Double Super-Exchange in Silicon Quantum Dots Connected by Short-Bridged Networks

NASA Astrophysics Data System (ADS)

Li, Huashan; Wu, Zhigang; Lusk, Mark

2013-03-01

Silicon quantum dots (QDs) with diameters in the range of 1-2 nm are attractive for photovoltaic applications. They absorb photons more readily, transport excitons with greater efficiency, and show greater promise in multiple-exciton generation and hot carrier collection paradigms. However, their high excitonic binding energy makes it difficult to dissociate excitons into separate charge carriers. One possible remedy is to create dot assemblies in which a second material creates a Type-II heterojunction with the dot so that exciton dissociation occurs locally. This talk will focus on such a Type-II heterojunction paradigm in which QDs are connected via covalently bonded, short-bridge molecules. For such interpenetrating networks of dots and molecules, our first principles computational investigation shows that it is possible to rapidly and efficiently separate electrons to QDs and holes to bridge units. The bridge network serves as an efficient mediator of electron superexchange between QDs while the dots themselves play the complimentary role of efficient hole superexchange mediators. Dissociation, photoluminescence and carrier transport rates will be presented for bridge networks of silicon QDs that exhibit such double superexchange. This material is based upon work supported by the Renewable Energy Materials Research Science and Engineering Center (REMRSEC) under Grant No. DMR-0820518 and Golden Energy Computing Organization (GECO).

Photorefractive InGaAs/GaAs multiple quantum wells in the Franz{endash}Keldysh geometry

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

Iwamoto, S.; Kageshima, H.; Yuasa, T.

2001-06-01

We fabricate semi-insulating InGaAs/GaAs multiple quantum wells and observe the excitonic enhancement of the photorefractivity in the Franz{endash}Keldysh geometry at wavelengths of 0.92{endash}0.94 {mu}m. A maximum two-wave mixing gain of 138 cm{sup {minus}1} and a maximum diffraction efficiency of 1.5{times}10{sup {minus}4} are obtained. The saturation intensity and the spatial resolution are also measured by four-wave mixing. The diffraction efficiency is saturated at a high external electric field. The dominant cause of this saturation is the deviation of the excitonic electroabsorption from its quadratic law. {copyright} 2001 American Institute of Physics.

Exciton localization in (11-22)-oriented semi-polar InGaN multiple quantum wells

NASA Astrophysics Data System (ADS)

Monavarian, Morteza; Rosales, Daniel; Gil, Bernard; Izyumskaya, Natalia; Das, Saikat; Özgür, Ümit; Morkoç, Hadis; Avrutin, Vitaliy

2016-02-01

Excitonic recombination dynamics in (11-22) -oriented semipolar In0.2Ga0.8N/In0.06Ga0.94N multiquantum wells (MQWs) grown on GaN/m-sapphire templates have been investigated by temperature-dependent time-resolved photoluminescence (TRPL). The radiative and nonradiative recombination contributions to the PL intensity at different temperatures were evaluated by analysing temperature dependences of PL peak intensity and decay times. The obtained data indicate the existence of exciton localization with a localization energy of Eloc(15K) =7meV and delocalization temperature of Tdeloc = 200K in the semipolar InGaN MQWs. Presence of such exciton localization in semipolar (11-22) -oriented structures could lead to improvement of excitonic emission and internal quantum efficiency.

Identification of a triplet pair intermediate in singlet exciton fission in solution

PubMed Central

Stern, Hannah L.; Musser, Andrew J.; Gelinas, Simon; Parkinson, Patrick; Herz, Laura M.; Bruzek, Matthew J.; Anthony, John; Friend, Richard H.; Walker, Brian J.

2015-01-01

Singlet exciton fission is the spin-conserving transformation of one spin-singlet exciton into two spin-triplet excitons. This exciton multiplication mechanism offers an attractive route to solar cells that circumvent the single-junction Shockley–Queisser limit. Most theoretical descriptions of singlet fission invoke an intermediate state of a pair of spin-triplet excitons coupled into an overall spin-singlet configuration, but such a state has never been optically observed. In solution, we show that the dynamics of fission are diffusion limited and enable the isolation of an intermediate species. In concentrated solutions of bis(triisopropylsilylethynyl)[TIPS]—tetracene we find rapid (<100 ps) formation of excimers and a slower (∼10 ns) break up of the excimer to two triplet exciton-bearing free molecules. These excimers are spectroscopically distinct from singlet and triplet excitons, yet possess both singlet and triplet characteristics, enabling identification as a triplet pair state. We find that this triplet pair state is significantly stabilized relative to free triplet excitons, and that it plays a critical role in the efficient endothermic singlet fission process. PMID:26060309

