the LED emission intensity by utilizing the strain-induced piezo-polarization charges. It could tune the energy band diagrams at the junction area and regulate the optoelectronic processes such as charge carriers generation, separation, recombination, and transport. This study achieves tuning silicon based devices through piezo-phototronic effect.

Nanoscale Interfaces in Colloidal Quantum Dot Solar Cells: Physical Insights and Materials Engineering Strategies

NASA Astrophysics Data System (ADS)

Kemp, Kyle Wayne

With growing global energy demand there will be an increased need for sources of renewable energy such as solar cells. To make these photovoltaic technologies more competitive with conventional energy sources such as coal and natural gas requires further reduction in manufacturing costs that can be realized by solution processing and roll-to-roll printing. Colloidal quantum dots are a bandgap tunable, solution processible, semiconductor material which may offer a path forward to efficient, inexpensive photovoltaics. Despite impressive progress in performance with these materials, there remain limitations in photocarrier collection that must be overcome. This dissertation focuses on the characterization of charge recombination and transport in colloidal quantum dot photovoltaics, and the application of this knowledge to the development of new and better materials. Core-shell, PbS-CdS, quantum dots were investigated in an attempt to achieve better surface passivation and reduce electronic defects which can limit performance. Optimization of this material led to improved open circuit voltage, exceeding 0.6 V for the first time, and record published performance of 6% efficiency. Using temperature-dependent and transient photovoltage measurements we explored the significance of interface recombination on the operation of these devices. Careful engineering of the electrode using atomic layer deposition of ZnO helped lead to better TiO2 substrate materials and allowed us to realize a nearly two-fold reduction in recombination rate and an enhancement upwards of 50 mV in open circuit voltage. Carrier extraction efficiency was studied in these devices using intensity dependent current-voltage data of an operational solar cell. By developing an analytical model to describe recombination loss within the active layer of the device we were able to accurately determine transport lengths ranging up to 90 nm. Transient absorption and photoconductivity techniques were used to study charge dynamics by identifying states in these quantum dot materials which facilitate carrier transport. Thermal activation energies for transport of 60 meV or lower were measured for different PbS quantum dot bandgaps, representing a relatively small barrier for carrier transport. From these measurements a dark, quantum confined energy level was attributed to the electronic bandedge of these materials which serves to govern their optoelectronic behavior.

A mechanistic dissection of polyethylenimine mediated transfection of CHO cells: to enhance the efficiency of recombinant DNA utilization.

PubMed

Mozley, Olivia L; Thompson, Ben C; Fernandez-Martell, Alejandro; James, David C

2014-01-01

In this study, we examine the molecular and cellular interactions that underpin efficient internalization and utilization of polyethylenimine (PEI):DNA complexes (polyplexes) by Chinese Hamster Ovary (CHO) cells. Cell surface polyplex binding and internalization was a biphasic process, consisting of an initial rapid Phase (I), lasting approximately 15 min, followed by a slower second Phase (II), saturating at approximately 240 min post transfection. The second Phase accounted for the majority (60-70%) of polyplex internalization. While cell surface heparan sulphate proteoglycans (HSPGs) were rapidly cointernalized with polyplexes during Phase I, cell surface polyplex binding was not dependent on HSPGs. However, Phase II polyplex internalization and HSPG regeneration onto the surface of trypsinized cells occurred at similar rates, suggesting that the rate of recycling of HSPG-containing membrane to the plasma membrane limits Phase II internalization rate. Under optimal transfection conditions, polyplexes had a near neutral surface charge (zeta potential) and cell surface binding was dependent on hydrophobic interactions, being significantly inhibited by both chemical sequestration of cholesterol from the plasma membrane and addition of nonionic surfactant. Induced alterations in polyplex zeta potential, using ferric (III) citrate to decrease surface charge and varying PEI:DNA ratio to increase surface charge, served to inhibit polyplex binding or reduce secreted alkaline phosphatase reporter expression and cell viability, respectively. To increase polyplex hydrophobicity and internalization an alkylated derivative of PEI, propyl-PEI, was chemically synthesized. Using Design of Experiments-Response Surface Modeling to optimize the transfection process, the function of propyl-PEI was compared to that of unmodified PEI in both parental CHO-S cells and a subclone (Clone 4), which exhibited superior transgene expression via an increased resistance to polyplex cytotoxicity. The combination of propyl-PEI and Clone 4 doubled the efficiency of recombinant DNA utilization and reporter protein production. These data show that for maximal efficacy, strategies to increase polyplex internalization into cells must be used in concert with strategies to offset the inherent cytotoxicity of this process. © 2014 American Institute of Chemical Engineers.

Charge Recombination, Transport Dynamics, and Interfacial Effects in Organic Solar Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heeger, Alan; Bazan, Guillermo; Nguyen, Thuc-Quyen

The need for renewable sources of energy is well known. Conversion of sunlight to electricity using solar cells is one of the most important opportunities for creating renewable energy sources. The research carried out under DE-FG02-08ER46535 focused on the science and technology of “Plastic” solar cells comprised of organic (i.e. carbon based) semiconductors. The Bulk Heterojunction concept involves a phase separated blend of two organic semiconductors each with dimensions in the nano-meter length scale --- one a material that functions as a donor for electrons and the other a material that functions as an acceptor for electrons. The nano-scale inter-penetratingmore » network concept for “Plastic” solar cells was created at UC Santa Barbara. A simple measure of the impact of this concept can be obtained from a Google search which gives 244,000 “hits” for the Bulk Heterojunction solar cell. Research funded through this program focused on four major areas: 1. Interfacial effects in organic photovoltaics, 2. Charge transfer and photogeneration of mobile charge carriers in organic photovoltaics, 3. Transport and recombination of the photogenerated charge carriers in organic photovoltaics, 4. Synthesis of novel organic semiconducting polymers and semiconducting small molecules, including conjugated polyelectrolytes. Following the discovery of ultrafast charge transfer at UC Santa Barbara in 1992, the nano-organic (Bulk Heterojunction) concept was formulated. The need for a morphology comprising two interpenetrating bicontinuous networks was clear: one network to carry the photogenerated electrons (negative charge) to the cathode and one network to carry the photo-generated holes (positive charge) to the anode. This remarkable self-assembled network morphology has now been established using Transmission electron Microscopy (TEM) either in the Phase Contrast mode or via TEM-Tomography. The steps involved in delivering power from a solar cell to an external circuit are the following: • Photo-excitation of the donor (or the acceptor). • Charge transfer with holes in the donor domain and electrons in the acceptor domain. • Sweep-out to electrodes prior to recombination by the internal electric field. • Energy delivered to the external circuit. Each of these four steps was studied in detail using a wide variety of organic semiconductors with different molecular structures. This UC Santa Barbara group was the first to clarify the origin and the mechanism involved in the ultrafast charge transfer process. The ultrafast charge transfer (time scale approximately 100 times faster than the first step in the photo-synthesis of green plants) is the fundamental reason for the potential for high power conversion efficiency of sunlight to electricity from plastic solar cells. The UCSB group was the first to emphasize, clarify and demonstrate the need for sweep-out to electrodes prior to recombination by the internal electric field. The UCSB group was the first to synthesize small molecule organic semiconductors capable of high power conversion efficiencies. The results of this research were published in high impact peer-reviewed journals. Our published papers (40 in number) provide answers to fundamental questions that have been heavily discussed and debated in the field of Bulk Heterojunction Solar Cells; scientific questions that must be resolved before this technology can be ready for commercialization in large scale for production of renewable energy. Of the forty publications listed, nineteen were co-authored by two or more of the PIs, consistent with the multi-investigator approach described in the original proposal. The specific advantages of this “plastic” solar cell technology are the following: a. Manufacturing by low-cost printing technology using soluble organic semiconductors; this approach can be implemented in large scale by roll-to-roll printing on plastic substrates. b. Low energy cost in manufacturing; all steps carried out at room temperature (approx. a factor of ten less than the use of Silicon which requires high temperature processing). c. Low carbon footprint d. Lightweight, flexible and rugged Because of the resolution of many scientific issues, a significant fraction of which were addressed in the research results of DE-FG02-08ER46535, the power conversion efficiencies are improving at an ever increasing rate. During the funding period of DE-FG02-08ER46535, the power conversion efficiencies of plastic solar cells improved from just a few per cent to values greater than 11% with contributions from our group and from researchers all over the world.« less

Carrier multiplication and charge transport in artificial quantum-dot solids probed by ultrafast photocurrent spectroscopy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Klimov, Victor I.

2017-05-01

Understanding and controlling carrier transport and recombination dynamics in colloidal quantum dot films is key to their application in electronic and optoelectronic devices. Towards this end, we have conducted transient photocurrent measurements to monitor transport through quantum confined band edge states in lead selenide quantum dots films as a function of pump fluence, temperature, electrical bias, and surface treatment. Room temperature dynamics reveal two distinct timescales of intra-dot geminate processes followed by non-geminate inter-dot processes. The non-geminate kinetics is well described by the recombination of holes with photoinjected and pre-existing electrons residing in mid-gap states. We find the mobility of the quantum-confined states shows no temperature dependence down to 6 K, indicating a tunneling mechanism of early time photoconductance. We present evidence of the importance of the exciton fine structure in controlling the low temperature photoconductance, whereby the nanoscale enhanced exchange interaction between electrons and holes in quantum dots introduces a barrier to charge separation. Finally, side-by-side comparison of photocurrent transients using excitation with low- and high-photon energies (1.5 vs. 3.0 eV) reveals clear signatures of carrier multiplication (CM), that is, generation of multiple excitons by single photons. Based on photocurrent measurements of quantum dot solids and optical measurements of solution based samples, we conclude that the CM efficiency is unaffected by strong inter-dot coupling. Therefore, the results of previous numerous spectroscopic CM studies conducted on dilute quantum dot suspensions should, in principle, be reproducible in electronically coupled QD films used in devices.

Modeling of protein-anion exchange resin interaction for the human growth hormone charge variants.

PubMed

Lapelosa, Mauro; Patapoff, Thomas W; Zarraga, Isidro E

2015-12-01

Modeling ion exchange chromatography (IEC) behavior has generated significant interest because of the wide use of IEC as an analytical technique as well as a preparative protein purification process; indeed there is a need for better understanding of what drives the unique behavior of protein charge variants. We hypothesize that a complex protein molecule, which contains both hydrophobic and charged moieties, would interact strongly with an in silico designed resin through charged electrostatic patches on the surface of the protein. In the present work, variants of recombinant human growth hormone that mimic naturally-occurring deamidation products were produced and characterized in silico. The study included these four variants: rhGH, N149D, N152D, and N149D/N152D. Poisson-Boltzmann calculations were used to determine surface electrostatic potential. Metropolis Monte Carlo simulations were carried out with the resulting variants to simulate IEC systems, examining the free energy of the interaction of the protein with an in silico anion exchange column represented by polylysine polypeptide. The results show that the charge variants have different average binding energies and the free energy of interaction can be used to predict the retention time for the different variants. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of broad recombination zone in multiple quantum well structures on lifetime and efficiency of blue organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Lee, Seok Jae; Lee, Song Eun; Lee, Dong Hyung; Koo, Ja Ryong; Lee, Ho Won; Yoon, Seung Soo; Park, Jaehoon; Kim, Young Kwan

2014-10-01

Blue phosphorescent organic light-emitting diodes with multiple quantum well (MQW) structures (from one to four quantum wells) within an emitting layer (EML) are fabricated with charge control layers (CCLs) to control carrier movement. The distributed recombination zone and balanced charge carrier injection within EML are achieved through the MQW structure with CCLs. Remarkably, the half-decay lifetime of a blue device with three quantum wells, measured at an initial luminance of 500 cd/m2, is 3.5 times longer than that using a conventional structure. Additionally, the device’s efficiency improved. These results are explained with the effects of triplet exciton confinement and triplet-triplet annihilation within each EML.

Guanidinium: A Route to Enhanced Carrier Lifetime and Open-Circuit Voltage in Hybrid Perovskite Solar Cells.

PubMed

De Marco, Nicholas; Zhou, Huanping; Chen, Qi; Sun, Pengyu; Liu, Zonghao; Meng, Lei; Yao, En-Ping; Liu, Yongsheng; Schiffer, Andy; Yang, Yang

2016-02-10

Hybrid perovskites have shown astonishing power conversion efficiencies owed to their remarkable absorber characteristics including long carrier lifetimes, and a relatively substantial defect tolerance for solution-processed polycrystalline films. However, nonradiative charge carrier recombination at grain boundaries limits open circuit voltages and consequent performance improvements of perovskite solar cells. Here we address such recombination pathways and demonstrate a passivation effect through guanidinium-based additives to achieve extraordinarily enhanced carrier lifetimes and higher obtainable open circuit voltages. Time-resolved photoluminescence measurements yield carrier lifetimes in guanidinium-based films an order of magnitude greater than pure-methylammonium counterparts, giving rise to higher device open circuit voltages and power conversion efficiencies exceeding 17%. A reduction in defect activation energy of over 30% calculated via admittance spectroscopy and confocal fluorescence intensity mapping indicates successful passivation of recombination/trap centers at grain boundaries. We speculate that guanidinium ions serve to suppress formation of iodide vacancies and passivate under-coordinated iodine species at grain boundaries and within the bulk through their hydrogen bonding capability. These results present a simple method for suppressing nonradiative carrier loss in hybrid perovskites to further improve performances toward highly efficient solar cells.

Study on charge carrier recombination zone with ultrathin rubrene layer as probe

NASA Astrophysics Data System (ADS)

Wen, Wen; Yu, Jungsheng; Li, Yi; Li, Lu; Jiang, Yadong

2009-05-01

The characteristic of charge carrier recombination zone in N,N'-bis-(1-naphthyl)-N,N'-biphenyl-1,1'-biphenyl-4,4'-diamine (NPB) based OLEDs is studied using an ultrathin 5,6,11,12-tetraphenylnaphthacene (rubrene) as a probe. By adjusting the rubrene thickness and location in NPB light-emitting layer, the luminescent spectra and electrical properties of the devices are investigated. The results show that when the thickness ranges from 0.2 to 0.8 nm, the surface morphology of rubrene exists as the discontinuous island-like state locating on the surface of NPB film and seldom affect the electrical characteristics. While the location of rubrene shifted from the interface of NPB/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) to NPB side, the maximum exciton concentration is found within 2 nm away from the interface, which is the main charge carrier recombination zone. With an optimized structure of indium-tin-oxide (ITO)/NPB (40nm)/rubrene (0.3nm)/NPB (7nm)/BCP (30nm)/Mg:Ag, the device exhibits a turn on voltage as low as 3 V and stable white light. The peaks of EL spectra are located at 431 and 555 nm corresponding to the Commissions Internationale De L'Eclairage (CIE) coordinates of (0.32, 0.32), which are relatively stable under the bias voltage from 5 to 15 V. A maximum luminance of 5630 cd/m2 and a maximum power efficiency of 0.6 lm/W is achieved. The balanced spectra are attributed to the stable confining of charge carriers and exciton by the thin emitting layers.

Trypsin treatment of reaction centers from Rhodobacter sphaeroides in the dark and under illumination: protein structural changes follow charge separation.

PubMed

Brzezinski, P; Andréasson, L E

1995-06-06

Reaction centers from Rhodobacter sphaeroides R-26 were treated with trypsin in the dark and during illumination (in the charge-separated state). Trypsination resulted in a time-dependent modification of the reaction centers, reflected in changes in the charge recombination rate, in the inhibition of QA- to QB electron transfer, and eventually to inhibition of charge separation. Comparisons of centers with ubiquinone or anthraquinone in the QA site, in which the charge recombination pathways are different, indicate that trypsination affects charges close to the QA(-)-binding site. Studies of light-induced voltage changes from moving charges in reaction centers incorporated in lipid layers on a Teflon film, a technique which allows the discrimination of effects on donor and acceptor sides, indicate that the acceptor side is preferentially degraded by trypsin in the dark. Tryptic digestion during illumination generally resulted in a marked strengthening and acceleration of the effects seen already during dark treatment, but new effects were also detected in gel electrophoretic peptide patterns, in optical spectra, and in the kinetic measurements. Optical kinetic measurements revealed that the donor side of the reaction centers became susceptible to modification by trypsin during illumination as seen in the value of the binding constant for soluble cytochrome c2 which increased by a factor of 2, whereas it was much less affected after trypsination of reaction centers in the dark. The influence of illumination on the rate and mode by which trypsin acts on reaction centers indicates that changes in the protein conformation follow charge separation.(ABSTRACT TRUNCATED AT 250 WORDS)

Improved utilization of photogenerated charge using fluorine-doped TiO(2) hollow spheres scattering layer in dye-sensitized solar cells.

PubMed

Song, Junling; Yang, Hong Bin; Wang, Xiu; Khoo, Si Yun; Wong, C C; Liu, Xue-Wei; Li, Chang Ming

2012-07-25

We demonstrate a strategy to improve utilization of photogenerated charge in dye-sensitized solar cells (DSSCs) with fluorine-doped TiO2 hollow spheres as the scattering layer, which improves the fill factor from 69.4% to 74.1% and in turn results in an overall efficiency of photoanode increased by 13% (from 5.62% to 6.31%) in comparison with the control device using undoped TiO2 hollow spheres. It is proposed that the fluorine-doping improves the charge transfer and inhibition of charge recombination to enhance the utilization of the photogenerated charge in the photoanode.

Stable High-Performance Perovskite Solar Cells Based on Inorganic Electron Transporting Bi-layers.

PubMed

Gu, Hao; Zhao, Chen; Zhang, Yiqiang; Shao, Guosheng

2018-06-27

As one of the significant electron transporting materials (ETM) in efficient planar heterojunction perovskite solar cells (PSCs), SnO₂ can collect/transfer photo-generated carriers produced in perovskite active absorbers and suppress the carrier recombination at interfaces. In this study, we demonstrate that mild solution-processed SnO₂ compact layer can be an eminent ETM for planar heterojunction PSCs. Here, the device based on chemical-bath-deposited SnO₂ electron transporting layer (ETL) exhibits a power conversion efficiency (PCE) of 16.10% and with obvious hysteresis effect (hysteresis index=19.5%), owing to the accumulation and recombination of charge carriers at SnO₂/perovskite interface. In order to improve the carrier dissociation and transport process, an ultrathin TiO₂ film was deposited on the top of SnO₂ ETL passivating nonradiative recombination center. The corresponding device based on TiO₂@SnO₂ electron transporting bi-layer (ETBL) exhibited a high PCE (17.45%) and a negligible hysteresis effect (hysteresis index=1.5%). These findings indicate that this facile solution-processed TiO₂@SnO₂ ETBL paves a scalable and inexpensive way for fabricating hysteresis-less and high-performance PSCs. © 2018 IOP Publishing Ltd.

The effect of protein acetylation on the formation and processing of inclusion bodies and endogenous protein aggregates in Escherichia coli cells.

PubMed

Kuczyńska-Wiśnik, Dorota; Moruno-Algara, María; Stojowska-Swędrzyńska, Karolina; Laskowska, Ewa

2016-11-10

Acetylation of lysine residues is a reversible post-translational modification conserved from bacteria to humans. Several recent studies have revealed hundreds of lysine-acetylated proteins in various bacteria; however, the physiological role of these modifications remains largely unknown. Since lysine acetylation changes the size and charge of proteins and thereby may affect their conformation, we assumed that lysine acetylation can stimulate aggregation of proteins, especially for overproduced recombinant proteins that form inclusion bodies. To verify this assumption, we used Escherichia coli strains that overproduce aggregation-prone VP1GFP protein. We found that in ΔackA-pta cells, which display diminished protein acetylation, inclusion bodies were formed with a delay and processed faster than in the wild-type cells. Moreover, in ΔackA-pta cells, inclusion bodies exhibited significantly increased specific GFP fluorescence. In CobB deacetylase-deficient cells, in which protein acetylation was enhanced, the formation of inclusion bodies was increased and their processing was significantly inhibited. Similar results were obtained with regard to endogenous protein aggregates formed during the late stationary phase in ΔackA-pta and ΔcobB cells. Our studies revealed that protein acetylation affected the aggregation of endogenous E. coli proteins and the yield, solubility, and biological activity of a model recombinant protein. In general, decreased lysine acetylation inhibited the formation of protein aggregates, whereas increased lysine acetylation stabilized protein aggregates. These findings should be considered during the designing of efficient strategies for the production of recombinant proteins in E. coli cells.

The Effect of Dopant-Free Hole-Transport Polymers on Charge Generation and Recombination in Cesium-Bismuth-Iodide Solar Cells.

PubMed

Zhu, Huimin; Johansson, Malin B; Johansson, Erik M J

2018-03-22

The photovoltaic characteristics of CsBi 3 I 10 -based solar cells with three dopant-free hole-conducting polymers are investigated. The effect on charge generation and charge recombination in the solar cells using the different polymers is studied and the results indicate that the choice of polymer strongly affects the device properties. Interestingly, for the solar cell with poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] (TQ1), the photon-to-current conversion spectrum is highly improved in the red wavelength region, suggesting that the polymer also contributes to the photocurrent generation in this case. This report provides a new direction for further optimization of Bi-halide solar cells by using dopant-free hole-transporting polymers and shows that the energy levels and the interaction between the Bi-halide and the conducting polymers are very important for solar cell performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fill factor in organic solar cells can exceed the Shockley-Queisser limit

NASA Astrophysics Data System (ADS)

Trukhanov, Vasily A.; Bruevich, Vladimir V.; Paraschuk, Dmitry Yu.

2015-06-01

The ultimate efficiency of organic solar cells (OSC) is under active debate. The solar cell efficiency is calculated from the current-voltage characteristic as a product of the open-circuit voltage (VOC), short-circuit current (JSC), and the fill factor (FF). While the factors limiting VOC and JSC for OSC were extensively studied, the ultimate FF for OSC is scarcely explored. Using numerical drift-diffusion modeling, we have found that the FF in OSC can exceed the Shockley-Queisser limit (SQL) established for inorganic p-n junction solar cells. Comparing charge generation and recombination in organic donor-acceptor bilayer heterojunction and inorganic p-n junction, we show that such distinctive properties of OSC as interface charge generation and heterojunction facilitate high FF, but the necessary condition for FF exceeding the SQL in OSC is field-dependence of charge recombination at the donor-acceptor interface. These findings can serve as a guideline for further improvement of OSC.

Pressure dependence of excited-state charge-carrier dynamics in organolead tribromide perovskites

NASA Astrophysics Data System (ADS)

Liu, X. C.; Han, J. H.; Zhao, H. F.; Yan, H. C.; Shi, Y.; Jin, M. X.; Liu, C. L.; Ding, D. J.

2018-05-01

Excited-state charge-carrier dynamics governs the performance of organometal trihalide perovskites (OTPs) and is strongly influenced by the crystal structure. Characterizing the excited-state charge-carrier dynamics in OTPs under high pressure is imperative for providing crucial insights into structure-property relations. Here, we conduct in situ high-pressure femtosecond transient absorption spectroscopy experiments to study the excited-state carrier dynamics of CH3NH3PbBr3 (MAPbBr3) under hydrostatic pressure. The results indicate that compression is an effective approach to modulate the carrier dynamics of MAPbBr3. Across each pressure-induced phase, carrier relaxation, phonon scattering, and Auger recombination present different pressure-dependent properties under compression. Responsiveness is attributed to the pressure-induced variation in the lattice structure, which also changes the electronic band structure. Specifically, simultaneous prolongation of carrier relaxation and Auger recombination is achieved in the ambient phase, which is very valuable for excess energy harvesting. Our discussion provides clues for optimizing the photovoltaic performance of OTPs.