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

Damtie, Fikeraddis A., E-mail: Fikeraddis.Damtie@teorfys.lu.se; Wacker, Andreas, E-mail: Andreas.Wacker@fysik.lu.se; Karki, Khadga J., E-mail: Khadga.Karki@chemphys.lu.se

Multiple exciton generation (MEG) is a process in which more than one electron hole pair is generated per absorbed photon. It allows us to increase the efficiency of solar energy harvesting. Experimental studies have shown the multiple exciton generation yield of 1.2 in isolated colloidal quantum dots. However real photoelectric devices require the extraction of electron hole pairs to electric contacts. We provide a systematic study of the corresponding quantum coherent processes including extraction and injection and show that a proper design of extraction and injection rates enhances the yield significantly up to values around 1.6.

Impact of biexcitons on the relaxation mechanisms of polaritons in III-nitride based multiple quantum well microcavities

NASA Astrophysics Data System (ADS)

Corfdir, P.; Levrat, J.; Rossbach, G.; Butté, R.; Feltin, E.; Carlin, J.-F.; Christmann, G.; Lefebvre, P.; Ganière, J.-D.; Grandjean, N.; Deveaud-Plédran, B.

2012-06-01

We report on the direct observation of biexcitons in a III-nitride based multiple quantum well microcavity operating in the strong light-matter coupling regime by means of nonresonant continuous wave and time-resolved photoluminescence at low temperature. First, the biexciton dynamics is investigated for the bare active medium (multiple quantum wells alone) evidencing localization on potential fluctuations due to alloy disorder and thermalization between both localized and free excitonic and biexcitonic populations. Then, the role of biexcitons is considered for the full microcavity: in particular, we observe that for specific detunings the bottom of the lower polariton branch is directly fed by the radiative dissociation of either cavity biexcitons or excitons mediated by one LO-phonon. Accordingly, minimum polariton lasing thresholds are observed, when the bottom of the lower polariton branch corresponds in energy to the exciton or cavity biexciton first LO-phonon replica. This singular observation highlights the role of excitonic molecules in the polariton condensate formation process as being a more efficient relaxation channel when compared to the usually assumed acoustical phonon emission one.

Iii-V Compound Multiple Quantum Well Based Modulator and Switching Devices.

NASA Astrophysics Data System (ADS)

Hong, Songcheol

A general formalism to study the absorption and photocurrent in multiple quantum well is provided with detailed consideration of quantum confined Stark shift, exciton binding energy, line broadening, tunneling, polarization, and strain effects. Results on variation of exciton size, binding energies and transition energies as a function electric field and well size have been presented. Inhomogeneous line broadening of exciton lines due to interface roughness, alloy disorder and well to well size fluctuation is calculated. The potential of material tailoring by introducing strain for specific optical response is discussed. Theoretical and experimental results on excitonic and band-to-band absorption spectra in strained multi-quantum well structures are shown. I also report on polarization dependent optical absorption for excitonic and interband transitions in lattice matched and strained multiquantum well structures in presence of transverse electric field. Photocurrent in a p-i(MQW)-n diode with monochromatic light is examined with respect to different temperatures and intensities. The negative resistance of I-V characteristic of the p-i-n diode is based on the quantum confined Stark effect of the heavy hole excitonic transition in a multiquantum well. This exciton based photocurrent characteristic allows efficient switching. A general purpose low power optical logic device using the controller-modulator concept bas been proposed and realized. The controller is a heterojunction phototransistor with multiquantum wells in the base-collector depletion region. This allows an amplified photocurrent controlled voltage feedback with low light intensity levels. Detailed analysis of the sensitivity of this device in various modes of operation is studied. Studies are also presented on the cascadability of the device as well as its integrating -thresholding properties. A multiquantum well heterojunction bipolar transistor (MHBT), which has N^+ -p^+-i(MQW)-N structure has been fabricated to test the concept. Gain (>30) is obtained in the MBE grown devices and efficient switching occurs due to the amplification of the exciton based photocurrent. The level shift operation of the base contacted MHBT are demonstrated.

Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers.

PubMed

Andernach, Rolf; Utzat, Hendrik; Dimitrov, Stoichko D; McCulloch, Iain; Heeney, Martin; Durrant, James R; Bronstein, Hugo

2015-08-19

We report the synthesis of a novel polythiophene-based host-guest copolymer incorporating a Pt-porphyrin complex (TTP-Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple time scales and investigated the mechanism of triplet exciton formation. During sensitization, singlet exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt-porphyrin to the polymer and found that 60% of the complex triplet excitons were transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet-triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and upconversion layers.

Determination of band offset using continuous-wave two-photon excitation in a ZnSe quantum-well waveguide structure

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

Wagner, H. P.; Kuhnelt, M.; Wenisch, H.

2001-06-15

We investigate exciton subband transitions in a ZnSe/Zn{sub 1{minus}x}Mg{sub x}S{sub y}Se{sub 1{minus}y} multiple-quantum-well grown by molecular beam epitaxy waveguide structure by photoluminescence excitation and two-photon excitation spectroscopy. A continuous-wave two-photon absorption is realized by an efficient waveguide coupling scheme within the cryostat. From the energetic position of the 1s and 2p exciton transitions exciton binding energies of 33 and 38 meV are deduced for heavy and light-hole excitons, respectively. With these values we are able to determine the strain free and dimensionless conduction-band-offset parameter to Q{sub c}=0.3{+-}0.1.

Generalized Master Equation with Non-Markovian Multichromophoric Förster Resonance Energy Transfer for Modular Exciton Densities

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

Jang, Seogjoo; Hoyer, Stephan; Fleming, Graham

2014-10-31

A generalized master equation (GME) governing quantum evolution of modular exciton density (MED) is derived for large scale light harvesting systems composed of weakly interacting modules of multiple chromophores. The GME-MED offers a practical framework to incorporate real time coherent quantum dynamics calculations of small length scales into dynamics over large length scales, and also provides a non-Markovian generalization and rigorous derivation of the Pauli master equation employing multichromophoric Förster resonance energy transfer rates. A test of the GME-MED for four sites of the Fenna-Matthews-Olson complex demonstrates how coherent dynamics of excitonic populations over coupled chromophores can be accurately describedmore » by transitions between subgroups (modules) of delocalized excitons. Application of the GME-MED to the exciton dynamics between a pair of light harvesting complexes in purple bacteria demonstrates its promise as a computationally efficient tool to investigate large scale exciton dynamics in complex environments.« less

Thin film solar cells grown by organic vapor phase deposition

NASA Astrophysics Data System (ADS)

Yang, Fan

Organic solar cells have the potential to provide low-cost photovoltaic devices as a clean and renewable energy resource. In this thesis, we focus on understanding the energy conversion process in organic solar cells, and improving the power conversion efficiencies via controlled growth of organic nanostructures. First, we explain the unique optical and electrical properties of organic materials used for photovoltaics, and the excitonic energy conversion process in donor-acceptor heterojunction solar cells that place several limiting factors of their power conversion efficiency. Then, strategies for improving exciton diffusion and carrier collection are analyzed using dynamical Monte Carlo models for several nanostructure morphologies. Organic vapor phase deposition is used for controlling materials crystallization and film morphology. We improve the exciton diffusion efficiency while maintaining good carrier conduction in a bulk heterojunction solar cell. Further efficiency improvement is obtained in a novel nanocrystalline network structure with a thick absorbing layer, leading to the demonstration of an organic solar cell with 4.6% efficiency. In addition, solar cells using simultaneously active heterojunctions with broad spectral response are presented. We also analyze the efficiency limits of single and multiple junction organic solar cells, and discuss the challenges facing their practical implementations.