Characterization of cross-section correction to charge exchange recombination spectroscopy rotation measurements using co- and counter-neutral-beam views.

PubMed

Solomon, W M; Burrell, K H; Feder, R; Nagy, A; Gohil, P; Groebner, R J

2008-10-01

Measurements of rotation using charge exchange recombination spectroscopy can be affected by the energy dependence of the charge exchange cross section. On DIII-D, the associated correction to the rotation can exceed 100 kms at high temperatures. In reactor-relevant low rotation conditions, the correction can be several times larger than the actual plasma rotation and therefore must be carefully validated. New chords have been added to the DIII-D CER diagnostic to view the counter-neutral-beam line. The addition of these views allows determination of the toroidal rotation without depending on detailed atomic physics calculations, while also allowing experimental characterization of the atomic physics. A database of rotation comparisons from the two views shows that the calculated cross-section correction can adequately describe the measurements, although there is a tendency for "overcorrection." In cases where accuracy better than about 15% is desired, relying on calculation of the cross-section correction may be insufficient.

Origin of Non-Radiative Voltage Losses in Fullerene-Based Organic Solar Cells

NASA Astrophysics Data System (ADS)

Benduhn, Johannes; Tvingstedt, Kristofer; Piersimoni, Fortunato; Ullbrich, Sascha; Neher, Dieter; Spoltore, Donato; Vandewal, Koen

The open-circuit voltage of organic solar cells (OSCs) is low as compared to the optical gap of the absorber molecules, indicating high energy losses per absorbed photon. These voltage losses arise only partly due to necessity of an electron transfer event to dissociate the excitons. A large part of these voltage losses is due to recombination of photo-generated charge carriers, including inevitable radiative recombination. In this work, we study the non-radiative recombination losses and we find that they increase when the energy difference between charge transfer (CT) state and ground state decreases. This behavior is in agreement with the \\x9Denergy gap law for non-radiative transition\\x9D, which implies that internal conversion from CT state to ground state is facilitated by skeletal molecular vibrations. This intrinsic loss mechanism, which until now has not been thoroughly considered for OSCs, is different in its nature as compared to the commonly considered inorganic photovoltaic loss mechanisms of defect, surface, and Auger recombination. As a consequence, the theoretical upper limit for the power conversion efficiency of a single junction OSC reduces by 25% as compared to the Shockley-Queisser limit for an optimal optical gap of the main absorber between (1.45-1.65) eV.

Endotoxin depletion of recombinant protein preparations through their preferential binding to histidine tags.

PubMed

Mack, Laura; Brill, Boris; Delis, Natalia; Groner, Bernd

2014-12-01

The presence of endotoxins in preparations of recombinantly produced therapeutic proteins poses serious problems for patients. Endotoxins can cause fever, respiratory distress syndromes, intravascular coagulation, or endotoxic shock. A number of methods have been devised to remove endotoxins from protein preparations using separation procedures based on molecular mass or charge properties. Most of the methods are limited in their endotoxin removal capacities and lack general applicability. We are describing a biotechnological approach for endotoxin removal. This strategy exploits the observation that endotoxins form micelles that expose negative charges on their surface, leading to preferential binding of endotoxins to cationic surfaces, allowing the separation from their resident protein. Endotoxins exhibit high affinity to stretches of histidines, which are widely used tools to facilitate the purification of recombinant proteins. They bind to nickel ions and are the basis for protein purification from cellular extracts by immobilized metal affinity chromatography. We show that the thrombin-mediated cleavage of two histidine tags from the purified recombinant protein and the adsorption of these histidine tags and their associated endotoxins to a nickel affinity column result in an appreciable depletion of the endotoxins in the purified protein fraction. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Impact of extended defects on recombination in CdTe heterostructures grown by molecular beam epitaxy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaunbrecher, Katherine N.; National Renewable Energy Laboratory, Golden, Colorado 80401; Kuciauskas, Darius

Heterostructures with CdTe and CdTe{sub 1-x}Se{sub x} (x ∼ 0.01) absorbers between two wider-band-gap Cd{sub 1-x}Mg{sub x}Te barriers (x ∼ 0.25–0.3) were grown by molecular beam epitaxy to study carrier generation and recombination in bulk materials with passivated interfaces. Using a combination of confocal photoluminescence (PL), time-resolved PL, and low-temperature PL emission spectroscopy, two extended defect types were identified and the impact of these defects on charge-carrier recombination was analyzed. The dominant defects identified by confocal PL were dislocations in samples grown on (211)B CdTe substrates and crystallographic twinning-related defects in samples on (100)-oriented InSb substrates. Low-temperature PL shows that twin-related defects have amore » zero-phonon energy of 1.460 eV and a Huang-Rhys factor of 1.50, while dislocation-dominated samples have a 1.473-eV zero-phonon energy and a Huang-Rhys factor of 1.22. The charge carrier diffusion length near both types of defects is ∼6 μm, suggesting that recombination is limited by diffusion dynamics. For heterostructures with a low concentration of extended defects, the bulk lifetime was determined to be 2.2 μs with an interface recombination velocity of 160 cm/s and an estimated radiative lifetime of 91 μs.« less

Quantitative analysis of optical and recombination losses in Cu(In,Ga)Se{sub 2} thin-film solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kosyachenko, L. A., E-mail: lakos@chv.ukrpack.net; Lytvynenko, V. Yu.; Maslyanchuk, O. L.

2016-04-15

Optical and recombination losses in a Cu(In,Ga)Se{sub 2} thin-film solar cell with a band gap of 1.36–1.38 eV are theoretically analyzed. The optical transmittance of the ZnO and CdS layers through which the radiation penetrates into the absorbing layer is determined. Using optical constants, the optical loss caused by reflection at the interfaces (7.5%) and absorption in the ZnO and CdS layers (10.2%) are found. To calculate the recombination loss, the spectral distribution of the quantum efficiency of CdS/CuIn{sub 1–x}Ga{sub x}Se{sub 2} is investigated. It is demonstrated that, taking the drift and diffusion components of recombination at the front andmore » rear surfaces of the absorber into account, the quantum efficiency spectra of the investigated solar cell can be analytically described in detail. The real parameters of the solar cell are determined by comparing the calculated results and experimental data. In addition, the losses caused by the recombination of photogenerated carriers at the front and rear surfaces of the absorbing layer (1.8% and <0.1%, respectively), at its neutral part (7.6%), and in the space-charge region of the p–n heterojunction (1.0%) are determined. A correction to the parameters of Cu(In,Ga)Se{sub 2} is proposed, which enhances the charge-accumulation efficiency.« less

Spatial Variation in Mobility-Lifetime Product in Bulk TlBr and CZT

NASA Astrophysics Data System (ADS)

Phillips, David; Haegel, Nancy; Blaine, Kevin; Kim, Hadong; Ciampi, Guido; Cirignano, Len

2012-02-01

The energy resolution of a semiconductor radiation detector depends on the charge transport properties of the semiconductor, and the mobility-lifetime (μτ) product is a key figure of merit for charge transport. In this work, we investigate the effects of two impurities, Na and Cu, on the μτ product in bulk thallium bromide (TlBr) using cathodoluminescence (CL) and transport imaging. Transport imaging uses a scanning electron microscope to generate a line of charge carriers on the surface of a bulk sample, and the intensity and spatial distribution of the recombination luminescence are recorded. A Green's function approach is used to model the generation, diffusion, and recombination of charge carriers under steady-state conditions. The luminescence distribution is fit to the model to extract the ambipolar diffusion length and the μτ product, providing a high-resolution correlation between the luminescence variations due to dopants/defects and the quantitative transport behavior. The μτ product has been mapped across a 40 μm segment of TlBr at a resolution of 2 μm. Additionally, this approach has been used to locally map variations in ambipolar diffusion length and μτ product due to extended defects in cadmium zinc telluride (CZT).

On electrode pinning and charge blocking layers in organic solar cells

NASA Astrophysics Data System (ADS)

Magen, Osnat; Tessler, Nir

2017-05-01

We use device modelling for studying the losses introduced by metallic electrodes in organic solar cells' device structure. We first discuss the inclusion of pinning at the integer charge transfer state in device models, with and without using the image charge potential. In the presence of disorder, the space charge introduced due to the image potential enhances the pinning by more than 0.2 eV. The explicit introduction of the image potential creates band-gap narrowing at the contact, thus affecting both dark leakage current and photo conversion efficiency. We find that there are two regimes in which the contacts may limit the performance. For low (moderate) barriers, the contacts introduce minority carrier recombination at the contacts that adds to the bulk recombination channels. Only for high barriers, the contacts directly limit the open circuit voltage and impose a value that is equal to the contact's energy difference. Examining the device structures with blocking layers, we find that these are mainly useful for the low to moderate contacts' barriers and that for the high barrier case, the enhancement of open circuit voltage may be accompanied by the introduction of serial resistance or S shape.

Polymer Solar Cells with 90% External Quantum Efficiency Featuring an Ideal Light- and Charge-Manipulation Layer.

PubMed

Chen, Jing-De; Li, Yan-Qing; Zhu, Jingshuai; Zhang, Qianqian; Xu, Rui-Peng; Li, Chi; Zhang, Yue-Xing; Huang, Jing-Sheng; Zhan, Xiaowei; You, Wei; Tang, Jian-Xin

2018-03-01

Rapid progress in the power conversion efficiency (PCE) of polymer solar cells (PSEs) is beneficial from the factors that match the irradiated solar spectrum, maximize incident light absorption, and reduce photogenerated charge recombination. To optimize the device efficiency, a nanopatterned ZnO:Al 2 O 3 composite film is presented as an efficient light- and charge-manipulation layer (LCML). The Al 2 O 3 shells on the ZnO nanoparticles offer the passivation effect that allows optimal electron collection by suppressing charge-recombination loss. Both the increased refractive index and the patterned deterministic aperiodic nanostructure in the ZnO:Al 2 O 3 LCML cause broadband light harvesting. Highly efficient single-junction PSCs for different binary blends are obtained with a peak external quantum efficiency of up to 90%, showing certified PCEs of 9.69% and 13.03% for a fullerene blend of PTB7:PC 71 BM and a nonfullerene blend, FTAZ:IDIC, respectively. Because of the substantial increase in efficiency, this method unlocks the full potential of the ZnO:Al 2 O 3 LCML toward future photovoltaic applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self healing of defected graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Jianhui; Shi, Tuwan; Cai, Tuocheng

For electronics applications, defects in graphene are usually undesirable because of their ability to scatter charge carriers, thereby reduce the carrier mobility. It would be extremely useful if the damage can be repaired. In this work, we employ Raman spectroscopy, X-ray photoemission spectroscopy, transmission electron microscopy, and electrical measurements to study defects in graphene introduced by argon plasma bombardment. We have found that majority of these defects can be cured by a simple thermal annealing process. The self-healing is attributed to recombination of mobile carbon adatoms with vacancies. With increasing level of plasma induced damage, the self-healing becomes less effective.

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Recombination in liquid-filled ionization chambers beyond the Boag limit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brualla-González, L.; Roselló, J.

Purpose: The high mass density and low mobilities of charge carriers can cause important recombination in liquid-filled ionization chambers (LICs). Saturation correction methods have been proposed for LICs. Correction methods for pulsed irradiation are based on Boag equation. However, Boag equation assumes that the charge ionized by one pulse is fully collected before the arrival of the next pulse. This condition does not hold in many clinical beams where the pulse repetition period may be shorter than the charge collection time, causing overlapping between charge carriers ionized by different pulses, and Boag equation is not applicable there. In this work,more » the authors present an experimental and numerical characterization of collection efficiencies in LICs beyond the Boag limit, with overlapping between charge carriers ionized by different pulses. Methods: The authors have studied recombination in a LIC array for different dose-per-pulse, pulse repetition frequency, and polarization voltage values. Measurements were performed in a Truebeam Linac using FF and FFF modalities. Dose-per-pulse and pulse repetition frequency have been obtained by monitoring the target current with an oscilloscope. Experimental collection efficiencies have been obtained by using a combination of the two-dose-rate method and ratios to the readout of a reference chamber (CC13, IBA). The authors have also used numerical simulation to complement the experimental data. Results: The authors have found that overlap significantly increases recombination in LICs, as expected. However, the functional dependence of collection efficiencies on the dose-per-pulse does not change (a linear dependence has been observed in the near-saturation region for different degrees of overlapping, the same dependence observed in the nonoverlapping scenario). On the other hand, the dependence of collection efficiencies on the polarization voltage changes in the overlapping scenario and does not follow that of Boag equation, the reason being that changing the polarization voltage also affects the charge collection time, thus changing the amount of overlapping. Conclusions: These results have important consequences for saturation correction methods for LICs. On one hand, the two-dose-rate method, which relies on the functional dependence of the collection efficiencies on dose-per-pulse, can also be used in the overlapping situation, provided that the two measurements needed to feed the method are performed at the same pulse repetition frequency (monitor unit rate). This result opens the door to computing collection efficiencies in LICs in many clinical setups where charge overlap in the LIC exists. On the other hand, correction methods based on the voltage-dependence of Boag equation like the three-voltage method or the modified two-voltage method will not work in the overlapping scenario due to the different functional dependence of collection efficiencies on the polarization voltage.« less

The Sheath Transport Observer for the Redistribution of Mass (STORM) Image

NASA Technical Reports Server (NTRS)

Kuntz, Kip; Collier, Michael; Sibeck, David G.; Porter, F. Scott; Carter, J. A.; Cravens, Thomas; Omidi, N.; Robertson, Ina; Sembay, S.; Snowden, Steven L.

2008-01-01

All of the solar wind energy that powers magnetospheric processes passes through the magnetosheath and magnetopause. Global images of the magnetosheath and magnetopause boundary layers will resolve longstanding controversy surrounding fundamental phenomena that occur at the magnetopause and provide information needed to improve operational space weather models. Recent developments showing that soft X-rays (0.15-1 keV) result from high charge state solar wind ions undergoing charge exchange recombination through collisions with exospheric neutral atoms has led to the realization that soft X-ray imaging can provide global maps of the high-density shocked solar wind within the magnetosheath and cusps, regions lying between the lower density solar wind and magnetosphere. We discuss an instrument concept called the Sheath Transport Observer for the Redistribution of Mass (STORM), an X-ray imager suitable for simultaneously imaging the dayside magnetosheath, the magnetopause boundary layers, and the cusps.

The Sheath Transport Observer for the Redistribution of Mass (STORM) Imager

NASA Technical Reports Server (NTRS)

Collier, Michael R.; Sibeck, David G.; Porter, F. Scott; Burch, J.; Carter, J. A.; Cravens, Thomas; Kuntz, Kip; Omidi, N.; Read, A.; Robertson, Ina;

The fate of electron-hole pairs in polymer:fullerene blends for organic photovoltaics

NASA Astrophysics Data System (ADS)

Causa', Martina; de Jonghe-Risse, Jelissa; Scarongella, Mariateresa; Brauer, Jan C.; Buchaca-Domingo, Ester; Moser, Jacques-E.; Stingelin, Natalie; Banerji, Natalie

2016-09-01

There has been long-standing debate on how free charges are generated in donor:acceptor blends that are used in organic solar cells, and which are generally comprised of a complex phase morphology, where intermixed and neat phases of the donor and acceptor material co-exist. Here we resolve this question, basing our conclusions on Stark effect spectroscopy data obtained in the absence and presence of externally applied electric fields. Reconciling opposing views found in literature, we unambiguously demonstrate that the fate of photogenerated electron-hole pairs--whether they will dissociate to free charges or geminately recombine--is determined at ultrafast times, despite the fact that their actual spatial separation can be much slower. Our insights are important to further develop rational approaches towards material design and processing of organic solar cells, assisting to realize their purported promise as lead-free, third-generation energy technology that can reach efficiencies over 10%.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Peijun; Xia, Yi; Gong, Jue

Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures.more » Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.« less

High-Resolution X-Ray Spectroscopy of the Galactic Supernova Remnant Puppis A with the XMM-Newton RGS

NASA Technical Reports Server (NTRS)

Katsuda, Satoru; Tsunemi, Hiroshi; Mori, Koji; Uchida, Hiroyuki; Petre, Robert; Yamada, Shinya; Akamatsu, Hiroki; Konami, Saori; Tamagawa, Toru

2012-01-01

We present high-resolution X-ray spectra of cloud-shock interaction regions in the eastern and northern rims of the Galactic supernova remnant Puppis A, using the Reflection Grating Spectrometer onboard the XMM-Newton satellite. A number of emission lines including K(alpha) triplets of He-like N, O , and Ne are clearly resolved for the first time. Intensity ratios of forbidden to resonance lines in the triplets are found to be higher than predictions by thermal emission models having plausible plasma parameters. The anomalous line ratios cannot be reproduced by effects of resonance scattering, recombination, or inner-shell ionization processes, but could be explained by charge-exchange emission that should arise at interfaces between the cold/warm clouds and the hot plasma. Our observations thus provide observational support for charge-exchange X-ray emission in supernova remnants.

Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

PubMed

Nastasi, Francesco; Puntoriero, Fausto; Natali, Mirco; Mba, Miriam; Maggini, Michele; Mussini, Patrizia; Panigati, Monica; Campagna, Sebastiano

2015-05-01

A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

A facile strategy to fabricate plasmonic Cu modified TiO{sub 2} nano-flower films for photocatalytic reduction of CO{sub 2} to methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Enzhou; Qi, Lulu; Bian, Juanjuan

Graphical abstract: Photoreduction of CO{sub 2} to CH{sub 3}OH over plasmonic Cu/TiO{sub 2} film. - Highlights: • Cu nanoparticles modified TiO{sub 2} nano-flower film was prepared by a facile strategy. • Cu nanoparticles can enhance the light absorption and the Raman scattering of TiO{sub 2}. • Cu nanoparticles can effectively restrain the recombination of the charge carriers. • A synergistic mechanism is proposed for photocatalytic reduction of CO{sub 2} on Cu/TiO{sub 2} film. - Abstract: Cu nanoparticles (NPs) deposited TiO{sub 2} nano-flower films were fabricated using a combination of a hydrothermal method and a microwave-assisted reduction process. The investigations indicatedmore » that Cu NPs and TiO{sub 2} film both exhibit visible light harvesting properties based on localized surface plasmon resonance (LSPR) of Cu NPs and unique nanostructures of TiO{sub 2} film. Fluorescence quenching was observed because the recombination of charge carriers was effectively suppressed by Cu NPs deposition. The experimental results indicate that Cu/TiO{sub 2} films exhibit better activity for the photocatalytic reduction of CO{sub 2} due to the charge transfer property and LSPR effect of Cu NPs. The CH{sub 3}OH production rate reached 1.8 μmol cm{sup −2} h{sup −1} (energy efficiency was 0.8%) over 0.5 Cu/TiO{sub 2} film under UV and visible light irradiation, which was 6.0 times higher than that observed over pure TiO{sub 2} film. In addition, a tentative photocatalytic mechanism is proposed to understand the experimental results over the Cu modified TiO{sub 2} nano-flower films.« less

Exciton transport, charge extraction, and loss mechanisms in organic photovoltaics

NASA Astrophysics Data System (ADS)

Scully, Shawn Ryan

Organic photovoltaics have attracted significant interest over the last decade due to their promise as clean low-cost alternatives to large-scale electric power generation such as coal-fired power, natural gas, and nuclear power. Many believe power conversion efficiency targets of 10-15% must be reached before commercialization is possible. Consequently, understanding the loss mechanisms which currently limit efficiencies to 4-5% is crucial to identify paths to reach higher efficiencies. In this work, we investigate the dominant loss mechanisms in some of the leading organic photovoltaic architectures. In the first class of architectures, which include planar heterojunctions and bulk heterojunctions with large domains, efficiencies are primarily limited by the distance photogenerated excitations (excitons) can be transported (termed the exciton diffusion length) to a heterojunction where the excitons may dissociate. We will discuss how to properly measure the exciton diffusion length focusing on the effects of optical interference and of energy transfer when using fullerenes as quenching layers and show how this explains the variety of diffusion lengths reported for the same material. After understanding that disorder and defects limit exciton diffusion lengths, we suggest some approaches to overcome this. We then extensively investigate the use of long-range resonant energy transfer to increase exciton harvesting. Using simulations and experiments as support, we discuss how energy transfer can be engineered into architectures to increase the distance excitons can be harvested. In an experimental model system, DOW Red/PTPTB, we will show how the distance excitons are harvested can be increased by almost an order of magnitude up to 27 nm from a heterojunction and give design rules and extensions of this concept for future architectures. After understanding exciton harvesting limitations we will look at other losses that are present in planar heterojunctions. One of the primary losses that puts stringent requirements on the charge carrier mobilities in these cells is the recombination losses due to space charge build up at the heterojunction. Because electrons are confined to the acceptor and holes to the donor, net charge density always exists even when mobilities are matched, in contrast to bulk heterojunctions wherein matched mobilities lead to zero net charge. This net charge creates an electric field which opposes the built-in field and limits the current that can be carried away from this heterojunction. Using simulations we show that for relevant current densities charge carrier mobilities must be higher than 10-4 cm2/V.s to avoid significant losses due to space charge formation. In the last part of this work, we will focus on the second class of architectures in which exciton harvesting is efficient. We will present a systematic analysis of one of the leading polymer:fullerene bulk heterojunction cells to show that losses in this architecture are due to charge recombination. Using optical measurements and simulations, exciton harvesting measurements, and device characteristics we will show that the dominant loss is likely due to field-dependent geminate recombination of the electron and hole pair created immediately following exciton dissociation. No losses in this system are seen due to bimolecular recombination or space charge which provides information on charge-carrier mobility targets necessary for the future design of high efficiency organic photovoltaics.

Dead layer on silicon p-i-n diode charged-particle detectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wall, B. L.; Amsbaugh, John F.; Beglarian, A.

Abstract Semiconductor detectors in general have a dead layer at their surfaces that is either a result of natural or induced passivation, or is formed during the process of making a contact. Charged particles passing through this region produce ionization that is incompletely collected and recorded, which leads to departures from the ideal in both energy deposition and resolution. The silicon p-i-n diode used in the KATRIN neutrinomass experiment has such a dead layer. We have constructed a detailed Monte Carlo model for the passage of electrons from vacuum into a silicon detector, and compared the measured energy spectra tomore » the predicted ones for a range of energies from 12 to 20 keV. The comparison provides experimental evidence that a substantial fraction of the ionization produced in the "dead" layer evidently escapes by discussion, with 46% being collected in the depletion zone and the balance being neutralized at the contact or by bulk recombination. The most elementary model of a thinner dead layer from which no charge is collected is strongly disfavored.« less

Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements

PubMed Central

Chen, Y.; Yi, H. T.; Wu, X.; Haroldson, R.; Gartstein, Y. N.; Rodionov, Y. I.; Tikhonov, K. S.; Zakhidov, A.; Zhu, X. -Y.; Podzorov, V.

2016-01-01

Impressive performance of hybrid perovskite solar cells reported in recent years still awaits a comprehensive understanding of its microscopic origins. In this work, the intrinsic Hall mobility and photocarrier recombination coefficient are directly measured in these materials in steady-state transport studies. The results show that electron-hole recombination and carrier trapping rates in hybrid perovskites are very low. The bimolecular recombination coefficient (10−11 to 10−10 cm3 s−1) is found to be on par with that in the best direct-band inorganic semiconductors, even though the intrinsic Hall mobility in hybrid perovskites is considerably lower (up to 60 cm2 V−1 s−1). Measured here, steady-state carrier lifetimes (of up to 3 ms) and diffusion lengths (as long as 650 μm) are significantly longer than those in high-purity crystalline inorganic semiconductors. We suggest that these experimental findings are consistent with the polaronic nature of charge carriers, resulting from an interaction of charges with methylammonium dipoles. PMID:27477058

The effects of electronic impurities and electron-hole recombination dynamics on large-grain organic-inorganic perovskite photovoltaic efficiencies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blancon, Jean-Christophe Robert; Nie, Wanyi; Neukirch, Amanda J.

2016-04-27

Hybrid organic-inorganic perovskites have attracted considerable attention after promising developments in energy harvesting and other optoelectronic applications. However, further optimization will require a deeper understanding of the intrinsic photophysics of materials with relevant structural characteristics. Here, the dynamics of photoexcited charge carriers in large-area grain organic-inorganic perovskite thin films is investigated via confocal time-resolved photoluminescence spectroscopy. It is found that the bimolecular recombination of free charges is the dominant decay mechanism at excitation densities relevant for photovoltaic applications. Bimolecular coefficients are found to be on the order of 10 –9 cm 3 s –1, comparable to typical direct-gap semiconductors, yetmore » significantly smaller than theoretically expected. It is also demonstrated that there is no degradation in carrier transport in these thin films due to electronic impurities. Here, suppressed electron–hole recombination and transport that is not limited by deep level defects provide a microscopic model for the superior performance of large-area grain hybrid perovskites for photovoltaic applications.« less

Charge transport in quantum dot organic solar cells with Si quantum dots sandwiched between poly(3-hexylthiophene) (P3HT) absorber and bathocuproine (BCP) transport layers

NASA Astrophysics Data System (ADS)

Verma, Upendra Kumar; Kumar, Brijesh

2017-10-01

We have modeled a multilayer quantum dot organic solar cell that explores the current-voltage characteristic of the solar cell whose characteristics can be tuned by varying the fabrication parameters of the quantum dots (QDs). The modeled device consists of a hole transport layer (HTL) which doubles up as photon absorbing layer, several quantum dot layers, and an electron transport layer (ETL). The conduction of charge carriers in HTL and ETL has been modeled by the drift-diffusion transport mechanism. The conduction and recombination in the quantum dot layers are described by a system of coupled rate equations incorporating tunneling and bimolecular recombination. Analysis of QD-solar cells shows improved device performance compared to the similar bilayer and trilayer device structures without QDs. Keeping other design parameters constant, solar cell characteristics can be controlled by the quantum dot layers. Bimolecular recombination coefficient of quantum dots is a prime factor which controls the open circuit voltage (VOC) without any significant reduction in short circuit current (JSC).

Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements

DOE PAGES

Chen, Y.; Yi, H. T.; Wu, X.; ...

2016-08-01

Impressive performance of hybrid perovskite solar cells reported in recent years still awaits a comprehensive understanding of its microscopic origins. In this work, the intrinsic Hall mobility and photocarrier recombination coefficient are directly measured in these materials in steady-state transport studies. The results show that electron-hole recombination and carrier trapping rates in hybrid perovskites are very low. The bimolecular recombination coefficient (10 –11 to 10 –10 cm 3 s –1) is found to be on par with that in the best direct-band inorganic semiconductors, even though the intrinsic Hall mobility in hybrid perovskites is considerably lower (up to 60 cmmore » 2 V –1 s –1). Measured here, steady-state carrier lifetimes (of up to 3 ms) and diffusion lengths (as long as 650 μm) are significantly longer than those in high-purity crystalline inorganic semiconductors. As a result, we suggest that these experimental findings are consistent with the polaronic nature of charge carriers, resulting from an interaction of charges with methylammonium dipoles.« less

Magnetic field effect on the optoelectronic response of amorphous hydrogenated silicon

NASA Astrophysics Data System (ADS)

McLaughlin, Ryan; Sun, Dali; Zhang, Chuang; Ehrenfreund, Eitan; Vardeny, Zeev Valy

We have studied the magneto-photoluminescence and magneto photoconductivity in amorphous hydrogenated silicon (a-Si:H) thin films and devices as a function of temperature up to field of 5 Tesla. The magnetic field effects (MFE) are interpreted as spin mixing between spin-singlet and spin-triplet charge pairs due to the ''delta- g'' mechanism that is based on the g-value difference between the paired electron and hole, which directly affects the rate of radiative recombination and charge carrier separation, respectively. We found that the MFE(B) response does not form a Lorentzian (that is expected from the ''delta- g'' mechanism) due to disorder in the film that results in a broad distribution of e-h recombination rates, which could be extracted directly by time-resolved photoluminescence.

VizieR Online Data Catalog: Radiative recombination electron energy loss data (Mao+, 2017)

NASA Astrophysics Data System (ADS)

Mao, J.; Kaastra, J.; Badnell, N. R.

2016-11-01

The weighted electron energy loss factors (dimensionless) are defined by weighting the electron energy loss rate coefficients (per ion) with respect to the total radiative recombination rates. Both the unparameterized and parameterized weighted electron energy-loss factors for H-like to Ne-like ions from H (z=1) up to and including Zn (z=30), in a wide temperature range, are available here. For the unparameterized data set, the temperatures are set to the conventional ADAS temperature grid, i.e. c2*(10,20,50,100,200,...,2*106,5*106,107)K, where c is the ionic charge of the recombined ion. For the fitting parameters, the temperature should be in units of eV. We refer to the recombined ion when we speak of the radiative recombination of a certain ion, for example, for a bare oxygen ion capturing a free electron via radiative recombination to form H-like oxygen (O VIII, s=1, z=8). The fitting accuracies are better than 4%. (2 data files).

Why the apparent order of bimolecular recombination in blend organic solar cells can be larger than two: A topological consideration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nenashev, A. V.; Dvurechenskii, A. V.; Novosibirsk State University, 630090 Novosibirsk

2016-07-18

The apparent order δ of non-geminate recombination higher than δ = 2 has been evidenced in numerous experiments on organic bulk heterojunction (BHJ) structures intensively studied for photovoltaic applications. This feature is claimed puzzling, since the rate of the bimolecular recombination in organic BHJ systems is proportional to the product of the concentrations of recombining electrons and holes and therefore the reaction order δ = 2 is expected. In organic BHJ structures, electrons and holes are confined to two different material phases: electrons to the acceptor material (usually a fullerene derivative) while holes to the donor phase (usually a polymer). The non-geminatemore » recombination of charge carriers can therefore happen only at the interfaces between the two phases. Considering a simple geometrical model of the BHJ system, we show that the apparent order of recombination can deviate from δ = 2 due solely to the topological structure of the system.« less

The effects of interfacial recombination and injection barrier on the electrical characteristics of perovskite solar cells

NASA Astrophysics Data System (ADS)

Shi, Lin Xing; Wang, Zi Shuai; Huang, Zengguang; Sha, Wei E. I.; Wang, Haoran; Zhou, Zhen

2018-02-01

Charge carrier recombination in the perovskite solar cells (PSCs) has a deep influence on the electrical performance, such as open circuit voltage, short circuit current, fill factor and ultimately power conversion efficiency. The impacts of injection barrier, recombination channels, doping properties of carrier transport layers and light intensity on the performance of PSCs are theoretically investigated by drift-diffusion model in this work. The results indicate that due to the injection barrier at the interfaces of perovskite and carrier transport layer, the accumulated carriers modify the electric field distribution throughout the PSCs. Thus, a zero electric field is generated at a specific applied voltage, with greatly increases the interfacial recombination, resulting in a local kink of current density-voltage (J-V) curve. This work provides an effective strategy to improve the efficiency of PSCs by pertinently reducing both the injection barrier and interfacial recombination.

Building mechanism for a high open-circuit voltage in an all-solution-processed tandem polymer solar cell.

PubMed

Kong, Jaemin; Lee, Jongjin; Kim, Geunjin; Kang, Hongkyu; Choi, Youna; Lee, Kwanghee

2012-08-14

Additional post-processing techniques, such as post-thermal annealing and UV illumination, were found to be required to obtain desirable values of the cell parameters in a tandem polymer solar cell incorporated with solution-processed basic n-type titanium sub-oxide (TiO(x))/acidic p-type poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) interlayers. Subsequent to the fabrication of the tandem polymer solar cells, the open-circuit voltage (V(OC)) of the cells exhibited half of the expected value. Only after the application of the post-treatments, the V(OC) of a tandem cell increased from the initial half-cell value (∼0.6 V) to its full-cell value (∼1.2 V). The selective light-biased incident photon-to-current efficiency (IPCE) measurements indicated that the initial V(OC) originated from the back subcell and that the application of the post-processing treatments revived the front subcell, such that the net photocurrent of the tandem cell was finally governed by a recombination process of holes from the back subcell and electrons from the front subcell. Based on our experimental results, we suggest that a V(OC) enhancement could be ascribed to two types of subsequent junction formations at the interface between the TiO(x) and PEDOT:PSS interlayers: an 'ion-mediated dipole junction', resulting from the electro-kinetic migration of cationic ions in the interlayers during post-thermal annealing in the presence of a low-work-function metal cathode, and a 'photoinduced Schottky junction', formed by increasing the charge carrier density in the n-type TiO(x) interlayer during UV illumination process. The two junctions separately contributed to the formation of a recombination junction through which the electrons in TiO(x) and the holes in PEDOT:PSS were able to recombine without substantial voltage drops.

Charge heterogeneity: Basic antibody charge variants with increased binding to Fc receptors.

PubMed

Hintersteiner, Beate; Lingg, Nico; Zhang, Peiqing; Woen, Susanto; Hoi, Kong Meng; Stranner, Stefan; Wiederkum, Susanne; Mutschlechner, Oliver; Schuster, Manfred; Loibner, Hans; Jungbauer, Alois

We identified active isoforms of the chimeric anti-GD2 antibody, ch14.18, a recombinant antibody produced in Chinese hamster ovary cells, which is already used in clinical trials. 1,2,3 We separated the antibody by high resolution ion-exchange chromatography with linear pH gradient elution into acidic, main and basic charge variants on a preparative scale yielding enough material for an in-depth study of the sources and the effects of microheterogeneity. The binding affinity of the charge variants toward the antigen and various cell surface receptors was studied by Biacore. Effector functions were evaluated using cellular assays for antibody-dependent cell-mediated cytotoxicity and complement-dependent cytotoxicity. Basic charge variants showed increased binding to cell surface receptor FcγRIIIa, which plays a major role in regulating effector functions. Furthermore, increased binding of the basic fractions to the neonatal receptor was observed. As this receptor mediates the prolonged half-life of IgG in human serum, this data may well hint at an increased serum half-life of these basic variants compared to their more acidic counterparts. Different glycoform patterns, C-terminal lysine clipping and N-terminal pyroglutamate formation were identified as the main structural sources for the observed isoform pattern. Potential differences in structural stability between individual charge variant fractions by nano differential scanning calorimetry could not been detected. Our in-vitro data suggests that the connection between microheterogeneity and the biological activity of recombinant antibody therapeutics deserves more attention than commonly accepted.

Charge Storage, Conductivity and Charge Profiles of Insulators as Related to Spacecraft Charging

NASA Technical Reports Server (NTRS)

Dennison, J. R.; Swaminathan, Prasanna; Frederickson, A. R.

2004-01-01

Dissipation of charges built up near the surface of insulators due to space environment interaction is central to understanding spacecraft charging. Conductivity of insulating materials is key to determine how accumulated charge will distribute across the spacecraft and how rapidly charge imbalance will dissipate. To understand these processes requires knowledge of how charge is deposited within the insulator, the mechanisms for charge trapping and charge transport within the insulator, and how the profile of trapped charge affects the transport and emission of charges from insulators. One must consider generation of mobile electrons and holes, their trapping, thermal de-trapping, mobility and recombination. Conductivity is more appropriately measured for spacecraft charging applications as the "decay" of charge deposited on the surface of an insulator, rather than by flow of current across two electrodes around the sample. We have found that conductivity determined from charge storage decay methods is 102 to 104 smaller than values obtained from classical ASTM and IEC methods for a variety of thin film insulating samples. For typical spacecraft charging conditions, classical conductivity predicts decay times on the order of minutes to hours (less than typical orbit periods); however, the higher charge storage conductivities predict decay times on the order of weeks to months leading to accumulation of charge with subsequent orbits. We found experimental evidence that penetration profiles of radiation and light are exceedingly important, and that internal electric fields due to charge profiles and high-field conduction by trapped electrons must be considered for space applications. We have also studied whether the decay constants depend on incident voltage and flux or on internal charge distributions and electric fields; light-activated discharge of surface charge to distinguish among differing charge trapping centers; and radiation-induced conductivity. Our experiments also show that "Malter" electron emission occurs for hours after turning off the electron beam. This Malter emission similar to emission due to negative electron affinity in semiconductors is a result of the prior radiation or optical excitations of valence electrons and their slow drift among traps towards the surface where they are subsequently emitted. This work is supported through funding from the NASA Space Environments and Effects Program.

Charge-carrier relaxation in sonochemically fabricated dendronized CaSiO3-SiO2-Si nanoheterostructures

NASA Astrophysics Data System (ADS)

Savkina, Rada; Smirnov, Aleksey; Kirilova, Svitlana; Shmid, Volodymyr; Podolian, Artem; Nadtochiy, Andriy; Odarych, Volodymyr; Korotchenkov, Oleg

2018-04-01

We present systematic studies of charge-carrier relaxation processes in sonochemically nanostructured silicon wafers. Impedance spectroscopy and transient photovoltage techniques are employed. It is found that interface potential in Si wafers remarkably increases upon their exposure to sonochemical treatments in Ca-rich environments. In contrast, the density of fast interface electron states remains almost unchanged. It is found that the initial photovoltage decay, taken before ultrasonic treatments, exhibits the involvement of shorter- and longer time recombination and trapping centers. The decay speeds up remarkably due to cavitation treatments, which is accompanied by a substantial quenching of the photovoltage magnitude. It is also found that, before the treatments, the photovoltage magnitude is markedly non-uniform over the wafer surface, implying the existence of distributed sites affecting distribution of photoexcited carriers. The treatments cause an overall broadening of the photovoltage distribution. Furthermore, impedance measurements monitor the progress in surface structuring relevant to several relaxation processes. We believe that sonochemical nanostructuring of silicon wafers with dendronized CaSiO3 may enable new promising avenue towards low-cost solar energy efficiency multilayered solar cell device structures.

Interspace modification of titania-nanorod arrays for efficient mesoscopic perovskite solar cells

NASA Astrophysics Data System (ADS)

Chen, Peng; Jin, Zhixin; Wang, Yinglin; Wang, Meiqi; Chen, Shixin; Zhang, Yang; Wang, Lingling; Zhang, Xintong; Liu, Yichun

2017-04-01

Morphology of electron transport layers (ETLs) has an important influence on the device architecture and electronic processes of mesostructured solar cells. In this work, we thoroughly investigated the effect of the interspace of TiO2 nanorod (NR) arrays on the photovoltaic performance of the perovskite solar cells (PSCs). Along with the interspace in TiO2-NR arrays increasing, the thickness as well as the crystal size of perovskite capping layer are reduced accordingly, and the filling of perovskite in the channel becomes incomplete. Electrochemical impedance spectroscopy measurements reveal that this variation of perovskite absorber layer, induced by interspace of TiO2 NR arrays, causes the change of charge recombination process at the TiO2/perovskite interface, suggesting that a balance between capping layer and the perovskite filling is critical to obtain high charge collection efficiency of PSCs. A power conversion efficiency of 10.3% could be achieved through careful optimization of interspace in TiO2-NR arrays. Our research will shed light on the morphology control of ETLs with 1D structure for heterojunction solar cells fabricated by solution-deposited method.

Time-domain ab initio modeling of photoinduced dynamics at nanoscale interfaces.

PubMed

Wang, Linjun; Long, Run; Prezhdo, Oleg V

2015-04-01

Nonequilibrium processes involving electronic and vibrational degrees of freedom in nanoscale materials are under active experimental investigation. Corresponding theoretical studies are much scarcer. The review starts with the basics of time-dependent density functional theory, recent developments in nonadiabatic molecular dynamics, and the fusion of the two techniques. Ab initio simulations of this kind allow us to directly mimic a great variety of time-resolved experiments performed with pump-probe laser spectroscopies. The focus is on the ultrafast photoinduced charge and exciton dynamics at interfaces formed by two complementary materials. We consider purely inorganic materials, inorganic-organic hybrids, and all organic interfaces, involving bulk semiconductors, metallic and semiconducting nanoclusters, graphene, carbon nanotubes, fullerenes, polymers, molecular crystals, molecules, and solvent. The detailed atomistic insights available from time-domain ab initio studies provide a unique description and a comprehensive understanding of the competition between electron transfer, thermal relaxation, energy transfer, and charge recombination processes. These advances now make it possible to directly guide the development of organic and hybrid solar cells, as well as photocatalytic, electronic, spintronic, and other devices relying on complex interfacial dynamics.

Low-Voltage Solution-Processed Hybrid Light-Emitting Transistors.

PubMed

Chaudhry, Mujeeb Ullah; Tetzner, Kornelius; Lin, Yen-Hung; Nam, Sungho; Pearson, Christopher; Groves, Chris; Petty, Michael C; Anthopoulos, Thomas D; Bradley, Donal D C

2018-06-06

We report the development of low operating voltages in inorganic-organic hybrid light-emitting transistors (HLETs) based on a solution-processed ZrO x gate dielectric and a hybrid multilayer channel consisting of the heterojunction In 2 O 3 /ZnO and the organic polymer "Super Yellow" acting as n- and p-channel/emissive layers, respectively. Resulting HLETs operate at the lowest voltages reported to-date (<10 V) and combine high electron mobility (22 cm 2 /(V s)) with appreciable current on/off ratios (≈10 3 ) and an external quantum efficiency of 2 × 10 -2 % at 700 cd/m 2 . The charge injection, transport, and recombination mechanisms within this HLET architecture are discussed, and prospects for further performance enhancement are considered.

Ultrafast spectroscopic investigation of a fullerene poly(3-hexylthiophene) dyad

NASA Astrophysics Data System (ADS)

Banerji, Natalie; Seifter, Jason; Wang, Mingfeng; Vauthey, Eric; Wudl, Fred; Heeger, Alan J.

2011-08-01

We present the femtosecond spectroscopic investigation of a covalently linked dyad, PCB-P3HT, formed by a segment of the conjugated polymer P3HT (regioregular poly(3-hexylthiophene)) that is end capped with the fullerene derivative PCB ([6,6]-phenyl-C61-butyric acid ester), adapted from PCBM. The fluorescence of the P3HT segment in tetrahydrofuran (THF) solution is reduced by 64% in the dyad compared to a control compound without attached fullerene (P3HT-OH). Fluorescence upconversion measurements reveal that the partial fluorescence quenching of PCB-P3HT in THF is multiphasic and occurs on an average time scale of 100 ps, in parallel to excited-state relaxation processes. Judging from ultrafast transient absorption experiments, the origin of the quenching is excitation energy transfer from the P3HT donor to the PCB acceptor. Due to the much higher solubility of P3HT compared to PCB in THF, the PCB-P3HT dyad molecules self-assemble into micelles. When pure C60 is added to the solution, it is incorporated into the fullerene-rich center of the micelles. This dramatically increases the solubility of C60 but does not lead to significant additional quenching of the P3HT fluorescence by the C60 contained in the micelles. In PCB-P3HT thin films drop-cast from THF, the micelle structure is conserved. In contrast to solution, quantitative and ultrafast (<150 fs) charge separation occurs in the solid-state films and leads to the formation of long-lived mobile charge carriers with characteristic transient absorption signatures similar to those that have been observed in P3HT:PCBM bulk heterojunction blends. While π-stacking interactions between neighboring P3HT chains are weak in the micelles, they are strong in thin films drop-cast from ortho-dichlorobenzene. Here, PCB-P3HT self-assembles into a network of long fibers, clearly seen in atomic force microscopy images. Ultrafast charge separation occurs also for the fibrous morphology, but the transient absorption experiments show fast loss of part of the charge carriers due to intensity-induced recombination and annihilation processes and monomolecular interfacial trap-mediated or geminate recombination. The yield of the long-lived charge carriers in the highly organized fibers is however comparable to that obtained with annealed P3HT:PCBM blends. PCB-P3HT can therefore be considered as an active material in organic photovoltaic devices.

Jeans instability of inhomogeneous dusty plasma with polarization force, ionization and recombination

NASA Astrophysics Data System (ADS)

Jain, Shweta; Sharma, Prerana; Chhajlani, R. K.

2017-05-01

The self-gravitational Jeans instability has been studied in dusty plasma containing significant background of neutral pressure and recombination of ions and electrons on the dust surface. The full dynamics of charged dust grains, ions and neutral species are employed considering the electrons as Maxwellian. We have derived the general dispersion relation for collisional dusty plasma with ionization, recombination and polarization force. The general dispersion relation describes the effects of considered parameters which are solved in different dusty plasma situations. Further, the dispersion relation is solved numerically. The present work is applicable to understand the structure formation of interstellar molecular clouds in astrophysical plasma.

Planar versus bulk heterojunction perovskite microstructures: Impact of morphology on photovoltaic properties and recombination dynamics

NASA Astrophysics Data System (ADS)

Singh, Ranbir; Shukla, Vivek Kumar

2018-05-01

In this work, we compare the planar and bulk heterojunction (BHJ) perovskite thin films for their morphologies, photovoltaic properties, and recombination dynamics. The BHJ perovskite thin films were prepared with the addition of fullerene derivative [6, 6]-Phenyl-C60 butyric acid methyl ester (PC60BM). The addition of PC60BM in perovskite provides a pinhole free film with high absorption coefficient and better charge transfer. The solar cells fabricated with BHJ perovskite exhibits power conversion efficiency (PCE) of 13.5%, with remarkably increased short-circuit current density (JSC) of 20.1 mAcm-2 and reduced recombination rate.

Ultrasensitive photodetectors exploiting electrostatic trapping and percolation transport

DOE PAGES

Zhang, Yingjie; Hellebusch, Daniel J.; Bronstein, Noah D.; ...