Harmonic Quantum Coherence of Multiple Excitons in PbS/CdS Core-Shell Nanocrystals

NASA Astrophysics Data System (ADS)

Tahara, Hirokazu; Sakamoto, Masanori; Teranishi, Toshiharu; Kanemitsu, Yoshihiko

2017-12-01

The generation and recombination dynamics of multiple excitons in nanocrystals (NCs) have attracted much attention from the viewpoints of fundamental physics and device applications. However, the quantum coherence of multiple exciton states in NCs still remains unclear due to a lack of experimental support. Here, we report the first observation of harmonic dipole oscillations in PbS/CdS core-shell NCs using a phase-locked interference detection method for transient absorption. From the ultrafast coherent dynamics and excitation-photon-fluence dependence of the oscillations, we found that multiple excitons cause the harmonic dipole oscillations with ω , 2 ω , and 3 ω oscillations, even though the excitation pulse energy is set to the exciton resonance frequency, ω . This observation is closely related to the quantum coherence of multiple exciton states in NCs, providing important insights into multiple exciton generation mechanisms.

Exciton localization in polar and semipolar (112̅2) In0.2Ga0.8N/GaN multiple quantum wells

NASA Astrophysics Data System (ADS)

Dinh, Duc V.; Presa, Silvino; Maaskant, Pleun P.; Corbett, Brian; Parbrook, Peter J.

2016-08-01

The exciton localization (ELZ) in polar (0001) and semipolar (112̅2) In{}0.2Ga{}0.8{{N}} multiple-quantum-well (MQW) structures has been studied by excitation power density and temperature dependent photoluminescence. The ELZ in the (112̅2) MQW was found to be much stronger (ELZ degree σ E ˜ 40 -70 meV) compared to the (0001) MQW (σ E ˜ 5-11 meV) that was attributed to the anisotropic growth on the (112̅2) surface. This strong ELZ was found to cause a blue-shift of the (112̅2) MQW exciton emission with rising temperature from 200 to 340 K, irrespective of excitation source used. A lower luminescence efficiency of the (112̅2) MQW was attributed to their anisotropic growth, and higher concentrations of unintentional impurities and point defects than the (0001) MQW.

Singlet exciton fission photovoltaics.

PubMed

Lee, Jiye; Jadhav, Priya; Reusswig, Philip D; Yost, Shane R; Thompson, Nicholas J; Congreve, Daniel N; Hontz, Eric; Van Voorhis, Troy; Baldo, Marc A

2013-06-18

Singlet exciton fission, a process that generates two excitons from a single photon, is perhaps the most efficient of the various multiexciton-generation processes studied to date, offering the potential to increase the efficiency of solar devices. But its unique characteristic, splitting a photogenerated singlet exciton into two dark triplet states, means that the empty absorption region between the singlet and triplet excitons must be filled by adding another material that captures low-energy photons. This has required the development of specialized device architectures. In this Account, we review work to develop devices that harness the theoretical benefits of singlet exciton fission. First, we discuss singlet fission in the archetypal material, pentacene. Pentacene-based photovoltaic devices typically show high external and internal quantum efficiencies. They have enabled researchers to characterize fission, including yield and the impact of competing loss processes, within functional devices. We review in situ probes of singlet fission that modulate the photocurrent using a magnetic field. We also summarize studies of the dissociation of triplet excitons into charge at the pentacene-buckyball (C60) donor-acceptor interface. Multiple independent measurements confirm that pentacene triplet excitons can dissociate at the C60 interface despite their relatively low energy. Because triplet excitons produced by singlet fission each have no more than half the energy of the original photoexcitation, they limit the potential open circuit voltage within a solar cell. Thus, if singlet fission is to increase the overall efficiency of a solar cell and not just double the photocurrent at the cost of halving the voltage, it is necessary to also harvest photons in the absorption gap between the singlet and triplet energies of the singlet fission material. We review two device architectures that attempt this using long-wavelength materials: a three-layer structure that uses long- and short-wavelength donors and an acceptor and a simpler, two-layer combination of a singlet-fission donor and a long-wavelength acceptor. An example of the trilayer structure is singlet fission in tetracene with copper phthalocyanine inserted at the C60 interface. The bilayer approach includes pentacene photovoltaic cells with an acceptor of infrared-absorbing lead sulfide or lead selenide nanocrystals. Lead selenide nanocrystals appear to be the most promising acceptors, exhibiting efficient triplet exciton dissociation and high power conversion efficiency. Finally, we review architectures that use singlet fission materials to sensitize other absorbers, thereby effectively converting conventional donor materials to singlet fission dyes. In these devices, photoexcitation occurs in a particular molecule and then energy is transferred to a singlet fission dye where the fission occurs. For example, rubrene inserted between a donor and an acceptor decouples the ability to perform singlet fission from other major photovoltaic properties such as light absorption.