2016-06-21

The sensitivity of semiconductor photodetectors is limited by photocarrier recombination during the carrier transport process. We developed a new photoactive material that reduces recombination by physically separating hole and electron charge carriers. This material has a specific detectivity (the ability to detect small signals) of 5 × 10 17 Jones, the highest reported in visible and infrared detectors at room temperature, and 4-5 orders of magnitude higher than that of commercial single-crystal silicon detectors. The material was fabricated by sintering chloride-capped CdTe nanocrystals into polycrystalline films, where Cl selectively segregates into grain boundaries acting as n-type dopants. Photogenerated electrons concentratemore » in and percolate along the grain boundaries - a network of energy valleys, while holes are confined in the grain interiors. This electrostatic field-assisted carrier separation and percolation mechanism enables an unprecedented photoconductive gain of 10 10 e - per photon, and allows for effective control of the device response speed by active carrier quenching.« less

Recombination luminescence of CaSO4:Tb3+ and CaSO4:Gd3+phosphors

NASA Astrophysics Data System (ADS)

Kudryavtseva, Irina; Lushchik, Aleksandr; Maaroos, Aarne; Azmaganbetova, Zhannur; Nurakhmetov, Turlybek; Salikhoja, Zhussupbek

2012-08-01

A comparative study of the excitation of luminescence by VUV radiation as well as of thermally and photostimulated luminescence has been carried out for CaSO4:Tb3+ and CaSO4:Gd3+ phosphors, where Na+ or F- ions are used for charge compensation. The distinction in hole processes for the phosphors with Na+ or F- compensators is determined by the differing thermal stability of the holes localized at/near Tb3+Na+ and Gd3+Na+ (up to 100-160 K) or at/near Tb3+F- V Ca and Gd3+F- V Ca centers involving also a cation vacancy (up to 400-550 K). Tunnel luminescence in the pairs of localized electrons and holes nearby Tb3+ or Gd3+ has been detected. The mechanisms of electron-hole, hole-electron and tunnel recombination luminescence as well as a subsequent released energy transfer to RE3+ ions are considered.

Ultrasensitive photodetectors exploiting electrostatic trapping and percolation transport

PubMed Central

Zhang, Yingjie; Hellebusch, Daniel J.; Bronstein, Noah D.; Ko, Changhyun; Ogletree, D. Frank; Salmeron, Miquel; Alivisatos, A. Paul

2016-01-01

The sensitivity of semiconductor photodetectors is limited by photocarrier recombination during the carrier transport process. We developed a new photoactive material that reduces recombination by physically separating hole and electron charge carriers. This material has a specific detectivity (the ability to detect small signals) of 5 × 1017 Jones, the highest reported in visible and infrared detectors at room temperature, and 4–5 orders of magnitude higher than that of commercial single-crystal silicon detectors. The material was fabricated by sintering chloride-capped CdTe nanocrystals into polycrystalline films, where Cl selectively segregates into grain boundaries acting as n-type dopants. Photogenerated electrons concentrate in and percolate along the grain boundaries—a network of energy valleys, while holes are confined in the grain interiors. This electrostatic field-assisted carrier separation and percolation mechanism enables an unprecedented photoconductive gain of 1010 e− per photon, and allows for effective control of the device response speed by active carrier quenching. PMID:27323904

Influence of the parent cation on the thermalization of subexcitation electrons in solid water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goulet, T.; Jay-Gerin, J.; Patau, J.

1990-09-06

The authors report the results of their Monte Carlo simulations of the thermalization, recombination, and dissociative attachment of subexcitation electrons in solid water. A particular emphasis is placed on the description of the electrons motion in the Coulomb field of its parent cation (H{sub 2}O{sup +}) and on the effect of this positive charge on the fate of the electron. In comparing the results obtained with and without the parent cation they find on the one hand, that the dissociative attachment probability and the electron thermalization distances and times remain practically unaffected by the presence of H{sub 2}O{sup +}. Onmore » the other hand, they find that a certain proportion of subexcitation electrons can be captured, before they thermalize, by a process of dissociative recombination which yields various species such as O, H, OH, and H{sub 2}. The variation of this proportion and of the average thermalization distances and times with the energy of the subexcitation electrons is investigated.« less

Individual dual-emitting CdS multi-branched nanowire arrays under various pumping powers

NASA Astrophysics Data System (ADS)

Guo, S.; Zhao, F. Y.; Li, Y.; Song, G. L.; Li, A.; Chai, K.; Liang, L.; Ma, Z.; Weller, D.; Liu, R. B.

2016-10-01

High-quality Tin doped Cadmium Sulfide (CdS) comb-like nanostructures have been synthesized by a simple in situ seeding chemical vapor deposition process. The color-tunable dual emission of these comb-like nanostructures is demonstrated by changing the excitation power intensity. In fact, the color-tunable emission is in principal due to the variation of the dual emission intensity, which is proven by photoluminescence spectra and real color photoluminescence charge-coupled device images. Especially for different parts in the nano comb, the emission color can be varied even under the same pumping power. This is mainly due to the difference in local structure. By comparison, the color variation was not observed in pure CdS multi-branched nanostructures. The lifetime results demonstrate that the green emission originate from the recombination of free excitons. The origin of red emission is from the recombination of the dopant-induced intrinsic or extrinsic defect states. These findings provide potential applications of laser assisted anti-counterfeit label and micro-size monitors.

Perovskite Solar Cells with Near 100% Internal Quantum Efficiency Based on Large Single Crystalline Grains and Vertical Bulk Heterojunctions

DOE PAGES

Yang, Bin; Dyck, Ondrej; Poplawsky, Jonathan; ...

2015-07-09

Grain boundaries (GBs) as defects in the crystal lattice detrimentally impact the power conversion efficiency (PCE) of polycrystalline solar cells, particularly in recently emerging hybrid perovskites where non-radiative recombination processes lead to significant carrier losses. Here, the beneficial effects of activated vertical GBs are demonstrated by first growing large, vertically-oriented methylammonium lead tri-iodide (CH 3NH 3PbI 3) single-crystalline grains. We show that infiltration of p-type doped 2 -7,7 -tetrakis(N,Ndi-p-methoxyphenylamine)-9,9-spirobifluorene (Spiro-OMeTAD) into CH 3NH 3PbI 3 films along the GBs creates space charge regions to suppress non-radiative recombination and enhance carrier collection efficiency. Solar cells with such activated GBs yielded averagemore » PCE of 16.3 ± 0.9%, which are among the best solution-processed perovskite devices. As an important alternative to growing ideal CH 3NH 3PbI 3 single crystal films, which is difficult to achieve for such fast-crystallizing perovskites, activating GBs paves a way to design a new type of bulk heterojunction hybrid perovskite photovoltaics toward theoretical maximum PCE.« less

Enhancing Photovoltaic Performance of Inverted Planar Perovskite Solar Cells by Cobalt-Doped Nickel Oxide Hole Transport Layer.

PubMed

Xie, Yulin; Lu, Kai; Duan, Jiashun; Jiang, Youyu; Hu, Lin; Liu, Tiefeng; Zhou, Yinhua; Hu, Bin

2018-04-25

Electron and hole transport layers have critical impacts on the overall performance of perovskite solar cells (PSCs). Herein, for the first time, a solution-processed cobalt (Co)-doped NiO X film was fabricated as the hole transport layer in inverted planar PSCs, and the solar cells exhibit 18.6% power conversion efficiency. It has been found that an appropriate Co-doping can significantly adjust the work function and enhance electrical conductivity of the NiO X film. Capacitance-voltage ( C- V) spectra and time-resolved photoluminescence spectra indicate clearly that the charge accumulation becomes more pronounced in the Co-doped NiO X -based photovoltaic devices; it, as a consequence, prevents the nonradiative recombination at the interface between the Co-doped NiO X and the photoactive perovskite layers. Moreover, field-dependent photoluminescence measurements indicate that Co-doped NiO X -based devices can also effectively inhibit the radiative recombination process in the perovskite layer and finally facilitate the generation of photocurrent. Our work indicates that Co-doped NiO X film is an excellent candidate for high-performance inverted planar PSCs.

Photo-Carrier Multi-Dynamical Imaging at the Nanometer Scale in Organic and Inorganic Solar Cells.

PubMed

Fernández Garrillo, Pablo A; Borowik, Łukasz; Caffy, Florent; Demadrille, Renaud; Grévin, Benjamin

2016-11-16

Investigating the photocarrier dynamics in nanostructured and heterogeneous energy materials is of crucial importance from both fundamental and technological points of view. Here, we demonstrate how noncontact atomic force microscopy combined with Kelvin probe force microscopy under frequency-modulated illumination can be used to simultaneously image the surface photopotential dynamics at different time scales with a sub-10 nm lateral resolution. The basic principle of the method consists in the acquisition of spectroscopic curves of the surface potential as a function of the illumination frequency modulation on a two-dimensional grid. We show how this frequency-spectroscopy can be used to probe simultaneously the charging rate and several decay processes involving short-lived and long-lived carriers. With this approach, dynamical images of the trap-filling, trap-delayed recombination and nongeminate recombination processes have been acquired in nanophase segregated organic donor-acceptor bulk heterojunction thin films. Furthermore, the spatial variation of the minority carrier lifetime has been imaged in polycrystalline silicon thin films. These results establish two-dimensional multidynamical photovoltage imaging as a universal tool for local investigations of the photocarrier dynamics in photoactive materials and devices.

Photosensitive dopants for liquid noble gases

DOEpatents

Anderson, David F.

1988-01-01

In an ionization type detector for high energy radiation wherein the energy of incident radiation is absorbed through the ionization of a liquid noble gas and resulting free charge is collected to form a signal indicative of the energy of the incident radiation, an improvement comprising doping the liquid noble gas with photosensitive molecules to convert scintillation light due to recombination of ions, to additional free charge.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samu, Gergely F.; Janaky, Csaba; Kamat, Prashant V.

Photoinduced segregation in mixed halide perovskites has a direct influence on decreasing the solar cell efficiency as segregated I-rich domains serve as charge recombination centers. Here, the changes in the external quantum efficiency mirror the spectral loss in the absorption; however, the time scale of the IPCE recovery in the dark is slower than the absorption recovery, showing the intricate nature of the photoinduced halide segregation and charge collection in solar cell devices.

Charge transport through split photoelectrodes in dye-sensitized solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fakharuddin, Azhar; Ahmed, Irfan; Yusoff, Mashitah M.

2014-04-28

Charge transport and recombination are relatively ignored parameters while upscaling dye-sensitized solar cells (DSCs). Enhanced photovoltaic parameters are anticipated by merely widening the devices physical dimensions, viz., thickness and area as evident from the device design adopted in reported large area DSCs. These strip designs lead to ≤50% loss in photocurrent compared to the high efficiency lab scale devices. Herein, we report that the key to achieving higher current density (J{sub SC}) is optimized diffusion volume rather than the increased photoelectrode area because kinetics of the devices is strongly influenced by the varied choices of diffusion pathways upon increasing themore » electrode area. For a given electrode area and thickness, we altered the photoelectrode design by splitting the electrode into multiple fractions to restrict the electron diffusion pathways. We observed a correlation between the device physical dimensions and its charge collection efficiency via current-voltage and impedance spectroscopy measurements. The modified electrode designs showed >50% increased J{sub SC} due to shorter transport time, higher recombination resistance and enhanced charge collection efficiency compared to the conventional ones despite their similar active volume (∼3.36 × 10{sup −4} cm{sup 3}). A detailed charge transport characteristic of the split devices and their comparison with single electrode configuration is described in this article.« less

MOLED: Simulation of multilayer organic light emitting diodes

NASA Astrophysics Data System (ADS)

Houili, H.; Tutiš, E.; Lütjens, H.; Bussac, M. N.; Zuppiroli, L.

2003-12-01

MOLED solves the dynamics of electrons and holes in multilayer Organic Light Emitting Diodes (OLED). The carriers are injected on the positive and negative electrodes of the device by tunneling through a potential barrier. Thermal excitation processes across the barrier are also included. In the interior of the device the electron-hole recombination occurs when the two carriers are close enough, according to a model inspired from the one of Langevin. A fraction of these recombined pairs gives photons. The charge transport inside the organic material occurs through hopping. Several choices of mobility formulae are available in the code. MOLED can be used for OLEDs with an arbitrary number of layers. The output consists of numerous fields that describe the device performance. For example, there are the current, the recombination and the charge density distributions, the electric field distribution, the current-voltage characteristics and the device internal quantum efficiency. Program summaryTitle of program: MOLED Catalogue identifier: ADSG Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADSG Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Operating systems under which the program has been tested: Unix, Linux Programming language used: FORTRAN 90 Memory required to execute with typical data: 2 MB No. of bytes in distributed program: 26 942 No. of bits in a word: 64 Peripherals used: permanent disk storage No. of lines in distributed program, including test data, etc.: 3695 Distribution format: tar gzip file Nature of the physical problem: Injection of electrons and holes into an organic electroluminescent material occurs through tunneling from metal electrodes. The transport of carriers inside the molecular medium proceeds by hopping from one molecule to another. The emission of light is a result of their radiative Langevin recombination (for a review see [Scott et al., Synthetic Metals 111-112 (2000) 289; Friend et al., Nature 397 (1999) 121]). Method of solution: The equations governing the time evolution of current, charge density and electric field in the device are solved after discretization in time. An implicit procedure is used to perform the time step. The nonlinear effects, originating from strong dependence of the hopping frequency on charge distribution, are treated within the first order in the implicit method [Press et al., Numerical Recipes, Cambridge Univ. Press, 1986, Ch. 17]. The molecular energy levels are updated at each time step to take into account the Coulomb interactions [Tutiš et al., J. Appl. Phys. 89 (2001) 430]. Typical running time: A typical calculation takes a few minutes on DEC Alpha 500 MHz or Pentium 4 1.8 GHz machines. The execution time may vary considerably, depending on the complexity of the problem. Unusual features of the program: This code has a GUI interface for input/output that can be obtained from the URL: http://lomm.epfl.ch/.

Theoretical study of dynamic electron-spin-polarization via the doublet-quartet quantum-mixed state and time-resolved ESR spectra of the quartet high-spin state.

PubMed

Teki, Yoshio; Matsumoto, Takafumi

2011-04-07

The mechanism of the unique dynamic electron polarization of the quartet (S = 3/2) high-spin state via a doublet-quartet quantum-mixed state and detail theoretical calculations of the population transfer are reported. By the photo-induced electron transfer, the quantum-mixed charge-separate state is generated in acceptor-donor-radical triad (A-D-R). This mechanism explains well the unique dynamic electron polarization of the quartet state of A-D-R. The generation of the selectively populated quantum-mixed state and its transfer to the strongly coupled pure quartet and doublet states have been treated both by a perturbation approach and by exact numerical calculations. The analytical solutions show that generation of the quantum-mixed states with the selective populations after de-coherence and/or accompanying the (complete) dephasing during the charge-recombination are essential for the unique dynamic electron polarization. Thus, the elimination of the quantum coherence (loss of the quantum information) is the key process for the population transfer from the quantum-mixed state to the quartet state. The generation of high-field polarization on the strongly coupled quartet state by the charge-recombination process can be explained by a polarization transfer from the quantum-mixed charge-separate state. Typical time-resolved ESR patterns of the quantum-mixed state and of the strongly coupled quartet state are simulated based on the generation mechanism of the dynamic electron polarization. The dependence of the spectral pattern of the quartet high-spin state has been clarified for the fine-structure tensor and the exchange interaction of the quantum-mixed state. The spectral pattern of the quartet state is not sensitive towards the fine-structure tensor of the quantum-mixed state, because this tensor contributes only as a perturbation in the population transfer to the spin-sublevels of the quartet state. Based on the stochastic Liouville equation, it is also discussed why the selective population in the quantum-mixed state is generated for the "finite field" spin-sublevels. The numerical calculations of the elimination of the quantum coherence (de-coherence and/or dephasing) are demonstrated. A new possibility of the enhanced intersystem crossing pathway in solution is also proposed.

Carotenoids as electron or excited-state energy donors in artificial photosynthesis: an ultrafast investigation of a carotenoporphyrin and a carotenofullerene dyad.

PubMed

Pillai, Smitha; Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; van Grondelle, Rienk; Frese, Raoul N; Moore, Thomas A; Gust, Devens; Moore, Ana L; Kennis, John T M

2013-04-07

Photophysical investigations of molecular donor-acceptor systems have helped elucidate many details of natural photosynthesis and revealed design principles for artificial photosynthetic systems. To obtain insights into the factors that govern the partition between excited-state energy transfer (EET) and electron transfer (ET) processes among carotenoids and tetrapyrroles and fullerenes, we have designed artificial photosynthetic dyads that are thermodynamically poised to favor ET over EET processes. The dyads were studied using transient absorption spectroscopy with ∼100 femtosecond time resolution. For dyad , a carotenoporphyrin, excitation to the carotenoid S2 state induces ultrafast ET, competing with internal conversion (IC) to the carotenoid S1 state. In addition, the carotenoid S1 state gives rise to ET. In contrast with biological photosynthesis and many artificial photosynthetic systems, no EET at all was detected for this dyad upon carotenoid S2 excitation. Recombination of the charge separated state takes place in hundreds of picoseconds and yields a triplet state, which is interpreted as a triplet delocalized between the porphyrin and carotenoid moieties. In dyad , a carotenofullerene, excitation of the carotenoid in the S2 band results in internal conversion to the S1 state, ET and probably EET to fullerene on ultrafast timescales. From the carotenoid S1 state EET to fullerene occurs. Subsequently, the excited-state fullerene gives rise to ET from the carotenoid to the fullerene. Again, the charge separated state recombines in hundreds of picoseconds. The results illustrate that for a given rate of EET, the ratio of ET to EET can be controlled by adjusting the driving force for electron transfer.

The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

PubMed

Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

2007-01-18

Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

Long-lived, charge-shift states in heterometallic, porphyrin-based dendrimers formed via click chemistry.

PubMed

Le Pleux, Loïc; Pellegrin, Yann; Blart, Errol; Odobel, Fabrice; Harriman, Anthony

2011-05-26

A series of multiporphyrin clusters has been synthesized and characterized in which there exists a logical gradient for either energy or electron transfer between the porphyrins. A central free-base porphyrin (FbP), for example, is equipped with peripheral zinc(II) porphyrins (ZnP) which act as ancillary light harvesters and transfer excitation energy to the FbP under visible light illumination. Additional energy-transfer steps occur at the triplet level, and the series is expanded by including magnesium(II) porphyrins and/or tin(IV) porphyrins as chromophores. Light-induced electron transfer is made possible by incorporating a gold(III) porphyrin (AuP(+)) into the array. Although interesting by themselves, these clusters serve as control compounds by which to understand the photophysical processes occurring within a three-stage dendrimer comprising an AuP(+) core, a second layer formed from four FbP units, and an outer layer containing 12 ZnP residues. Here, illumination into a peripheral ZnP leads to highly efficient electronic energy transfer to FbP, followed by charge transfer to the central AuP(+). Charge recombination within the resultant charge-shift state is intercepted by secondary hole transfer to the ZnP, which occurs with a quantum yield of around 20%. The final charge-shift state survives for some microseconds in fluid solution at room temperature.

Momentum and Heat Flux Measurements in the Exhaust of VASIMR Using Helium Propellant

NASA Technical Reports Server (NTRS)

Chavers, D. Gregory

2002-01-01

Electromagnetic thrusters typically use electric and magnetic fields to accelerate and exhaust plasma through interactions with the charged particles in the plasma. The energy required to create the plasma, i.e. ionization energy, is potential energy between the electron and ion. This potential energy is typically lost since it is not recovered as the plasma is exhausted and is known as frozen flow loss. If the frozen flow energy is a small fraction of the total plasma energy, this frozen flow loss may be negligible. However, if the frozen flow energy is a major fraction of the total plasma energy, this loss can severely reduce the energy efficiency of the thruster. Recovery and utilization of this frozen flow energy can improve the energy efficiency of a thruster during low specific impulse operating regimes when the ionization energy is a large fraction of the total plasma energy. This paper quantifies the recovery of the frozen flow energy, i.e. recombination energy, via the process of surface recombination for helium. To accomplish this task the momentum flux and heat flux of the plasma flow were measured and compared to calculated values from electrostatic probe data. This information was used to deduce the contribution of recombination energy to the total heat flux on a flat plate as well as to characterize the plasma conditions. Helium propellant was investigated initially due to its high ionization potential and hence available recombination energy.

Organic-inorganic hybrid perovskite quantum dots with high PLQY and enhanced carrier mobility through crystallinity control by solvent engineering and solid-state ligand exchange.

PubMed

Woo Choi, Jin; Woo, Hee Chul; Huang, Xiaoguang; Jung, Wan-Gil; Kim, Bong-Joong; Jeon, Sie-Wook; Yim, Sang-Youp; Lee, Jae-Suk; Lee, Chang-Lyoul

2018-05-22

The photoluminescence quantum yield (PLQY) and charge carrier mobility of organic-inorganic perovskite QDs were enhanced by the optimization of crystallinity and surface passivation as well as solid-state ligand exchange. The crystallinity of perovskite QDs was determined by the Effective solvent field (Esol) of various solvents for precipitation. The solvent with high Esol could more quickly countervail the localized field generated by the polar solvent, and it causes fast crystallization of the dissolved precursor, which results in poor crystallinity. The post-ligand adding process (PLAP) and post-ligand exchange process (PLEP) increase the PLQY of perovskite QDs by reducing non-radiative recombination and the density of surface defect states through surface passivation. Particularly, the post ligand exchange process (PLEP) in the solid-state improved the charge carrier mobility of perovskite QDs in addition to the PLQY enhancement. The ligand exchange with short alkyl chain length ligands could improve the packing density of perovskite QDs in films by reducing the inter-particle distance between perovskite QDs. The maximum hole mobility of 6.2 × 10-3 cm2 V-1 s-1, one order higher than that of pristine QDs without the PLEP, is obtained at perovskite QDs with hexyl ligands. By using PLEP treatment, compared to the pristine device, a 2.5 times higher current efficiency in perovskite QD-LEDs was achieved due to the improved charge carrier mobility and PLQY.

Dissociation and recombination of positive holes in minerals

NASA Technical Reports Server (NTRS)

Freund, Friedemann; Batllo, Francois; Freund, Minoru M.

1990-01-01

The formation mechanisms are described of positive holes - electronic defects in the O2 sublattice - with attention given to detecting the positive surface charge of minerals with these holes. Charge distribution analysis (CDA) is presented which measures dielectric polarization in an inhomogeneous field. CDA can be applied to the detection of the peroxide/superoxide functionality caused by positive holes on the surface. It is demonstrated with obsidian that the measurements provide data on O(-) mobility as a function of surface-charge carrier density and on O(-) generation as a function of temperature.

Interface design principles for high-performance organic semiconductor devices

DOE PAGES

Nie, Wanyi; Gupta, Gautam; Crone, Brian K.; ...

2015-03-23

Organic solar cells (OSCs) are a promising cost-effective candidate in next generation photovoltaic technology. However, a critical bottleneck for OSCs is the electron/hole recombination loss through charge transfer state at the interface, which greatly limits the power conversion efficiency. W. Nie, A. Mohite, and co-workers demonstrate a simple strategy of suppressing the recombination rate by inserting a spacer layer at the donor-acceptor interface, resulting in a dramatic increase in power conversion efficiency.

Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy

DOE PAGES

Penfold, Thomas J.; Szlachetko, Jakub; Santomauro, Fabio G.; ...

2018-02-02

Nanostructures of transition metal oxides (TMO), such as ZnO, have attracted considerable interest for solar-energy conversion and photocatalysis. For the latter, trapping of charge carriers has an essential role. The probing of electron trapping in the conduction band of room temperature photoexcited TMOs has recently become possible owing to the emergence of time-resolved element-sensitive methods, such as X-ray spectroscopy. However, because the valence band of TMOs is dominated by the oxygen 2p orbitals,holes have so far escaped observation. Herein we use a novel dispersive X-ray emission spectrometer combined with X-ray absorption spectroscopy to directly probe the charge carrier relaxation andmore » trapping pro-cesses in ZnO nanoparticles after above band-gap photoexcitation. Here, our results, supported by simulations, demonstrate that within our temporal resolution of 80 ps, photo-excited holes are trapped at singly charged oxygen vacancies, turning them into doubly charged vacancies, which causes an outward displacement by approximately 15% of the four surrounding Zn atoms away from the central vacancy. These traps recombine radiatively with the delocalised electrons of the conduction band yielding the commonly observed green luminescence. This identification of the hole traps and their evolution provides new insight for future developments of TMO-based nanodevices.« less

Revealing hole trapping in zinc oxide nanoparticles by time-resolved X-ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Penfold, Thomas J.; Szlachetko, Jakub; Santomauro, Fabio G.

Nanostructures of transition metal oxides (TMO), such as ZnO, have attracted considerable interest for solar-energy conversion and photocatalysis. For the latter, trapping of charge carriers has an essential role. The probing of electron trapping in the conduction band of room temperature photoexcited TMOs has recently become possible owing to the emergence of time-resolved element-sensitive methods, such as X-ray spectroscopy. However, because the valence band of TMOs is dominated by the oxygen 2p orbitals,holes have so far escaped observation. Herein we use a novel dispersive X-ray emission spectrometer combined with X-ray absorption spectroscopy to directly probe the charge carrier relaxation andmore » trapping pro-cesses in ZnO nanoparticles after above band-gap photoexcitation. Here, our results, supported by simulations, demonstrate that within our temporal resolution of 80 ps, photo-excited holes are trapped at singly charged oxygen vacancies, turning them into doubly charged vacancies, which causes an outward displacement by approximately 15% of the four surrounding Zn atoms away from the central vacancy. These traps recombine radiatively with the delocalised electrons of the conduction band yielding the commonly observed green luminescence. This identification of the hole traps and their evolution provides new insight for future developments of TMO-based nanodevices.« less

Low-Temperature Synthesis of Anatase TiO2 Nanoparticles with Tunable Surface Charges for Enhancing Photocatalytic Activity

PubMed Central

Li, Ye; Qin, Zhenping; Guo, Hongxia; Yang, Hanxiao; Zhang, Guojun; Ji, Shulan; Zeng, Tingying

2014-01-01

In this work, the positively or negatively charged anatase TiO2 nanoparticles were synthesized via a low temperature precipitation-peptization process (LTPPP) in the presence of poly(ethyleneimine) (PEI) and poly(sodium4- styrenesulfonate) (PSS). X-ray diffraction (XRD) pattern and high-resolution transmission electron microscope (HRTEM) confirmed the anatase crystalline phase. The charges of the prepared TiO2, PEI-TiO2 and PSS-TiO2 nanoparticles were investigated by zeta potentials. The results showed that the zeta potentials of PEI-TiO2 nanoparticles can be tuned from +39.47 mV to +95.46 mV, and that of PSS-TiO2 nanoparticles can be adjusted from −56.63 mV to −119.32 mV. In comparison with TiO2, PSS-TiO2 exhibited dramatic adsorption and degradation of dye molecules, while the PEI modified TiO2 nanoparticles showed lower photocatalytic activity. The photocatalytic performances of these charged nanoparticles were elucidated by the results of UV-vis diffuse reflectance spectra (DRS) and the photoluminescence (PL) spectra, which indicated that the PSS-TiO2 nanoparticles showed a lower recombination rate of electron-hole pairs than TiO2 and PEI-TiO2. PMID:25506839

Temperature influence on luminescent coupling efficiency in concentrator MJ SCs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shvarts, Maxim, E-mail: shvarts@scell.ioffe.ru; Emelyanov, Viktor; Mintairov, Mikhail

2015-09-28

In the work, presented are the results of investigation of temperature dependencies of the luminescent coupling effectiveness in lattice-matched (LM) GaInP/GaAs/Ge and metamorphic (MM) GaInP/GaInAs/Ge solar cells. The “ordinary” luminescent coupling effectiveness rise has been observed with temperature decrease for GaAs-Ge, GaInP-GaInAs and GaInAs-Ge pairs of subcells, and its limiting values have been defined. A “reverse” behavior of the luminescent coupling effectiveness for the GaInP-GaAs pair has been found, determined emittance potential drop of wideband GaInP p-n junction. It is shown that the established “unusual” behavior of the LC efficiency may be determined by the presence of thermalized centers ofmore » non-radiative recombination of charge carriers for the GaInP subcell in GaInP/GaAs/Ge LM structure. Estimation of characteristic parameters for the nonradiative recombination processes in wideband GaInP p-n junction has been carried out, and values for the energy of the nonradiative center thermalization (E{sub nrad2} =79.42meV) and for the activation energy of nonradiative band-to-band recombination (E{sub A}=33.4meV) have been obtained.« less

Studies with an immobilized metal affinity chromatography cassette system involving binuclear triazacyclononane-derived ligands: automation of batch adsorption measurements with tagged recombinant proteins.

PubMed

Petzold, Martin; Coghlan, Campbell J; Hearn, Milton T W

2014-07-18

This study describes the determination of the adsorption isotherms and binding kinetics of tagged recombinant proteins using a recently developed IMAC cassette system and employing automated robotic liquid handling procedures for IMAC resin screening. These results confirm that these new IMAC resins, generated from a variety of different metal-charged binuclear 1,4,7-triaza-cyclononane (tacn) ligands, interact with recombinant proteins containing a novel N-terminal metal binding tag, NT1A, with static binding capacities similar to those obtained with conventional hexa-His tagged proteins, but with significantly increased association constants. In addition, higher kinetic binding rates were observed with these new IMAC systems, an attribute that can be positively exploited to increase process productivity. The results from this investigation demonstrate that enhancements in binding capacities and affinities were achieved with these new IMAC resins and chosen NT1A tagged protein. Further, differences in the binding performances of the bis(tacn) xylenyl-bridged ligands were consistent with the distance between the metal binding centres of the two tacn moieties, the flexibility of the ligand and the potential contribution from the aromatic ring of the xylenyl group to undergo π/π stacking interactions with the tagged proteins. Copyright © 2014 Elsevier B.V. All rights reserved.

Tailoring TiO2 Nanotube-Interlaced Graphite Carbon Nitride Nanosheets for Improving Visible-Light-Driven Photocatalytic Performance.

PubMed

Wang, Yang; Liu, Xueqin; Zheng, Cunchuan; Li, Yinchang; Jia, Songru; Li, Zhen; Zhao, Yanli

2018-06-01

Rapid recombination of photoinduced electron-hole pairs is one of the major defects in graphitic carbon nitride (g-C 3 N 4 )-based photocatalysts. To address this issue, perforated ultralong TiO 2 nanotube-interlaced g-C 3 N 4 nanosheets (PGCN/TNTs) are prepared via a template-based process by treating g-C 3 N 4 and TiO 2 nanotubes polymerized hybrids in alkali solution. Shortened migration distance of charge transfer is achieved from perforated PGCN/TNTs on account of cutting redundant g-C 3 N 4 nanosheets, leading to subdued electron-hole recombination. When PGCN/TNTs are employed as photocatalysts for H 2 generation, their in-plane holes and high hydrophilicity accelerate cross-plane diffusion to dramatically promote the photocatalytic reaction in kinetics and supply plentiful catalytic active centers. By having these unique features, PGCN/TNTs exhibit superb visible-light H 2 -generation activity of 1364 µmol h -1 g -1 (λ > 400 nm) and a notable quantum yield of 6.32% at 420 nm, which are much higher than that of bulk g-C 3 N 4 photocatalysts. This study demonstrates an ingenious design to weaken the electron recombination in g-C 3 N 4 for significantly enhancing its photocatalytic capability.

Highly Efficient Visible Colloidal Lead-Halide Perovskite Nanocrystal Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Yan, Fei; Xing, Jun; Xing, Guichuan; Quan, Lina; Tan, Swee Tiam; Zhao, Jiaxin; Su, Rui; Zhang, Lulu; Chen, Shi; Zhao, Yawen; Huan, Alfred; Sargent, Edward H.; Xiong, Qihua; Demir, Hilmi Volkan

2018-05-01

Lead-halide perovskites have been attracting attention for potential use in solid-state lighting. Following the footsteps of solar cells, the field of perovskite light-emitting diodes (PeLEDs) has been growing rapidly. Their application prospects in lighting, however, remain still uncertain due to a variety of shortcomings in device performance including their limited levels of luminous efficiency achievable thus far. Here we show high-efficiency PeLEDs based on colloidal perovskite nanocrystals (PeNCs) synthesized at room temperature possessing dominant first-order excitonic radiation (enabling a photoluminescence quantum yield of 71% in solid film), unlike in the case of bulk perovskites with slow electron-hole bimolecular radiative recombination (a second-order process). In these PeLEDs, by reaching charge balance in the recombination zone, we find that the Auger nonradiative recombination, with its significant role in emission quenching, is effectively suppressed in low driving current density range. In consequence, these devices reach a record high maximum external quantum efficiency of 12.9% reported to date and an unprecedentedly high power efficiency of 30.3 lm W-1 at luminance levels above 1000 cd m-2 as required for various applications. These findings suggest that, with feasible levels of device performance, the PeNCs hold great promise for their use in LED lighting and displays.

Design of charge exchange recombination spectroscopy for the joint Texas experimental tokamak

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chi, Y.; Zhuang, G., E-mail: ge-zhuang@hust.edu.cn; Cheng, Z. F.

The old diagnostic neutral beam injector first operated at the University of Texas at Austin is ready for rejoining the joint Texas experimental tokamak (J-TEXT). A new set of high voltage power supplies has been equipped and there is no limitation for beam modulation or beam pulse duration henceforth. Based on the spectra of fully striped impurity ions induced by the diagnostic beam the design work for toroidal charge exchange recombination spectroscopy (CXRS) system is presented. The 529 nm carbon VI (n = 8 − 7 transition) line seems to be the best choice for ion temperature and plasma rotationmore » measurements and the considered hardware is listed. The design work of the toroidal CXRS system is guided by essential simulation of expected spectral results under the J-TEXT tokamak operation conditions.« less

Improved edge charge exchange recombination spectroscopy in DIII-D

NASA Astrophysics Data System (ADS)

Chrystal, C.; Burrell, K. H.; Grierson, B. A.; Haskey, S. R.; Groebner, R. J.; Kaplan, D. H.; Briesemeister, A.

2016-11-01

The charge exchange recombination spectroscopy diagnostic on the DIII-D tokamak has been upgraded with the addition of more high radial resolution view chords near the edge of the plasma (r/a > 0.8). The additional views are diagnosed with the same number of spectrometers by placing fiber optics side-by-side at the spectrometer entrance with a precise separation that avoids wavelength shifted crosstalk without the use of bandpass filters. The new views improve measurement of edge impurity parameters in steep gradient, H-mode plasmas with many different shapes. The number of edge view chords with 8 mm radial separation has increased from 16 to 38. New fused silica fibers have improved light throughput and clarify the observation of non-Gaussian spectra that suggest the ion distribution function can be non-Maxwellian in low collisionality plasmas.

Energy conversion modeling of the intrinsic persistent luminescence of solids via energy transfer paths between transition levels.

PubMed

Huang, Bolong; Sun, Mingzi

2017-04-05

An energy conversion model has been established for the intrinsic persistent luminescence in solids related to the native point defect levels, formations, and transitions. In this study, we showed how the recombination of charge carriers between different defect levels along the zero phonon line (ZPL) can lead to energy conversions supporting the intrinsic persistent phosphorescence in solids. This suggests that the key driving force for this optical phenomenon is the pair of electrons hopping between different charged defects with negative-U eff . Such a negative correlation energy will provide a sustainable energy source for electron-holes to further recombine in a new cycle with a specific quantum yield. This will help us to understand the intrinsic persistent luminescence with respect to native point defect levels as well as the correlations of electronics and energetics.

Confinement of holes and electrons in blue organic light-emitting diodes with additional red emissive layers

NASA Astrophysics Data System (ADS)

Kang, Jin Sung; Yoo, Seung Il; Kim, Jin Wook; Yoon, Geum Jae; Yi, Seungjun; Kim, Woo Young

2016-02-01

We used various emissive layer (EML) structures with ultrathin red EMLs to enhance the charge carrier balance and carrier recombination rate in blue PHOLED devices. These EML materials have different energy gaps between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. The ultrathin red EMLs, which were inserted in between the blue EMLs, effectively confined the charge carriers in EML, and increased the carrier recombination rate. The thickness of the individual EML was optimized, under 30 nm of the total thickness of EML. The blue PHOLEDs with ultrathin red EMLs achieved a luminous efficiency of 19.24 cd/A, which was 28.7% higher than those without ultrathin red EMLs, and the maximum external quantum efficiency was 11.81% at 500 cd/m2.

Improved edge charge exchange recombination spectroscopy in DIII-D.

PubMed

Chrystal, C; Burrell, K H; Grierson, B A; Haskey, S R; Groebner, R J; Kaplan, D H; Briesemeister, A

2016-11-01

The charge exchange recombination spectroscopy diagnostic on the DIII-D tokamak has been upgraded with the addition of more high radial resolution view chords near the edge of the plasma (r/a > 0.8). The additional views are diagnosed with the same number of spectrometers by placing fiber optics side-by-side at the spectrometer entrance with a precise separation that avoids wavelength shifted crosstalk without the use of bandpass filters. The new views improve measurement of edge impurity parameters in steep gradient, H-mode plasmas with many different shapes. The number of edge view chords with 8 mm radial separation has increased from 16 to 38. New fused silica fibers have improved light throughput and clarify the observation of non-Gaussian spectra that suggest the ion distribution function can be non-Maxwellian in low collisionality plasmas.

Multichordal charge exchange recombination spectroscopy on Doublet III (abstract)

NASA Astrophysics Data System (ADS)

Seraydarian, R. P.; Burrell, K. H.; Kahn, C.

1985-05-01

Single shot, multipoint ion temperature and plasma rotation profiles have been routinely obtained on the Doublet III tokamak for 32 consecutive time slices with 20-ms resolution. A six-chord tangentially viewing spectroscopic diagnostic has been built to look at radiation emitted by fully stripped low-Z impurity ions (He, C, O) that have undergone charge exchange recombination with hydrogen atoms from a 3-MW heating beam. The main components of the instrument are a single monochromator for wavelength dispersion, a single image intensifier tube for photon gain, and a pair of 1024-element linear photodiode arrays for detection. A special arrangement of fiber optics allows simultaneous data acquisition from all chords without the use of scanning mirrors or other moving parts. Ion temperature profiles taken under a variety of plasma conditions will be presented.

Comparison of chitosan and chitosan nanoparticles on the performance and charge recombination of water-based gel electrolyte in dye sensitized solar cells.

PubMed

Khalili, Malihe; Abedi, Mohammad; Amoli, Hossein Salar; Mozaffari, Seyed Ahmad

2017-11-01

In commercialization of liquid dye-sensitized solar cells (DSSCs), whose leakage, evaporation and toxicity of organic solvents are limiting factors, replacement of organic solvents with water-based gel electrolyte is recommended. This work reports on utilizing and comparison of chitosan and chitosan nanoparticle as different gelling agents in preparation of water-based gel electrolyte in fabrication of dye sensitized solar cells. All photovoltaic parameters such as open circuit voltage (V oc ), fill factor (FF), short circuit current density (J sc ) and conversion efficiency (η) were measured. For further characterization, electrochemical impedance spectroscopy (EIS) was used to study the charge transfer at Pt/electrolyte interface and charge recombination and electron transport at TiO 2 /dye/electrolyte interface. Significant improvements in conversion efficiency and short circuit current density of DSSCs fabricated by chitosan nanoparticle were observed that can be attributed to the higher mobility of I 3 - due to the lower viscosity and smaller size of chitosan nanoparticles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electro-optical modeling of bulk heterojunction solar cells

NASA Astrophysics Data System (ADS)

Kirchartz, Thomas; Pieters, Bart E.; Taretto, Kurt; Rau, Uwe

2008-11-01

We introduce a model for charge separation in bulk heterojunction solar cells that combines exciton transport to the interface between donor and acceptor phases with the dissociation of the bound electron/hole pair. We implement this model into a standard semiconductor device simulator, thereby creating a convenient method to simulate the optical and electrical characteristics of a bulk heterojunction solar cell with a commercially available program. By taking into account different collection probabilities for the excitons in the polymer and the fullerene, we are able to reproduce absorptance, internal and external quantum efficiency, as well as current/voltage curves of bulk heterojunction solar cells. We further investigate the influence of mobilities of the free excitons as well as the mobilities of the free charge carriers on the performance of bulk heterojunction solar cells. We find that, in general, the highest efficiencies are achieved with the highest mobilities. However, an optimum finite mobility of free charge carriers can result from a large recombination velocity at the contacts. In contrast, Langevin-type of recombination cannot lead to finite optimum mobilities even though this mechanism has a strong dependence on the free carrier mobilities.

Crystallization of calcium oxalates is controlled by molecular hydrophilicity and specific polyanion-crystal interactions.

PubMed

Grohe, Bernd; Taller, Adam; Vincent, Peter L; Tieu, Long D; Rogers, Kem A; Heiss, Alexander; Sørensen, Esben S; Mittler, Silvia; Goldberg, Harvey A; Hunter, Graeme K

2009-10-06

To gain more insight into protein structure-function relationships that govern ectopic biomineralization processes in kidney stone formation, we have studied the ability of urinary proteins (Tamm-Horsfall protein, osteopontin (OPN), prothrombin fragment 1 (PTF1), bikunin, lysozyme, albumin, fetuin-A), and model compounds (a bikunin fragment, recombinant-, milk-, bone osteopontin, poly-L-aspartic acid (poly asp), poly-L-glutamic acid (poly glu)) in modulating precipitation reactions of kidney stone-related calcium oxalate mono- and dihydrates (COM, COD). Combining scanning confocal microscopy and fluorescence imaging, we determined the crystal faces of COM with which these polypeptides interact; using scanning electron microscopy, we characterized their effects on crystal habits and precipitated volumes. Our findings demonstrate that polypeptide adsorption to COM crystals is dictated first by the polypeptide's affinity for the crystal followed by its preference for a crystal face: basic and relatively hydrophobic macromolecules show no adsorption, while acidic and more hydrophilic polypeptides adsorb either nonspecifically to all faces of COM or preferentially to {100}/{121} edges and {100} faces. However, investigating calcium oxalates grown in the presence of these polypeptides showed that some acidic proteins that adsorb to crystals do not affect crystallization, even if present in excess of physiological concentrations. These proteins (albumin, bikunin, PTF1, recombinant OPN) have estimated total hydrophilicities from 200 to 850 kJ/mol and net negative charges from -9 to -35, perhaps representing a "window" in which proteins adsorb and coat urinary crystals (support of excretion) without affecting crystallization. Strongest effects on crystallization were observed for polypeptides that are either highly hydrophilic (>950 kJ/mol) and highly carboxylated (poly asp, poly glu), or else highly hydrophilic and highly phosphorylated (native OPN isoforms), suggesting that highly hydrophilic proteins strongly affect precipitation processes in the urinary tract. Therefore, the level of hydrophilicity and net charge is a critical factor in the ability of polypeptides to affect crystallization and to regulate biomineralization processes.

Bulk lifetime characterization of corona charged silicon wafers with high resistivity by means of microwave detected photoconductivity

NASA Astrophysics Data System (ADS)

Engst, C. R.; Rommel, M.; Bscheid, C.; Eisele, I.; Kutter, C.

2017-12-01

Minority carrier lifetime (lifetime) measurements are performed on corona-charged silicon wafers by means of Microwave Detected Photoconductivity (MDP). The corona charge is deposited on the front and back sides of oxidized wafers in order to adjust accumulation conditions. Once accumulation is established, interface recombination is suppressed and bulk lifetimes are obtained. Neither contacts nor non-CMOS compatible preparation techniques are required in order to achieve accumulation conditions, which makes the method ideally suited for inline characterization. The novel approach, termed ChargedMDP (CMDP), is used to investigate neutron transmutation doped (NTD) float zone silicon with resistivities ranging from 6.0 to 8.2 kΩ cm. The bulk properties of 150 mm NTD wafers are analyzed in detail by performing measurements of the carrier lifetime and the steady-state photoconductivity at various injection levels. The results are compared with MDP measurements of uncharged wafers as well as to the established charged microwave detected Photoconductance Decay (charge-PCD) method. Besides analyzing whole wafers, CMDP measurements are performed on oxide test-structures on a patterned wafer. Finally, the oxide properties are characterized by means of charge-PCD as well as capacitance-voltage measurements. With CMDP, average bulk lifetimes up to 33.1 ms are measured, whereby significant variations are observed among wafers, which are produced out of the same ingot but oxidized in different furnaces. The observed lifetime variations are assumed to be caused by contaminations, which are introduced during the oxidation process. The results obtained by CMDP were neither accessible by means of conventional MDP measurements of uncharged wafers nor with the established charge-PCD method.

Charge heterogeneity: Basic antibody charge variants with increased binding to Fc receptors

PubMed Central

Hintersteiner, Beate; Lingg, Nico; Zhang, Peiqing; Woen, Susanto; Hoi, Kong Meng; Stranner, Stefan; Wiederkum, Susanne; Mutschlechner, Oliver; Schuster, Manfred; Loibner, Hans; Jungbauer, Alois

2016-01-01

ABSTRACT We identified active isoforms of the chimeric anti-GD2 antibody, ch14.18, a recombinant antibody produced in Chinese hamster ovary cells, which is already used in clinical trials.1,2,3 We separated the antibody by high resolution ion-exchange chromatography with linear pH gradient elution into acidic, main and basic charge variants on a preparative scale yielding enough material for an in-depth study of the sources and the effects of microheterogeneity. The binding affinity of the charge variants toward the antigen and various cell surface receptors was studied by Biacore. Effector functions were evaluated using cellular assays for antibody-dependent cell-mediated cytotoxicity and complement-dependent cytotoxicity. Basic charge variants showed increased binding to cell surface receptor FcγRIIIa, which plays a major role in regulating effector functions. Furthermore, increased binding of the basic fractions to the neonatal receptor was observed. As this receptor mediates the prolonged half-life of IgG in human serum, this data may well hint at an increased serum half-life of these basic variants compared to their more acidic counterparts. Different glycoform patterns, C-terminal lysine clipping and N-terminal pyroglutamate formation were identified as the main structural sources for the observed isoform pattern. Potential differences in structural stability between individual charge variant fractions by nano differential scanning calorimetry could not been detected. Our in-vitro data suggests that the connection between microheterogeneity and the biological activity of recombinant antibody therapeutics deserves more attention than commonly accepted. PMID:27559765

Characterization of memory and measurement history in photoconductivity of nanocrystal arrays

NASA Astrophysics Data System (ADS)

Fairfield, Jessamyn A.; Dadosh, Tali; Drndic, Marija

2010-10-01

Photoconductivity in nanocrystal films has been previously characterized, but memory effects have received little attention despite their importance for device applications. We show that the magnitude and temperature dependence of the photocurrent in CdSe/ZnS core-shell nanocrystal arrays depends on the illumination and electric field history. Changes in photoconductivity occur on a few-hour timescale, and subband gap illumination of nanocrystals prior to measurements modifies the photocurrent more than band gap illumination. The observed effects can be explained by charge traps within the band gap that are filled or emptied, which may alter nonradiative recombination processes and affect photocurrent.

Raman spectroscopy and time-resolved photoluminescence of BN and BxCyNz nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, J.; Han, Wei-Qiang; Walukiewicz, W.