Ultrafast terahertz snapshots of excitonic Rydberg states and electronic coherence in an organometal halide perovskite

DOE PAGES

Luo, Liang; Men, Long; Liu, Zhaoyu; ...

2017-06-01

How photoexcitations evolve into Coulomb-bound electron and hole pairs, called excitons, and unbound charge carriers is a key cross-cutting issue in photovoltaics and optoelectronics. Until now, the initial quantum dynamics following photoexcitation remains elusive in the hybrid perovskite system. Furthermore we reveal excitonic Rydberg states with distinct formation pathways by observing the multiple resonant, internal quantum transitions using ultrafast terahertz quasi-particle transport. Nonequilibrium emergent states evolve with a complex co-existence of excitons, carriers and phonons, where a delayed buildup of excitons under on- and off-resonant pumping conditions allows us to distinguish between the loss of electronic coherence and hot statemore » cooling processes. The nearly ~1 ps dephasing time, efficient electron scattering with discrete terahertz phonons and intermediate binding energy of ~13.5 meV in perovskites are distinct from conventional photovoltaic semiconductors. In addition to providing implications for coherent energy conversion, these are potentially relevant to the development of light-harvesting and electron-transport devices.« less

Ultrafast terahertz snapshots of excitonic Rydberg states and electronic coherence in an organometal halide perovskite

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

Luo, Liang; Men, Long; Liu, Zhaoyu

How photoexcitations evolve into Coulomb-bound electron and hole pairs, called excitons, and unbound charge carriers is a key cross-cutting issue in photovoltaics and optoelectronics. Until now, the initial quantum dynamics following photoexcitation remains elusive in the hybrid perovskite system. Furthermore we reveal excitonic Rydberg states with distinct formation pathways by observing the multiple resonant, internal quantum transitions using ultrafast terahertz quasi-particle transport. Nonequilibrium emergent states evolve with a complex co-existence of excitons, carriers and phonons, where a delayed buildup of excitons under on- and off-resonant pumping conditions allows us to distinguish between the loss of electronic coherence and hot statemore » cooling processes. The nearly ~1 ps dephasing time, efficient electron scattering with discrete terahertz phonons and intermediate binding energy of ~13.5 meV in perovskites are distinct from conventional photovoltaic semiconductors. In addition to providing implications for coherent energy conversion, these are potentially relevant to the development of light-harvesting and electron-transport devices.« less

Programmed coherent coupling in a synthetic DNA-based excitonic circuit

NASA Astrophysics Data System (ADS)

Boulais, Étienne; Sawaya, Nicolas P. D.; Veneziano, Rémi; Andreoni, Alessio; Banal, James L.; Kondo, Toru; Mandal, Sarthak; Lin, Su; Schlau-Cohen, Gabriela S.; Woodbury, Neal W.; Yan, Hao; Aspuru-Guzik, Alán; Bathe, Mark

2018-02-01

Natural light-harvesting systems spatially organize densely packed chromophore aggregates using rigid protein scaffolds to achieve highly efficient, directed energy transfer. Here, we report a synthetic strategy using rigid DNA scaffolds to similarly program the spatial organization of densely packed, discrete clusters of cyanine dye aggregates with tunable absorption spectra and strongly coupled exciton dynamics present in natural light-harvesting systems. We first characterize the range of dye-aggregate sizes that can be templated spatially by A-tracts of B-form DNA while retaining coherent energy transfer. We then use structure-based modelling and quantum dynamics to guide the rational design of higher-order synthetic circuits consisting of multiple discrete dye aggregates within a DX-tile. These programmed circuits exhibit excitonic transport properties with prominent circular dichroism, superradiance, and fast delocalized exciton transfer, consistent with our quantum dynamics predictions. This bottom-up strategy offers a versatile approach to the rational design of strongly coupled excitonic circuits using spatially organized dye aggregates for use in coherent nanoscale energy transport, artificial light-harvesting, and nanophotonics.

Selectively Modulating Triplet Exciton Formation in Host Materials for Highly Efficient Blue Electrophosphorescence.