2004-01-21

We report Raman and time-resolved photoluminescence spectroscopic studies of multiwalled BN and B{sub x}C{sub y}N{sub z} nanotubes. The Raman spectroscopy shows that the as-grown B{sub x}C{sub y}N{sub z} charge recombination, respectively. Comparison of the photoluminescence of BN nanotubes to that decay process is characterized by two time constants that are attributed to intra- and inter-BN sheet nanotubes as predicted by theory. nanotubes are radially phase separated into BN shells and carbon shells. The photoluminescence of hexagonal BN is consistent with the existence of a spatially indirect band gap in multi-walled BN.

Science Notes.

ERIC Educational Resources Information Center

Talbot, Chris; And Others

1991-01-01

Twenty science experiments are presented. Topics include recombinant DNA, physiology, nucleophiles, reactivity series, molar volume of gases, spreadsheets in chemistry, hydrogen bonding, composite materials, radioactive decay, magnetism, speed, charged particles, compression waves, heat transfer, Ursa Major, balloons, current, and expansion of…

Recombination in Enteroviruses Is a Biphasic Replicative Process Involving the Generation of Greater-than Genome Length ‘Imprecise’ Intermediates

PubMed Central

Lowry, Kym; Woodman, Andrew; Cook, Jonathan; Evans, David J.

2014-01-01

Recombination in enteroviruses provides an evolutionary mechanism for acquiring extensive regions of novel sequence, is suggested to have a role in genotype diversity and is known to have been key to the emergence of novel neuropathogenic variants of poliovirus. Despite the importance of this evolutionary mechanism, the recombination process remains relatively poorly understood. We investigated heterologous recombination using a novel reverse genetic approach that resulted in the isolation of intermediate chimeric intertypic polioviruses bearing genomes with extensive duplicated sequences at the recombination junction. Serial passage of viruses exhibiting such imprecise junctions yielded progeny with increased fitness which had lost the duplicated sequences. Mutations or inhibitors that changed polymerase fidelity or the coalescence of replication complexes markedly altered the yield of recombinants (but did not influence non-replicative recombination) indicating both that the process is replicative and that it may be possible to enhance or reduce recombination-mediated viral evolution if required. We propose that extant recombinants result from a biphasic process in which an initial recombination event is followed by a process of resolution, deleting extraneous sequences and optimizing viral fitness. This process has implications for our wider understanding of ‘evolution by duplication’ in the positive-strand RNA viruses. PMID:24945141

Solution-Processed Phosphorescent Organic Light-Emitting Diodes with Ultralow Driving Voltage and Very High Power Efficiency

NASA Astrophysics Data System (ADS)

Wang, Shumeng; Wang, Xingdong; Yao, Bing; Zhang, Baohua; Ding, Junqiao; Xie, Zhiyuan; Wang, Lixiang

2015-07-01

To realize power efficient solution-processed phosphorescent organic light-emitting diodes (s-PhOLEDs), the corresponding high driving voltage issue should be well solved. To solve it, efforts have been devoted to the exploitation of novel host or interfacial materials. However, the issues of charge trapping of phosphor and/or charge injection barrier are still serious, largely restraining the power efficiency (PE) levels. Herein, with the utilization of an exciplex-forming couple 4, 4‧, 4″ -tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA) and 1,3,5-tri(m-pyrid-3-yl-phenyl)benzene (TmPyPB), the efficient charge injection and transporting, barrier-free hole-electron recombination for the formation of the interfacial exciplex, and elimination of charge traps of phosphors in the emissive layer are realized simultaneously, resulting in a turn-on voltage of 2.36 V, a record high PE of 97.2 lm W-1, as well as extremely low driving voltage of 2.60 V at 100 cd m-2, 3.03 V at 1000 cd m-2 and 4.08 V at 10000 cd m-2. This report is the first time that the PE performance of s-PhOLED approaches 100 lm W-1 high level, even superior to the corresponding state-of-the-art performance of the same color vacuum-deposited PhOLED (v-PhOLED) counterpart. We anticipate this report opens a new avenue for achieving power efficient monochromatic and white s-PhOLEDs with simple structures.

Solution-Processed Phosphorescent Organic Light-Emitting Diodes with Ultralow Driving Voltage and Very High Power Efficiency

PubMed Central

Wang, Shumeng; Wang, Xingdong; Yao, Bing; Zhang, Baohua; Ding, Junqiao; Xie, Zhiyuan; Wang, Lixiang

2015-01-01

To realize power efficient solution-processed phosphorescent organic light-emitting diodes (s-PhOLEDs), the corresponding high driving voltage issue should be well solved. To solve it, efforts have been devoted to the exploitation of novel host or interfacial materials. However, the issues of charge trapping of phosphor and/or charge injection barrier are still serious, largely restraining the power efficiency (PE) levels. Herein, with the utilization of an exciplex-forming couple 4, 4′, 4″ -tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA) and 1,3,5-tri(m-pyrid-3-yl-phenyl)benzene (TmPyPB), the efficient charge injection and transporting, barrier-free hole-electron recombination for the formation of the interfacial exciplex, and elimination of charge traps of phosphors in the emissive layer are realized simultaneously, resulting in a turn-on voltage of 2.36 V, a record high PE of 97.2 lm W−1, as well as extremely low driving voltage of 2.60 V at 100 cd m−2, 3.03 V at 1000 cd m−2 and 4.08 V at 10000 cd m−2. This report is the first time that the PE performance of s-PhOLED approaches 100 lm W−1 high level, even superior to the corresponding state-of-the-art performance of the same color vacuum-deposited PhOLED (v-PhOLED) counterpart. We anticipate this report opens a new avenue for achieving power efficient monochromatic and white s-PhOLEDs with simple structures. PMID:26204810

Solution-Processed Phosphorescent Organic Light-Emitting Diodes with Ultralow Driving Voltage and Very High Power Efficiency.

PubMed

Wang, Shumeng; Wang, Xingdong; Yao, Bing; Zhang, Baohua; Ding, Junqiao; Xie, Zhiyuan; Wang, Lixiang

2015-07-24

To realize power efficient solution-processed phosphorescent organic light-emitting diodes (s-PhOLEDs), the corresponding high driving voltage issue should be well solved. To solve it, efforts have been devoted to the exploitation of novel host or interfacial materials. However, the issues of charge trapping of phosphor and/or charge injection barrier are still serious, largely restraining the power efficiency (PE) levels. Herein, with the utilization of an exciplex-forming couple 4, 4', 4″-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA) and 1,3,5-tri(m-pyrid-3-yl-phenyl)benzene (TmPyPB), the efficient charge injection and transporting, barrier-free hole-electron recombination for the formation of the interfacial exciplex, and elimination of charge traps of phosphors in the emissive layer are realized simultaneously, resulting in a turn-on voltage of 2.36 V, a record high PE of 97.2 lm W(-1), as well as extremely low driving voltage of 2.60 V at 100 cd m(-2), 3.03 V at 1000 cd m(-2) and 4.08 V at 10000 cd m(-2). This report is the first time that the PE performance of s-PhOLED approaches 100 lm W(-1) high level, even superior to the corresponding state-of-the-art performance of the same color vacuum-deposited PhOLED (v-PhOLED) counterpart. We anticipate this report opens a new avenue for achieving power efficient monochromatic and white s-PhOLEDs with simple structures.

A dynamic Monte Carlo study of anomalous current voltage behaviour in organic solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feron, K., E-mail: Krishna.Feron@csiro.au; Fell, C. J.; CSIRO Energy Flagship, Newcastle, NSW 2300

2014-12-07

We present a dynamic Monte Carlo (DMC) study of s-shaped current-voltage (I-V) behaviour in organic solar cells. This anomalous behaviour causes a substantial decrease in fill factor and thus power conversion efficiency. We show that this s-shaped behaviour is induced by charge traps that are located at the electrode interface rather than in the bulk of the active layer, and that the anomaly becomes more pronounced with increasing trap depth or density. Furthermore, the s-shape anomaly is correlated with interface recombination, but not bulk recombination, thus highlighting the importance of controlling the electrode interface. While thermal annealing is known tomore » remove the s-shape anomaly, the reason has been not clear, since these treatments induce multiple simultaneous changes to the organic solar cell structure. The DMC modelling indicates that it is the removal of aluminium clusters at the electrode, which act as charge traps, that removes the anomalous I-V behaviour. Finally, this work shows that the s-shape becomes less pronounced with increasing electron-hole recombination rate; suggesting that efficient organic photovoltaic material systems are more susceptible to these electrode interface effects.« less

Combination of a recombinant bacterium with organonitrile-degrading and biofilm-forming capability and a positively charged carrier for organonitriles removal.

PubMed

Li, Chunyan; Sun, Yueling; Yue, Zhenlei; Huang, Mingyan; Wang, Jinming; Chen, Xi; An, Xuejiao; Zang, Hailian; Li, Dapeng; Hou, Ning

2018-04-10

The immobilization of organonitrile-degrading bacteria via the addition of biofilm-forming bacteria represents a promising technology for the treatment of organonitrile-containing wastewater, but biofilm-forming bacteria simply mixed with degrading bacteria may reduce the biodegradation efficiency. Nitrile hydratase and amidase genes, which play critical roles in organonitriles degradation, were cloned and transformed into the biofilm-forming bacterium Bacillus subtilis N4 to construct a recombinant bacterium B. subtilis N4/pHTnha-ami. Modified polyethylene carriers with positive charge was applied to promote bacterial adherence and biofilm formation. The immobilized B. subtilis N4/pHTnha-ami was resistant to organonitriles loading shocks and could remove organic cyanide ion with a initial concentration of 392.6 mg/L for 24 h in a moving bed biofilm reactor. The imputed quorum-sensing signal and the high-throughput sequencing analysis of the biofilm indicated that B. subtilis N4/pHTnha-ami was successfully immobilized and became dominant. The successful application of the immobilized recombinant bacterium offers a novel strategy for the biodegradation of recalcitrant compounds. Copyright © 2018 Elsevier B.V. All rights reserved.

Signal yields, energy resolution, and recombination fluctuations in liquid xenon

NASA Astrophysics Data System (ADS)

Akerib, D. S.; Alsum, S.; Araújo, H. M.; Bai, X.; Bailey, A. J.; Balajthy, J.; Beltrame, P.; Bernard, E. P.; Bernstein, A.; Biesiadzinski, T. P.; Boulton, E. M.; Bramante, R.; Brás, P.; Byram, D.; Cahn, S. B.; Carmona-Benitez, M. C.; Chan, C.; Chiller, A. A.; Chiller, C.; Currie, A.; Cutter, J. E.; Davison, T. J. R.; Dobi, A.; Dobson, J. E. Y.; Druszkiewicz, E.; Edwards, B. N.; Faham, C. H.; Fiorucci, S.; Gaitskell, R. J.; Gehman, V. M.; Ghag, C.; Gibson, K. R.; Gilchriese, M. G. D.; Hall, C. R.; Hanhardt, M.; Haselschwardt, S. J.; Hertel, S. A.; Hogan, D. P.; Horn, M.; Huang, D. Q.; Ignarra, C. M.; Ihm, M.; Jacobsen, R. G.; Ji, W.; Kamdin, K.; Kazkaz, K.; Khaitan, D.; Knoche, R.; Larsen, N. A.; Lee, C.; Lenardo, B. G.; Lesko, K. T.; Lindote, A.; Lopes, M. I.; Manalaysay, A.; Mannino, R. L.; Marzioni, M. F.; McKinsey, D. N.; Mei, D.-M.; Mock, J.; Moongweluwan, M.; Morad, J. A.; Murphy, A. St. J.; Nehrkorn, C.; Nelson, H. N.; Neves, F.; O'Sullivan, K.; Oliver-Mallory, K. C.; Palladino, K. J.; Pease, E. K.; Phelps, P.; Reichhart, L.; Rhyne, C.; Shaw, S.; Shutt, T. A.; Silva, C.; Solmaz, M.; Solovov, V. N.; Sorensen, P.; Stephenson, S.; Sumner, T. J.; Szydagis, M.; Taylor, D. J.; Taylor, W. C.; Tennyson, B. P.; Terman, P. A.; Tiedt, D. R.; To, W. H.; Tripathi, M.; Tvrznikova, L.; Uvarov, S.; Verbus, J. R.; Webb, R. C.; White, J. T.; Whitis, T. J.; Witherell, M. S.; Wolfs, F. L. H.; Xu, J.; Yazdani, K.; Young, S. K.; Zhang, C.; LUX Collaboration

2017-01-01

This work presents an analysis of monoenergetic electronic recoil peaks in the dark-matter-search and calibration data from the first underground science run of the Large Underground Xenon (LUX) detector. Liquid xenon charge and light yields for electronic recoil energies between 5.2 and 661.7 keV are measured, as well as the energy resolution for the LUX detector at those same energies. Additionally, there is an interpretation of existing measurements and descriptions of electron-ion recombination fluctuations in liquid xenon as limiting cases of a more general liquid xenon recombination fluctuation model. Measurements of the standard deviation of these fluctuations at monoenergetic electronic recoil peaks exhibit a linear dependence on the number of ions for energy deposits up to 661.7 keV, consistent with previous LUX measurements between 2 and 16 keV with 3H. We highlight similarities in liquid xenon recombination for electronic and nuclear recoils with a comparison of recombination fluctuations measured with low-energy calibration data.

Signal yields, energy resolution, and recombination fluctuations in liquid xenon

DOE PAGES

Akerib, D. ?S.; Alsum, S.; Ara?jo, H. ?M.; ...

2017-01-19

This study presents an analysis of monoenergetic electronic recoil peaks in the dark-matter-search and calibration data from the first underground science run of the Large Underground Xenon (LUX) detector. Liquid xenon charge and light yields for electronic recoil energies between 5.2 and 661.7 keV are measured, as well as the energy resolution for the LUX detector at those same energies. Additionally, there is an interpretation of existing measurements and descriptions of electron-ion recombination fluctuations in liquid xenon as limiting cases of a more general liquid xenon recombination fluctuation model. Measurements of the standard deviation of these fluctuations at monoenergetic electronicmore » recoil peaks exhibit a linear dependence on the number of ions for energy deposits up to 661.7 keV, consistent with previous LUX measurements between 2 and 16 keV with 3H. We highlight similarities in liquid xenon recombination for electronic and nuclear recoils with a comparison of recombination fluctuations measured with low-energy calibration data.« less

Ionospheric chemistry. [minor neutrals and ionized constituents of thermosphere

NASA Technical Reports Server (NTRS)

Torr, D. G.

1979-01-01

This report deals primarily with progress in the chemistry of minor neutrals and ionized constituents of the thermosphere. Significant progress was made over the last few years in quantitative studies of many chemical processes. This success was primarily due to the advent of multiparameter multisatellite programs which permitted accurate simultaneous measurements to be made of many important parameters. In many cases studies of chemical reactions were made with laboratory-like precision. Rate coefficients have been derived as functions of temperature for a number of important reactions. New information has been acquired on nearly every major process which occurs in the thermosphere, including the recombination rates of all major molecular ions, charge transfer reactions, ion atom interchange reactions, and reactions of neutral and ionized metastable atoms and molecules.

Interfacial Charge Transfer States in Condensed Phase Systems

NASA Astrophysics Data System (ADS)

Vandewal, Koen

2016-05-01

Intermolecular charge transfer (CT) states at the interface between electron-donating (D) and electron-accepting (A) materials in organic thin films are characterized by absorption and emission bands within the optical gap of the interfacing materials. CT states efficiently generate charge carriers for some D-A combinations, and others show high fluorescence quantum efficiencies. These properties are exploited in organic solar cells, photodetectors, and light-emitting diodes. This review summarizes experimental and theoretical work on the electronic structure and interfacial energy landscape at condensed matter D-A interfaces. Recent findings on photogeneration and recombination of free charge carriers via CT states are discussed, and relations between CT state properties and optoelectronic device parameters are clarified.

Cycle of charge carrier states with formation and extinction of a floating gate in an ambipolar tetracyanoquaterthienoquinoid-based field-effect transistor

NASA Astrophysics Data System (ADS)

Itoh, Takuro; Toyota, Taro; Higuchi, Hiroyuki; Matsushita, Michio M.; Suzuki, Kentaro; Sugawara, Tadashi

2017-03-01

A tetracyanoquaterthienoquinoid (TCT4Q)-based field effect transistor is characterized by the ambipolar transfer characteristics and the facile shift of the threshold voltage induced by the bias stress. The trapping and detrapping kinetics of charge carriers was investigated in detail by the temperature dependence of the decay of source-drain current (ISD). We found a repeatable formation of a molecular floating gate is derived from a 'charge carrier-and-gate' cycle comprising four stages, trapping of mobile carriers, formation of a floating gate, induction of oppositely charged mobile carriers, and recombination between mobile and trapped carriers to restore the initial state.

Dynamics and mechanisms of interfacial photoinduced electron transfer processes of third generation photovoltaics and photocatalysis.

PubMed

Bauer, Christophe; Teuscher, Joël; Brauer, Jan C; Punzi, Angela; Marchioro, Arianna; Ghadiri, Elham; De Jonghe, Jelissa; Wielopolski, Mateusz; Banerji, Natalie; Moser, Jacques E

2011-01-01

Photoinduced electron transfer (PET) across molecular/bulk interfaces has gained attention only recently and is still poorly understood. These interfaces offer an excellent case study, pertinent to a variety of photovoltaic systems, photo- and electrochemistry, molecular electronics, analytical detection, photography, and quantum confinement devices. They play in particular a key role in the emerging fields of third-generation photovoltaic energy converters and artificial photosynthetic systems aimed at the production of solar fuels, creating a need for a better understanding and theoretical treatment of the dynamics and mechanisms of interfacial PET processes. We aim to achieve a fundamental understanding of these phenomena by designing experiments that can be used to test and alter modern theory and computational modeling. One example illustrating recent investigations into the details of the ultrafast processes that form the basis for photoinduced charge separation at a molecular/bulk interface relevant to dye-sensitized solar cells is briefly presented here: Kinetics of interfacial PET and charge recombination processes were measured by fs and ns transient spectroscopy in a heterogeneous donor-bridge-acceptor (D-B-A) system, where D is a Ru(II)(terpyridyl-PO3)(NCS)3 complex, B an oligo-p-phenylene bridge, and A nanocrystalline TiO2. The forward ET reaction was found to be faster than vibrational relaxation of the vibronic excited state of the donor. Instead, the back ET occurred on the micros time scale and involved fully thermalized species. The D-A distance dependence of the electron transfer rate was studied by varying the number of p-phenylene units contained in the bridge moiety. The remarkably low damping factor beta = 0.16 angstroms(-1) observed for the ultrafast charge injection from the dye excited state into the conduction band of TiO2 is attributed to the coupling of electron tunneling with nonequilibrium vibrations redistributed on the bridge, giving rise to polaronic transport of charges from the donor ligand to the acceptor solid oxide surface.

Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

NASA Astrophysics Data System (ADS)

Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J.; Johnston, Michael B.; Herz, Laura M.

2014-08-01

The optoelectronic properties of the mixed hybrid lead halide perovskite CH3NH3PbI3-xClx have been subject to numerous recent studies related to its extraordinary capabilities as an absorber material in thin film solar cells. While the greatest part of the current research concentrates on the behavior of the perovskite at room temperature, the observed influence of phonon-coupling and excitonic effects on charge carrier dynamics suggests that low-temperature phenomena can give valuable additional insights into the underlying physics. Here, we present a temperature-dependent study of optical absorption and photoluminescence (PL) emission of vapor-deposited CH3NH3PbI3-xClx exploring the nature of recombination channels in the room- and the low-temperature phase of the material. On cooling, we identify an up-shift of the absorption onset by about 0.1 eV at about 100 K, which is likely to correspond to the known tetragonal-to-orthorhombic transition of the pure halide CH3NH3PbI3. With further decreasing temperature, a second PL emission peak emerges in addition to the peak from the room-temperature phase. The transition on heating is found to occur at about 140 K, i.e., revealing significant hysteresis in the system. While PL decay lifetimes are found to be independent of temperature above the transition, significantly accelerated recombination is observed in the low-temperature phase. Our data suggest that small inclusions of domains adopting the room-temperature phase are responsible for this behavior rather than a spontaneous increase in the intrinsic rate constants. These observations show that even sparse lower-energy sites can have a strong impact on material performance, acting as charge recombination centres that may detrimentally affect photovoltaic performance but that may also prove useful for optoelectronic applications such as lasing by enhancing population inversion.

A novel multimodal chromatography based single step purification process for efficient manufacturing of an E. coli based biotherapeutic protein product.

PubMed

Bhambure, Rahul; Gupta, Darpan; Rathore, Anurag S

2013-11-01

Methionine oxidized, reduced and fMet forms of a native recombinant protein product are often the critical product variants which are associated with proteins expressed as bacterial inclusion bodies in E. coli. Such product variants differ from native protein in their structural and functional aspects, and may lead to loss of biological activity and immunogenic response in patients. This investigation focuses on evaluation of multimodal chromatography for selective removal of these product variants using recombinant human granulocyte colony stimulating factor (GCSF) as the model protein. Unique selectivity in separation of closely related product variants was obtained using combined pH and salt based elution gradients in hydrophobic charge induction chromatography. Simultaneous removal of process related impurities was also achieved in flow-through leading to single step purification process for the GCSF. Results indicate that the product recovery of up to 90.0% can be obtained with purity levels of greater than 99.0%. Binding the target protein at pH

Free energy gap laws for the pulse-induced and stationary fluorescence quenching by reversible charge transfer in polar solutions.

PubMed

Khokhlova, Svetlana S; Burshtein, Anatoly I

2011-01-21

The Stern-Volmer constants for either pulse-induced or stationary fluorescence being quenched by a contact charge transfer are calculated and their free energy dependencies (the free energy gap laws) are specified. The reversibility of charge transfer is taken into account as well as spin conversion in radical ion pairs, followed by their recombination in either singlet or triplet neutral products. The natural decay of triplets as well as their impurity quenching by ionization are accounted for when estimating the fluorescence quantum yield and its free energy dependence.

Modelling charge interactions in the prion protein: predictions for pathogenesis.

PubMed

Warwicker, J

1999-04-30

Calculations are presented for the pH-dependence of stability and membrane charge complementarity of prion protein fragments. The theoretical results are compared with reported characterisations of prion protein folding in vitro. Discussion of models for conformational change and pathogenesis in vivo leads to the prediction of amino acids that could mediate sensitivity to the endosomal pH and to a design strategy for recombinant prion proteins with an increased susceptibility to prion proteinSc-like properties in vitro. In this model, the protective effect of certain basic polymorphisms can be interpreted in terms of oligomerisation on a negatively-charged surface.

Phosphorene quantum dot-fullerene nanocomposites for solar energy conversion: An unexplored inorganic-organic nanohybrid with novel photovoltaic properties

NASA Astrophysics Data System (ADS)

Rajbanshi, Biplab; Kar, Moumita; Sarkar, Pallavi; Sarkar, Pranab

2017-10-01

Using the self-consistent charge density-functional based tight-binding (SCC-DFTB) method, coupled with time-dependent density functional theory (TDDFT) calculations, for the first time we explore the possibility of use of phosphorene quantum dots in solar energy harvesting devices. The phosphorene quantum dots-fullerene (PQDs-PCBA) nanocomposites show type-II band alignment indicating spatial separation of charge carriers. The TDDFT calculations also show that the PQD-fullerene nanocomposites seem to be exciting material for future generation solar energy harvester, with extremely fast charge transfer and very poor recombination rate.

Dielectronic recombination experiments at the storage rings: From the present CSR to the future HIAF

NASA Astrophysics Data System (ADS)

Huang, Z. K.; Wen, W. Q.; Xu, X.; Wang, H. B.; Dou, L. J.; Chuai, X. Y.; Zhu, X. L.; Zhao, D. M.; Li, J.; Ma, X. M.; Mao, L. J.; Yang, J. C.; Yuan, Y. J.; Xu, W. Q.; Xie, L. Y.; Xu, T. H.; Yao, K.; Dong, C. Z.; Zhu, L. F.; Ma, X.

2017-10-01

Dielectronic recombination (DR) experiments of highly charged ions at the storage rings have been developed as a precision spectroscopic tool to investigate the atomic structure as well as nuclear properties of stable and unstable nuclei. The DR experiment on lithium-like argon ions was successfully performed at main Cooler Storage Ring (CSRm) at Heavy Ion Research Facility in Lanzhou (HIRFL) accelerator complex. The DR experiments on heavy highly charged ions and even radioactive ions are currently under preparation at the experimental Cooler Storage Ring (CSRe) at HIRFL. The current status of DR experiments at the CSRm and the preparation of the DR experiments at the CSRe are presented. In addition, an overview of DR experiments by employing an electron cooler and a separated ultra-cold electron target at the upcoming High Intensity heavy ion Accelerator Facility (HIAF) will be given.

Improved edge charge exchange recombination spectroscopy in DIII-D

DOE PAGES

Chrystal, Colin; Burrell, K. H.; Grierson, Brian A.; ...

2016-08-02

The charge exchange recombination spectroscopy diagnostic on the DIII-D tokamak has been upgraded with the addition of more high radial resolution view chords near the edge of the plasma ( r/a > 0.8). The additional views are diagnosed with the same number of spectrometers by placing fiber optics side-by-side at the spectrometer entrance with a precise separation that avoids wavelength shifted crosstalk without the use of bandpass filters. The new views improve measurement of edge impurity parameters in steep gradient, H-mode plasmas with many different shapes. The number of edge view chords with 8 mm radial separation has increased frommore » 16 to 38.As a result, new fused silica fibers have improved light throughput and clarify the observation of non-Gaussian spectra that suggest the ion distribution function can be non-Maxwellian in low collisionality plasmas.« less

Anion Order and Spontaneous Polarization in LaTiO2N Oxynitride Thin Films

NASA Astrophysics Data System (ADS)

Vonrüti, Nathalie; Aschauer, Ulrich

2018-01-01

The perovskite oxynitride LaTiO2N is a promising material for photocatalytic water splitting under visible light. One of the obstacles towards higher efficiencies of this and similar materials stems from charge-carrier recombination, which could be suppressed by the surface charges resulting from the dipolar field in polar materials. In this study, we investigate the spontaneous polarization in epitaxially strained LaTiO2N thin films via density functional theory calculations. The effect of epitaxial strain on the anion order, resulting out-of-plane polarization, energy barriers for polarization reversal, and corresponding coercive fields are studied. We find that for compressive strains larger than 4% the thermodynamically stable anion order is polar along the out-of-plane direction and has a coercive field comparable to other switchable ferroelectrics. Our results show that strained LaTiO2N could indeed suppress carrier recombination and lead to enhanced photocatalytic activities.

Dynamics of Photoexcited State of Semiconductor Quantum Dots

NASA Astrophysics Data System (ADS)

Trivedi, Dhara J.

In this thesis, non-adiabatic molecular dynamics (NAMD) of excited states in semiconductor quantum dots are investigated. Nanoscale systems provide important opportunities for theory and computation for research because the experimental tools often provide an incomplete picture of the structure and/or function of nanomaterials, and theory can often fill in missing features crucial in understanding what is being measured. The simulation of NAMD is an indispensable tool for understanding complex ultrafast photoinduced processes such as charge and energy transfer, thermal relaxation, and charge recombination. Based on the state-of-the-art ab initio approaches in both the energy and time domains, the thesis presents a comprehensive discussion of the dynamical processes in quantum dots, ranging from the initial photon absorption to the final emission. We investigate the energy relaxation and transfer rates in pure and surface passivated quantum dots of different sizes. The study establishes the fundamental mechanisms of the electron and hole relaxation processes with and without hole traps. We develop and implement more accurate and efficient methods for NAMD. These methods are advantageous over the traditional ones when one encounters classically forbidden transitions. We also explore the effect of decoherence and non-adiabatic couplings on the dynamics. The results indicate significant influence on the accuracy and related computational cost of the simulated dynamics.

Non-Radiative Carrier Recombination Enhanced by Two-Level Process: A First-Principles Study

NASA Astrophysics Data System (ADS)

Yang, Ji-Hui; Shi, Lin; Wang, Lin-Wang; Wei, Su-Huai

2016-02-01

Non-radiative recombination plays an important role in the performance of optoelectronic semiconductor devices such as solar cells and light-emitting diodes. Most textbook examples assume that the recombination process occurs through a single defect level, where one electron and one hole are captured and recombined. Based on this simple picture, conventional wisdom is that only defect levels near the center of the bandgap can be effective recombination centers. Here, we present a new two-level recombination mechanism: first, one type of carrier is captured through a defect level forming a metastable state; then the local defect configuration rapidly changes to a stable state, where the other type of carrier is captured and recombined through another defect level. This novel mechanism is applied to the recombination center in CdTe. We show that this two-level process can significantly increase the recombination rate (by three orders of magnitude) in agreement with experiments. We expect that this two-level recombination process can exist in a wide range of semiconductors, so its effect should be carefully examined in characterizing optoelectronic materials.

Time-resolved spectroscopic studies of photosynthetic reaction centers and tetrapyrrole chromophores for biomedical and solar-energy applications

NASA Astrophysics Data System (ADS)

Kee, Hooi Ling

2008-10-01

The photophysical properties of diverse tetrapyrrole chromophores as well as energy and electron transfer processes in tetrapyrrole dyads are investigated using static and time-resolved (femtoseconds to seconds) absorption and fluorescence spectroscopy. The goal of these studies is to elucidate the molecular design principals necessary to construct chromophores with the specific and tunable properties that will enhance applications in optical molecular imaging, photodynamic therapy, and solar-energy conversion. The kinetic properties of the transient intermediate P+H B- involving the bacteriopheophytin molecule HB on the normally inactive (B) cofactor branch of the bacterial photosynthetic reaction center are examined in Rhodobacter capsulatus mutants. Using nanosecond flash photolysis and F(L181)Y/Y(M208)F/L(M212)H mutant, the decay pathways and yields of P+HB- were measured, giving an overall yield of 13% for B-side charge separation P* → P+HB- → P+ QB- in this mutant. The goal of these studies is to understand the fundamental differences in the rates, yields, and mechanisms of charge separation and charge recombination along the two parallel electron-transport chains in the bacterial reaction center.

Charge Carrier Conduction Mechanism in PbS Quantum Dot Solar Cells: Electrochemical Impedance Spectroscopy Study.

PubMed

Wang, Haowei; Wang, Yishan; He, Bo; Li, Weile; Sulaman, Muhammad; Xu, Junfeng; Yang, Shengyi; Tang, Yi; Zou, Bingsuo

2016-07-20

With its properties of bandgap tunability, low cost, and substrate compatibility, colloidal quantum dots (CQDs) are becoming promising materials for optoelectronic applications. Additionally, solution-processed organic, inorganic, and hybrid ligand-exchange technologies have been widely used in PbS CQDs solar cells, and currently the maximum certified power conversion efficiency of 9.9% has been reported by passivation treatment of molecular iodine. Presently, there are still some challenges, and the basic physical mechanism of charge carriers in CQDs-based solar cells is not clear. Electrochemical impedance spectroscopy is a monitoring technology for current by changing the frequency of applied alternating current voltage, and it provides an insight into its electrical properties that cannot be measured by direct current testing facilities. In this work, we used EIS to analyze the recombination resistance, carrier lifetime, capacitance, and conductivity of two typical PbS CQD solar cells Au/PbS-TBAl/ZnO/ITO and Au/PbS-EDT/PbS-TBAl/ZnO/ITO, in this way, to better understand the charge carriers conduction mechanism behind in PbS CQD solar cells, and it provides a guide to design high-performance quantum-dots solar cells.

Hidden Charge States in Soft-X-Ray Laser-Produced Nanoplasmas Revealed by Fluorescence Spectroscopy

NASA Astrophysics Data System (ADS)

Schroedter, L.; Müller, M.; Kickermann, A.; Przystawik, A.; Toleikis, S.; Adolph, M.; Flückiger, L.; Gorkhover, T.; Nösel, L.; Krikunova, M.; Oelze, T.; Ovcharenko, Y.; Rupp, D.; Sauppe, M.; Wolter, D.; Schorb, S.; Bostedt, C.; Möller, T.; Laarmann, T.

2014-05-01

Highly charged ions are formed in the center of composite clusters by strong free-electron laser pulses and they emit fluorescence on a femtosecond time scale before competing recombination leads to neutralization of the nanoplasma core. In contrast to mass spectrometry that detects remnants of the interaction, fluorescence in the extreme ultraviolet spectral range provides fingerprints of transient states of high energy density matter. Spectra from clusters consisting of a xenon core and a surrounding argon shell show that a small fraction of the fluorescence signal comes from multiply charged xenon ions in the cluster core. Initially, these ions are as highly charged as the ions in the outer shells of pure xenon clusters with charge states up to at least 11+.

Dendronized fullerene-porphyrin conjugates in ortho, meta, and para positions: a charge-transfer assay.

PubMed

Krokos, Evangelos; Schubert, Christina; Spänig, Fabian; Ruppert, Michaela; Hirsch, Andreas; Guldi, Dirk M

2012-06-01

The physicochemical characterization, that is, ground and excited state, of a new series of dendronized porphyrin/fullerene electron donor-acceptor conjugates in nonaqueous and aqueous environments is reported. In contrast to previous work, we detail the charge-separation and charge-recombination dynamics in zinc and copper metalloporphyrins as a function of first- and second-generation dendrons as well as a function of ortho, meta, and para substitution. Both have an appreciable impact on the microenvironments of the redox-active constituents, namely the porphyrins and the fullerenes. As a matter of fact, the resulting charge-transfer dynamics were considerably impacted by the interplay between the associated forces that reach from dendron-induced shielding to dipole-charge interactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-ray spectroscopy diagnostics of a recombining plasma in laboratory astrophysics studies

NASA Astrophysics Data System (ADS)

Ryazantsev, S. N.; Skobelev, I. Yu.; Faenov, A. Ya.; Pikuz, T. A.; Grum-Grzhimailo, A. N.; Pikuz, S. A.

2015-12-01

The investigation of a recombining laser plasma is topical primarily because it can be used to simulate the interaction between plasma jets in astrophysical objects. It has been shown that the relative intensities of transitions of a resonance series of He-like multicharged ions can be used for the diagnostics of the recombining plasma. It has been found that the intensities of the indicated transitions for ions with the nuclear charge number Z n ~ 10 are sensitive to the plasma density in the range N e ~ 1016-1020 cm-3 at temperatures of 10-100 eV. The calculations performed for the F VIII ion have determined the parameters of plasma jets created at the ELFIE nanosecond laser facility (Ecole Polytechnique, France) in order to simulate astrophysical phenomena. The resulting universal calculation dependences can be used to diagnose different recombining plasmas containing helium-like fluorine ions.

Methods for passivating silicon devices at low temperature to achieve low interface state density and low recombination velocity while preserving carrier lifetime

DOEpatents

Chen, Zhizhang; Rohatgi, Ajeet

1995-01-01

A new process has been developed to achieve a very low SiO.sub.x /Si interface state density D.sub.it, low recombination velocity S (<2 cm/s), and high effective carrier lifetime T.sub.eff (>5 ms) for oxides deposited on silicon substrates at low temperature. The technique involves direct plasma-enhanced chemical vapor deposition (PECVD), with appropriate growth conditions, followed by a photo-assisted rapid thermal annealing (RTA) process. Approximately 500-A-thick SiO.sub.x layers are deposited on Si by PECVD at 250.degree. C. with 0.02 W/cm.sup.-2 rf power, then covered with SiN or an evaporated thin aluminum layer, and subjected to a photo-assisted anneal in forming gas ambient at 350.degree. C., resulting in an interface state density D.sub.it in the range of about 1-4.times.10.sup.10 cm.sup.-2 eV.sup.-1, which sets a record for the lowest interface state density D.sub.it for PECVD oxides fabricated to date. Detailed analysis shows that the PECVD deposition conditions, photo-assisted anneal, forming gas ambient, and the presence of an aluminum layer on top of the oxides during the anneal, all contributed to this low value of interface state density D.sub.it. Detailed metal-oxide semiconductor analysis and model calculations show that such a low recombination velocity S is the result of moderately high positive oxide charge (5.times.10.sup.11 -1.times.10.sup.12 cm.sup.-2) and relatively low midgap interface state density (1.times.10.sup.10 -4.times.10.sup.10 cm.sup.-2 eV.sup.-1). Photo-assisted anneal was found to be superior to furnace annealing, and a forming gas ambient was better than a nitrogen ambient for achieving a very low surface recombination velocity S.

Combined effects of space charge and energetic disorder on photocurrent efficiency loss of field-dependent organic photovoltaic devices

NASA Astrophysics Data System (ADS)

Yoon, Sangcheol; Park, Byoungchoo; Hwang, Inchan

2015-11-01

The loss of photocurrent efficiency by space-charge effects in organic solar cells with energetic disorder was investigated to account for how energetic disorder incorporates space-charge effects, utilizing a drift-diffusion model with field-dependent charge-pair dissociation and suppressed bimolecular recombination. Energetic disorder, which induces the Poole-Frenkel behavior of charge carrier mobility, is known to decrease the mobility of charge carriers and thus reduces photovoltaic performance. We found that even if the mobilities are the same in the absence of space-charge effects, the degree of energetic disorder can be an additional parameter affecting photocurrent efficiency when space-charge effects occur. Introducing the field-dependence parameter that reflects the energetic disorder, the behavior of efficiency loss with energetic disorder can differ depending on which charge carrier is subject to energetic disorder. While the energetic disorder that is applied to higher-mobility charge carriers decreases photocurrent efficiency further, the efficiency loss can be suppressed when energetic disorder is applied to lower-mobility charge carriers.

Quantitative analysis of intramolecular exciplex and electron transfer in a double-linked zinc porphyrin-fullerene dyad.

PubMed

Al-Subi, Ali Hanoon; Niemi, Marja; Tkachenko, Nikolai V; Lemmetyinen, Helge

2012-10-04

Photoinduced charge transfer in a double-linked zinc porphyrin-fullerene dyad is studied. When the dyad is excited at the absorption band of the charge-transfer complex (780 nm), an intramolecular exciplex is formed, followed by the complete charge separated (CCS) state. By analyzing the results obtained from time-resolved transient absorption and emission decay measurements in a range of solvents with different polarities, we derived a dependence between the observable lifetimes and internal parameters controlling the reaction rate constants based on the semiquantum Marcus electron-transfer theory. The critical value of the solvent polarity was found to be ε(r) ≈ 6.5: in solvents with higher dielectric constants, the energy of the CCS state is lower than that of the exciplex and the relaxation takes place via the CCS state predominantly, whereas in solvents with lower polarities the energy of the CCS state is higher and the exciplex relaxes directly to the ground state. In solvents with moderate polarities the exciplex and the CCS state are in equilibrium and cannot be separated spectroscopically. The degree of the charge shift in the exciplex relative to that in the CCS state was estimated to be 0.55 ± 0.02. The electronic coupling matrix elements for the charge recombination process and for the direct relaxation of the exciplex to the ground state were found to be 0.012 ± 0.001 and 0.245 ± 0.022 eV, respectively.

Two-dimensional porous architecture of protonated GCN and reduced graphene oxide via electrostatic self-assembly strategy for high photocatalytic hydrogen evolution under visible light

NASA Astrophysics Data System (ADS)

Pu, Chenchen; Wan, Jun; Liu, Enzhou; Yin, Yunchao; Li, Juan; Ma, Yongning; Fan, Jun; Hu, Xiaoyun

2017-03-01

Herein, porous protonated graphitic carbon nitride (pGCN) is prepared from bulk g-C3N4 (GCN) directly by acidic cutting and hydrothermal process. The holey structure not only provides a lot of bounds on the accelerated and photo induced charge transfer and thus reduce the aggregation, but also endows the GCN with more exposure to the active site. The pGCN is obtained with an increased band gap of 2.91 eV together with a higher specific surface area of 82.76 m2g-1. Meanwhile, the positively charged GCN resulted from the protonation pretreatment is beneficial for improving the interaction with negatively charged GO sheets. Compared with GCN, pGCN-rGO displays a significant decrease of PL intensities and an apparently enhancement of visible-light absorption, resulting a lower charge recombination rate and a better light absorption. Besides, the enhanced charge separation is demonstrated by photoluminescence emission spectroscopy and the transient photocurrent measurement. The photocatalytic performance studies for the degradation of MB indicate that pGCN-rGO exhibits the highest adsorption ability towards dye molecules. In addition, the pGCN-5 wt% rGO composite shows the optimal photocatalytic activity, the photodegradation rate of MB is 99.4% after 80 min of irradiation and the H2 evolution performance up to 557 μmol g-1h-1 under visible light, which is much higher than the other control samples.

Artificial twin-layer configurations of Zn(O,S) films by radio frequency sputtering in all dry processed eco-friendly Cu(In,Ga)Se2 solar cells

NASA Astrophysics Data System (ADS)

Liu, Wei; Fan, Yu; Li, Xiaodong; Lin, Shuping; Liu, Yang; Shi, Sihan; Wang, He; Zhou, Zhiqiang; Zhang, Yi; Sun, Yun

2018-03-01

Cu(In,Ga)Se2 thin film solar cells are of great interest for research and industrial applications with their high conversion efficiencies, long-term stability and significant lifetimes. Such a solar cell of a p-n junction consists of p-type Cu(In,Ga)Se2 films as a light absorber and n-type CdS as a buffer layer, which often emerges with intrinsic ZnO. Aimed at eco-friendly fabrication protocols, a large number of strategies have been investigated to fabricate a Cd-free n-type buffer layer such as Zn(O,S) in Cu(In,Ga)Se2 solar cells. Also, if the Zn(O,S) films are prepared by coevaporation or sputtering, it will offer high compatibility with the preferred mass production. Here, we propose and optimize a dry method for Zn(O,S) deposition in a radio frequency sputtering. In particular, the strategy for the twin-layer configurations of Zn(O,S) films not only greatly improve their electrical conductance and suppress charge carrier recombination, but also avoid degradation of the Zn(O,S)/Cu(In,Ga)Se2 interfaces. Indeed, the high quality of such twin Zn(O,S) layers have been reflected in the similar conversion efficiencies of the complete solar cells as well as the large short-circuit current density, which exceeds the CdS reference device. In addition, Zn(O,S) twin layers have reduced the production time and materials by replacing the CdS/i-ZnO layers, which removes two fabrication steps in the multilayered thin film solar cells. Furthermore, the device physics for such improvements have been fully unveiled with both experimental current-voltage and capacitance-voltage spectroscopies and device simulations via wxAMPS program. Finally, the proposed twin-layer Zn(O,S)/Cu(In,Ga)Se2 interfaces account for the broadening of the depletion region of photogenerated charge carriers, which greatly suppress the carrier recombination at the space charge region, and eventually lead to the more efficient collection of charge carriers at both electrodes.

An investigation of the generation and properties of laboratory-produced ball lightning

NASA Astrophysics Data System (ADS)

Oreshko, A. G.

2015-06-01

The experiments revealed that ball lightning is a self-confining quasi-neutral in a whole plasma system that rotates around its axis. Ball lightning has a structure of a spherical electric domain, consisting of a kernel with excess negative charge and an external spherical layer with excess positive charge. The excess of charges of one sort and the lack of charges of the other sort in the kernel or in the external spherical layer significantly reduces the possibility of electron capture by means of an electric field, created by the nearest ions and leads to a drastic slowdown of recombination process. Direct proof has been obtained that inside of ball lightning - in an external spherical layer that rotates around the axis - there is a circular current of sub-relativistic particles. This current creates and maintains its own poloidal magnetic field of ball lightning, i.e. it carries out the function of magnetic dynamo. The kernel of ball lightning is situated in a region with minimum values of induction of the magnetic field. The inequality of positive and negative charges in elements of ball lightning also significantly reduces losses of the charged plasma on bremsstrahlung. Ball lightning generation occurs in a plasmic vortex. The ball lightning energy in the region of its generation significantly differs from the ball lightning energy, which is drifting in space. The axial component of kinetic energy of particles slightly exceeds 100 keV and the rotational component of the ions energy is a bit greater than 1 MeV. Ball lightning is `embedded' in atmosphere autonomous accelerator of charged particles of a cyclotron type due to self-generation of strong crossed electric and magnetic fields. A discussion of the conditions of stability and long-term existence of ball lightning is given.

Study on isopropanol degradation by UV/TiO2 nanotube

NASA Astrophysics Data System (ADS)

Cheng, Hsiu-Yueh; Chang, Kai-Chau; Lin, Kae-Long; Ma, Chih-Ming

2018-04-01

When a semiconductor molecule absorbs photons with energy equal to or greater than its band-gap, electrons in the valence band can be excited and jump up into the conduction band and thus charge carriers are generated. When these charge carriers successfully migrate to the solid surface without recombining, the electrons and holes may undergo electron-transfer processes with adsorbates of suitable redox potentials. The photogenerated holes react with the water to produce hydroxyl radicals, while the photogenerated electrons react with molecular oxygen to give superoxide radical anions. These radicals so produced are highly reactive and they work together to completely oxidize the organic species. In this study, TiO2 nanotube has been prepared and was to be used to control acetone. In this work, mesoporous nanotubes by hydrothermal treatment in aqueous sodium hydroxide solution have been synthesized. Direct hydrothermal synthesis method is easy and efficient to synthesize titanate nanotubes. Using sodium hydroxide, the considerable decrease in reaction time and reaction temperature was achieved.

Understanding the Unique Properties of Organometal Trihalide Perovskite with Single Crystals

NASA Astrophysics Data System (ADS)

Huang, Jinsong

Organometal Trihalide Perovskite has been discovered to be all-round optoelectronic materials many types of electronic devices. The understanding of this family of materials is however limited yet due to the complicated grain structures in polycrystalline films which are generally used in most of the devices. In this contribution, I will present our recent progress in understanding the fundamental properties, including optoelectronic properties and electromechanical properties, using the high quality organometal trihalide perovskite single crystals. I will report the crystallographic orientation dependent charge transport and collection, surface and bulk charge recombination process, and direction measuring of carrier diffusion length using the lasing induced photocurrent scanning. The polarity of the organometal trihalide perovskite crystals will also be examined. We thank financial support from SunShot Initiative at Department of Energy under Award DE-EE0006709, and from National Science Foundation Grant DMR-1505535 and Grant DMR-1420645, and from Office of Naval Research under Award N00014-15-1-2713.

Micro-cones on a liquid interface in high electric field: Ionization effects

NASA Astrophysics Data System (ADS)

Subbotin, Andrey V.; Semenov, Alexander N.

2018-02-01

We formulate and explore electrohydrodynamic equations for conductive liquids taking dissociation/recombination processes into account and discover a novel type of liquid cones which carry both surface and net bulk charge and can be formed on a liquid interface in an electric field. The bulk charge is generated by the corona discharge due to a high electric field at the cone apex. We establish correlation between the cone angle and physical parameters of the liquid on the one hand and the electric current passing through the cone on the other hand. It is shown that the current strongly increases when the cone angle tends to a critical value which is a function of the dielectric permittivity of the liquid. The cone stability with respect to axially symmetric perturbations is analyzed. It is shown that the cones with apex angles close to the critical angle are likely to be stable. The effect of the imposed flow on the cone apex stability is also discussed.

Power output and carrier dynamics studies of perovskite solar cells under working conditions.

PubMed

Yu, Man; Wang, Hao-Yi; Hao, Ming-Yang; Qin, Yujun; Fu, Li-Min; Zhang, Jian-Ping; Ai, Xi-Cheng

2017-08-02

Perovskite solar cells have emerged as promising photovoltaic systems with superb power conversion efficiency. For the practical application of perovskite devices, the greatest concerns are the power output density and the related dynamics under working conditions. In this study, the working conditions of planar and mesoscopic perovskite solar cells are simulated and the power output density evolutions with the working voltage are highlighted. The planar device exhibits higher capability of outputting power than the mesoscopic one. The transient photoelectric conversion dynamics are investigated under the open circuit, short circuit and working conditions. It is found that the power output and dynamic processes are correlated intrinsically, which suggests that the power output is the competitive result of the charge carrier recombination and transport. The present work offers a unique view to elucidating the relationship between the power output and the charge carrier dynamics for perovskite solar cells in a comprehensive manner, which would be beneficial to their future practical applications.

Towards zero-threshold optical gain using charged semiconductor quantum dots

DOE PAGES

Wu, Kaifeng; Park, Young -Shin; Lim, Jaehoon; ...

2017-10-16

Colloidal semiconductor quantum dots are attractive materials for the realization of solution-processable lasers. However, their applications as optical-gain media are complicated by a non-unity degeneracy of band-edge states, because of which multiexcitons are required to achieve the lasing regime. This increases the lasing thresholds and leads to very short optical gain lifetimes limited by nonradiative Auger recombination. Here, we show that these problems can be at least partially resolved by employing not neutral but negatively charged quantum dots. By applying photodoping to specially engineered quantum dots with impeded Auger decay, we demonstrate a considerable reduction of the optical gain thresholdmore » due to suppression of ground-state absorption by pre-existing carriers. Moreover, by injecting approximately one electron per dot on average, we achieve a more than twofold reduction in the amplified spontaneous emission threshold, bringing it to the sub-single-exciton level. Furthermore, these measurements indicate the feasibility of ‘zero-threshold’ gain achievable by completely blocking the band-edge state with two electrons.« less

Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies

DOE PAGES

Guo, Peijun; Xia, Yi; Gong, Jue; ...

2017-09-28

Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures.more » Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.« less

Towards zero-threshold optical gain using charged semiconductor quantum dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Kaifeng; Park, Young -Shin; Lim, Jaehoon

Colloidal semiconductor quantum dots are attractive materials for the realization of solution-processable lasers. However, their applications as optical-gain media are complicated by a non-unity degeneracy of band-edge states, because of which multiexcitons are required to achieve the lasing regime. This increases the lasing thresholds and leads to very short optical gain lifetimes limited by nonradiative Auger recombination. Here, we show that these problems can be at least partially resolved by employing not neutral but negatively charged quantum dots. By applying photodoping to specially engineered quantum dots with impeded Auger decay, we demonstrate a considerable reduction of the optical gain thresholdmore » due to suppression of ground-state absorption by pre-existing carriers. Moreover, by injecting approximately one electron per dot on average, we achieve a more than twofold reduction in the amplified spontaneous emission threshold, bringing it to the sub-single-exciton level. Furthermore, these measurements indicate the feasibility of ‘zero-threshold’ gain achievable by completely blocking the band-edge state with two electrons.« less

Variation in recombination frequency and distribution across eukaryotes: patterns and processes

PubMed Central

Feulner, Philine G. D.; Johnston, Susan E.; Santure, Anna W.; Smadja, Carole M.

2017-01-01

Recombination, the exchange of DNA between maternal and paternal chromosomes during meiosis, is an essential feature of sexual reproduction in nearly all multicellular organisms. While the role of recombination in the evolution of sex has received theoretical and empirical attention, less is known about how recombination rate itself evolves and what influence this has on evolutionary processes within sexually reproducing organisms. Here, we explore the patterns of, and processes governing recombination in eukaryotes. We summarize patterns of variation, integrating current knowledge with an analysis of linkage map data in 353 organisms. We then discuss proximate and ultimate processes governing recombination rate variation and consider how these influence evolutionary processes. Genome-wide recombination rates (cM/Mb) can vary more than tenfold across eukaryotes, and there is large variation in the distribution of recombination events across closely related taxa, populations and individuals. We discuss how variation in rate and distribution relates to genome architecture, genetic and epigenetic mechanisms, sex, environmental perturbations and variable selective pressures. There has been great progress in determining the molecular mechanisms governing recombination, and with the continued development of new modelling and empirical approaches, there is now also great opportunity to further our understanding of how and why recombination rate varies. This article is part of the themed issue ‘Evolutionary causes and consequences of recombination rate variation in sexual organisms’. PMID:29109219

Zwitterion mediator/quenchers. Coulombic minimization of the back-reaction in photocatalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brugger, P.A.; Graetzel, M.; Guarr, T.

1982-03-18

Zwitterionic analogues of methyl viologen, N,N'-bis(carboxyethyl)-4,4'-bipyridyl (CEB), and N,N'-bis(sulfonatopropyl)-4,4'-bipyridyl (SPB) have been studied as electron-transfer quenchers of excited-state photocatalysts. The molecules are formally neutral when oxidized but become negatively charged when reduced. This charge buildup minimizes undesirable back-recombination of the photogenerated redox products. This Coulombic effect is demonstrated both by direct flash photolysis measurements of back-recombination and by catalytic studies of water reduction. Results are compared for the zwitterion quenchers and methyl viologen, reacting with soluble anionic porphyrins and with micelle-associated reactants. For the anionic porphyrin system zinc tetrakis (sulfonatophenyl)porphyrin(4-) the rates of back-recombination are as follows: ZnTSPP/sup 3 -/more » + MV/sup +/...-->.. ZnTSPP/sup 4 -/ + MV/sup 2 +/ (k), k = 2 x 10/sup 9/M/sup -1/s/sup -1/; ZnTSPP/sup 3 -/ + CEB/sup -/. ..-->.. ZnTSPP/sup 4 -/ + CEB +- (k), k = 6 x 10/sup 8/ M/sup -1/ s/sup -1/. In a corresponding catalytic system incorporating ZnTPPS as the photoacceptor, CEB or methyl viologen as the quencher, and N-phenylglycine as the electron donor, a >2-fold enhancement of catalysis is observed by replacing MV/sup 2 +/ with CEB. These events can be greatly accentuated by increasing the charge on the components, via micellar localization. Thus, by using an amphiphilic derivative of Ru(bpy)/sub 3//sup 2 +/ as photoactive donor solubilized in anionic micelles and SPB as electron acceptor, one can achieve 200-fold reduction in the rate of the back-reaction.« less

Photocatalytic removal of 2,4-dichlorophenoxyacetic acid herbicide on copper oxide/titanium dioxide prepared by co-precipitation method

NASA Astrophysics Data System (ADS)

Lee, Shu Chin; Hasan, Norhasnita; Lintang, Hendrik O.; Shamsuddin, Mustaffa; Yuliati, Leny

2016-02-01

In this work, suppression of the charge recombination on the titanium dioxide (TiO2) was reported by the addition of copper oxide (CuO), which led to a higher activity of TiO2 for removal of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide. A series of CuO/TiO2 with CuO loadings of 0.1-1 wt% was prepared through a co-precipitation method. X-ray diffraction patterns revealed that the presence of CuO could not be detected as the low loading amount of CuO might have good dispersion on the surface of TiO2. Diffuse reflectance UV-visible spectra suggested that low loading amount of CuO did not influence the optical property of TiO2. Fluorescence spectroscopy revealed that TiO2 possessed a dominant emission peak of 407 nm at an excitation wavelength of 218 nm. The increasing loading amount of CuO decreased the emission intensity of TiO2, suggesting the successful reduction of charge recombination. After irradiation under UV light for 1 h, CuO(0.1 wt%)/TiO2 gave the highest percentage removal of the herbicide among the samples. The optimum loading amount of CuOmight improve the charge separation and reduce the electron-hole recombination on TiO2 without blocking the active sites, thus leading to the improved photocatalytic activity. This work showed that CuO/TiO2 is a potential photocatalyst for environmental remediation.

Energy-transfer processes in neon-hydrogen mixtures excited by electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morozov, A.; Kruecken, R.; Ulrich, A.

2005-12-15

Energy- and charge-transfer processes in neon-hydrogen mixtures (500-1400 hPa neon and 0.001-3 hPa hydrogen partial pressures) excited by a pulsed low-energy ({approx}10 keV) electron beam were investigated using time-resolved spectroscopy. Time spectra of the hydrogen Lyman-{alpha} line, neon excimer emission (second continuum), and neon atomic lines (3p-3s transitions) were recorded. The time-integrated intensity of the Lyman-{alpha} emission was measured for the same range of gas mixtures. It is shown that direct energy transfer from Ne{sub 2}* excimers and neon atoms in the four lowest excited states as well as recombination of H{sub 3}{sup +} ions are the main channels populatingmore » atomic hydrogen in the n=2 state. A rate constant of (4.2{+-}1.4)x10{sup -11} cm{sup 3} s{sup -1} was obtained for the charge transfer from Ne{sub 2}{sup +} ions to molecular hydrogen. A lower limit for the depopulation rate constant of Ne{sub 2}* excimers by molecular hydrogen (combination of energy transfer and ionization) was found to be 1.0x10{sup -10} cm{sup 3} s{sup -1}.« less

Quantum efficiency harmonic analysis of exciton annihilation in organic light emitting diodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Price, J. S.; Giebink, N. C., E-mail: ncg2@psu.edu

2015-06-29

Various exciton annihilation processes are known to impact the efficiency roll-off of organic light emitting diodes (OLEDs); however, isolating and quantifying their contribution in the presence of other factors such as changing charge balance continue to be a challenge for routine device characterization. Here, we analyze OLED electroluminescence resulting from a sinusoidal dither superimposed on the device bias and show that nonlinearity between recombination current and light output arising from annihilation mixes the quantum efficiency measured at different dither harmonics in a manner that depends uniquely on the type and magnitude of the annihilation process. We derive a series ofmore » analytical relations involving the DC and first harmonic external quantum efficiency that enable annihilation rates to be quantified through linear regression independent of changing charge balance and evaluate them for prototypical fluorescent and phosphorescent OLEDs based on the emitters 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran and platinum octaethylporphyrin, respectively. We go on to show that, in most cases, it is sufficient to calculate the needed quantum efficiency harmonics directly from derivatives of the DC light versus current curve, thus enabling this analysis to be conducted solely from standard light-current-voltage measurement data.« less

Hydrodynamic model for expansion and collisional relaxation of x-ray laser-excited multi-component nanoplasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saxena, Vikrant, E-mail: vikrant.saxena@desy.de; Hamburg Center for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg; Ziaja, Beata, E-mail: ziaja@mail.desy.de

The irradiation of an atomic cluster with a femtosecond x-ray free-electron laser pulse results in a nanoplasma formation. This typically occurs within a few hundred femtoseconds. By this time the x-ray pulse is over, and the direct photoinduced processes no longer contributing. All created electrons within the nanoplasma are thermalized. The nanoplasma thus formed is a mixture of atoms, electrons, and ions of various charges. While expanding, it is undergoing electron impact ionization and three-body recombination. Below we present a hydrodynamic model to describe the dynamics of such multi-component nanoplasmas. The model equations are derived by taking the moments ofmore » the corresponding Boltzmann kinetic equations. We include the equations obtained, together with the source terms due to electron impact ionization and three-body recombination, in our hydrodynamic solver. Model predictions for a test case, expanding spherical Ar nanoplasma, are obtained. With this model, we complete the two-step approach to simulate x-ray created nanoplasmas, enabling computationally efficient simulations of their picosecond dynamics. Moreover, the hydrodynamic framework including collisional processes can be easily extended for other source terms and then applied to follow relaxation of any finite non-isothermal multi-component nanoplasma with its components relaxed into local thermodynamic equilibrium.« less

Perovskite-sensitized solar cells-based Ga-TiO2 nanodiatom-like photoanode: the improvement of performance by perovskite crystallinity refinement

NASA Astrophysics Data System (ADS)

Umar, Akrajas Ali; Al-She'irey, Altaf Yahya Ahmed; Rahman, Mohd Yusri Abd; Salleh, Muhamad Mat; Oyama, Munetaka

2018-05-01

The structure and crystallinity of the photoactive materials in solar cell determines the exciton formation, carrier's recombination, life-time and transportation in the devices. Here, we report that enhanced charge transportation, internal quantum efficiency and the carrier life-time can be achieved by modifying the structure, morphology of the organic perovskite thin film, enabling the improvement of the solar cell performance. The thin film structure modification was achieved via a thermal annealing in vacuum. In typical procedure, the power conversion efficiency of the PSC device can be upgraded from 0.5 to 2.9%, which is approximately 6 times increment, when the surface structure disorders are limited in the organic perovskite thin film. By optimizing the organic perovskite loading on the Ga-TiO2 diatom-like nanostructures photoanode and combining with a fine control of organic perovskite thin film structure, power conversion efficiency as high as 6.58% can be generated from the device. Electrochemical impedance spectroscopy and current-voltage analysis in the dark indicated that this process has effectively augmented the carrier life-time and limited the carrier recombination, enhancing the overall performance of the solar cell device. The preparation process and mechanism of the device performance improvement will be discussed.

Reversible Strain-Induced Electron-Hole Recombination in Silicon Nanowires Observed with Femtosecond Pump-Probe Microscopy

DTIC Science & Technology

2014-01-01

devices with indirect-bandgap materials such as silicon . KEYWORDS: Ultrafast imaging , strained nanomaterials, spectroscopy Lattice strain produced by...photogenerated charge cloud as a result of carrier diffusion . Normalized carrier profiles, generated by integrating the images along the direction normal to the...To test this idea, Figure 2. Charge carrier diffusion in a Si NW locally strained by a bending deformation (A) SEM image of a bent Si nanowire ∼100

Improvement of Charge Transportation in Si Quantum Dot-Sensitized Solar Cells Using Vanadium Doped TiO2.

PubMed

Seo, Hyunwoong; Ichida, Daiki; Hashimoto, Shinji; Itagaki, Naho; Koga, Kazunori; Shiratani, Masaharu; Nam, Sang-Hun; Boo, Jin-Hyo

2016-05-01

The multiple exciton generation characteristics of quantum dots have been expected to enhance the performance of photochemical solar cells. In previous work, we first introduced Si quantum dot for sensitized solar cells. The Si quantum dots were fabricated by multi-hollow discharge plasma chemical vapor deposition, and were characterized optically and morphologically. The Si quantum dot-sensitized solar cells had poor performance due to significant electron loss by charge recombination. Although the large Si particle size resulted in the exposure of a large TiO2 surface area, there was a limit to ho much the particle size could be decreased due to the reduced absorbance of small particles. Therefore, this work focused on decreasing the internal impedance to improve charge transfer. TiO2 was electronically modified by doping with vanadium, which can improve electron transfer in the TiO2 network, and which is stable in the redox electrolyte. Photogenerated electrons can more easily arrive at the conductive electrode due to the decreased internal impedance. The dark photovoltaic properties confirmed the reduction of charge recombination, and the photon-to-current conversion efficiency reflected the improved electron transfer. Impedance analysis confirmed a decrease in internal impedance and an increased electron lifetime. Consequently, these improvements by vanadium doping enhanced the overall performance of Si quantum dot-sensitized solar cells.

Structural and dynamical properties of recombining ultracold neutral plasma

NASA Astrophysics Data System (ADS)

Tiwari, Sanat Kumar; Shaffer, Nathaniel R.; Baalrud, Scott D.

2017-10-01

An ultracold plasma (UCP) is an evolving collection of free charges and bound charges (Rydberg atoms). Over time, bound species concentration increases due to recombination. We present the structural and dynamical properties of an evolving UCP using classical molecular dynamics simulation. Coulomb collapse is avoided using a repulsive core with the attractive Coulomb potential. The repulsive core size controls the concentration of bound states, as it determines the depth of the potential well between opposite charges. We vary the repulsive core size to emulate the quasi-static state of plasma at different time during the evolution. Binary, chain and ring-like bound states are observed in the simulation carried out at different coupling strengths and repulsive core size. The effect of bound states can be seen as molecular peaks in the radial distribution function (RDF). The thermodynamic properties associated with the free charges can be analyzed from RDF by separating free from bound states. These bound states also change the dynamical properties of the plasma. The electron velocity auto-correlation displays oscillations due to the orbital motion in bound states. These bound states act like a neutral species, damping electron plasmon modes and broadening the ion acoustic mode. This work is supported by AFOSR Grant Number FA9550-16-1-0221. It used computational resources by XSEDE, which is supported by NSF Grant Number ACI-1053575.

Description of bipolar charge transport in polyethylene using a fluid model with a constant mobility: model prediction

NASA Astrophysics Data System (ADS)

LeRoy, S.; Segur, P.; Teyssedre, G.; Laurent, C.

2004-01-01

We present a conduction model aimed at describing bipolar transport and space charge phenomena in low density polyethylene under dc stress. In the first part we recall the basic requirements for the description of charge transport and charge storage in disordered media with emphasis on the case of polyethylene. A quick review of available conduction models is presented and our approach is compared with these models. Then, the bases of the model are described and related assumptions are discussed. Finally, results on external current, trapped and free space charge distributions, field distribution and recombination rate are presented and discussed, considering a constant dc voltage, a step-increase of the voltage, and a polarization-depolarization protocol for the applied voltage. It is shown that the model is able to describe the general features reported for external current, electroluminescence and charge distribution in polyethylene.

First-principles prediction of new photocatalyst materials with visible-light absorption and improved charge separation: surface modification of rutile TiO₂ with nanoclusters of MgO and Ga₂O₃.

PubMed

Nolan, Michael

2012-11-01

Titanium dioxide is an important and widely studied photocatalytic material, but to achieve photocatalytic activity under visible-light absorption, it needs to have a narrower band gap and reduced charge carrier recombination. First-principles simulations are presented in this paper to show that heterostructures of rutil TiO₂ modified with nanoclusters of MgO and Ga₂O₃ will be new photocatalytically active materials in the UV (MgO-TiO₂) and visible (Ga₂O₃-TiO₂) regions of the solar spectrum. In particular, our investigations of a model of the excited state of the heterostructures demonstrate that upon light excitation electrons and holes can be separated onto the TiO₂ surface and the metal oxide nanocluster, which will reduce charge recombination and improve photocatalytic activity. For MgO-modified TiO₂, no significant band gap change is predicted, but for Ga₂O₃-modified TiO₂ we predict a band gap change of up to 0.6 eV, which is sufficient to induce visible light absorption. Comparisons with unmodified TiO₂ and other TiO₂-based photocatalyst structures are presented.

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

PubMed Central

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; Lupton, John M.; Boehme, Christoph

2015-01-01

Weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm. PMID:25868686

Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

DOE PAGES

van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; ...

2015-04-14

Here, weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices,more » which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair’s zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.« less

Polaronic Charge Carrier-Lattice Interactions in Lead Halide Perovskites.

PubMed

Wolf, Christoph; Cho, Himchan; Kim, Young-Hoon; Lee, Tae-Woo

2017-10-09

Almost ten years after the renaissance of the popular perovskite-type semiconductors based on lead salts with the general formula AMX 3 (A=organic or inorganic cation; M=divalent metal; X=halide), many facets of photophysics continue to puzzle researchers. In this Minireview, light is shed on the low mobilities of charge carriers in lead halide perovskites with special focus on the lattice properties at non-zero temperature. The polar and soft lattice leads to pronounced electron-phonon coupling, limiting carrier mobility and retarding recombination. We propose that the proper picture of excited charge carriers at temperature ranges that are relevant for device operations is that of a polaron, with Fröhlich coupling constants between 1<α<3. Under the aspect of light-emitting diode application, APbX 3 perovskite show moderate second order (bimolecular) recombination rates and high third-order (Auger) rate constants. It has become apparent that this is a direct consequence of the anisotropic polar A-site cation in organic-inorganic hybrid perovskites and might be alleviated by replacing the organic moiety with an isotropic cation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of dislocation density on internal quantum efficiency of GaN-based semiconductors

NASA Astrophysics Data System (ADS)

Yu, Jiadong; Hao, Zhibiao; Li, Linsen; Wang, Lai; Luo, Yi; Wang, Jian; Sun, Changzheng; Han, Yanjun; Xiong, Bing; Li, Hongtao

2017-03-01

By considering the effects of stress fields coming from lattice distortion as well as charge fields coming from line charges at edge dislocation cores on radiative recombination of exciton, a model of carriers' radiative and non-radiative recombination has been established in GaN-based semiconductors with certain dislocation density. Using vector average of the stress fields and the charge fields, the relationship between dislocation density and the internal quantum efficiency (IQE) is deduced. Combined with related experimental results, this relationship is fitted well to the trend of IQEs of bulk GaN changing with screw and edge dislocation density, meanwhile its simplified form is fitted well to the IQEs of AlGaN multiple quantum well LEDs with varied threading dislocation densities but the same light emission wavelength. It is believed that this model, suitable for different epitaxy platforms such as MOCVD and MBE, can be used to predict to what extent the luminous efficiency of GaN-based semiconductors can still maintain when the dislocation density increases, so as to provide a reasonable rule of thumb for optimizing the epitaxial growth of GaN-based devices.

Synthesis of Nb doped TiO2 nanotube/reduced graphene oxide heterostructure photocatalyst with high visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Niu, Xiaoyou; Yan, Weijing; Zhao, Hongli; Yang, Jingkai

2018-05-01

Limited by the narrowed photoresponse range and unsatisfactory recombination of photoinduced electron-hole pairs, the photocatalytic efficiency of TiO2 is still far below what is expected. Here, we initially doped TiO2 nanotubes (TNTS) by transition metal ion Nb, then it is coupled with reduced graphene oxide (rGO) to construct a heterostructure photocatalyst. The defect state presented in TiO2 leading to the formation of localized midgap states (MS) in the bandgap, which regulating the band structure of TiO2 and extending the optical absorption to visible light region. The internal charge transport and transfer behavior analyzed by electrochemical impedance spectroscopy (EIS) reveal that the coupling of rGO with TNTS results in the formation of electron transport channel in the heterostructure, which makes a great contribution to the photoinduced charge separation. As expected, the Nb-TNTS/rGO exhibits a stable and remarkably enhanced photocatalytic activity in the visible-light irradiation degradation of methylene blue (MB), up to ∼5 times with respect to TNTS, which is attributed to the effective inhibition of charge recombination, the reduction of bandgap and higher redox potential, as well as the great adsorptivity.