PubMed

Li, Huanhuan; Bi, Ran; Chen, Ting; Yuan, Kai; Chen, Runfeng; Tao, Ye; Zhang, Hongmei; Zheng, Chao; Huang, Wei

2016-03-23

The concept of limiting the triplet exciton formation to fundamentally alleviate triplet-involved quenching effects is introduced to construct host materials for highly efficient and stable blue phosphorescent organic light-emitting diodes (PhOLEDs). The low triplet exciton formation is realized by small triplet exciton formation fraction and rate with high binding energy and high reorganization energy of triplet exciton. Demonstrated in two analogue molecules in conventional donor-acceptor molecule structure for bipolar charge injection and transport with nearly the same frontier orbital energy levels and triplet excited energies, the new concept host material shows significantly suppressed triplet exciton formation in the host to avoid quenching effects, leading to much improved device efficiencies and stabilities. The low-voltage-driving blue PhOLED devices exhibit maximum efficiencies of 43.7 cd A(-1) for current efficiency, 32.7 lm W(-1) for power efficiency, and 20.7% for external quantum efficiency with low roll-off and remarkable relative quenching effect reduction ratio up to 41%. Our fundamental solution for preventing quenching effects of long-lived triplet excitons provides exciting opportunities for fabricating high-performance devices using the advanced host materials with intrinsically small triplet exciton formation cross section.

Exciton size and quantum transport in nanoplatelets

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

Pelzer, Kenley M., E-mail: kpelzer@anl.gov; Gray, Stephen K.; Darling, Seth B.

2015-12-14

Two-dimensional nanoplatelets (NPLs) are an exciting class of materials with promising optical and energy transport properties. The possibility of efficient energy transport between nanoplatelets raises questions regarding the nature of energy transfer in these thin, laterally extended systems. A challenge in understanding exciton transport is the uncertainty regarding the size of the exciton. Depending on the material and defects in the nanoplatelet, an exciton could plausibly extend over an entire plate or localize to a small region. The variation in possible exciton sizes raises the question how exciton size impacts the efficiency of transport between nanoplatelet structures. Here, we exploremore » this issue using a quantum master equation approach. This method goes beyond the assumptions of Förster theory to allow for quantum mechanical effects that could increase energy transfer efficiency. The model is extremely flexible in describing different systems, allowing us to test the effect of varying the spatial extent of the exciton. We first discuss qualitative aspects of the relationship between exciton size and transport and then conduct simulations of exciton transport between NPLs for a range of exciton sizes and environmental conditions. Our results reveal that exciton size has a strong effect on energy transfer efficiency and suggest that manipulation of exciton size may be useful in designing NPLs for energy transport.« less

Exciton size and quantum transport in nanoplatelets.

PubMed

Pelzer, Kenley M; Darling, Seth B; Gray, Stephen K; Schaller, Richard D

2015-12-14

Two-dimensional nanoplatelets (NPLs) are an exciting class of materials with promising optical and energy transport properties. The possibility of efficient energy transport between nanoplatelets raises questions regarding the nature of energy transfer in these thin, laterally extended systems. A challenge in understanding exciton transport is the uncertainty regarding the size of the exciton. Depending on the material and defects in the nanoplatelet, an exciton could plausibly extend over an entire plate or localize to a small region. The variation in possible exciton sizes raises the question how exciton size impacts the efficiency of transport between nanoplatelet structures. Here, we explore this issue using a quantum master equation approach. This method goes beyond the assumptions of Förster theory to allow for quantum mechanical effects that could increase energy transfer efficiency. The model is extremely flexible in describing different systems, allowing us to test the effect of varying the spatial extent of the exciton. We first discuss qualitative aspects of the relationship between exciton size and transport and then conduct simulations of exciton transport between NPLs for a range of exciton sizes and environmental conditions. Our results reveal that exciton size has a strong effect on energy transfer efficiency and suggest that manipulation of exciton size may be useful in designing NPLs for energy transport.

Carrier Multiplication Mechanisms and Competing Processes in Colloidal Semiconductor Nanostructures

PubMed Central

Kershaw, Stephen V.; Rogach, Andrey L.

2017-01-01

Quantum confined semiconductor nanoparticles, such as colloidal quantum dots, nanorods and nanoplatelets have broad extended absorption spectra at energies above their bandgaps. This means that they can absorb light at high photon energies leading to the formation of hot excitons with finite excited state lifetimes. During their existence, the hot electron and hole that comprise the exciton may start to cool as they relax to the band edge by phonon mediated or Auger cooling processes or a combination of these. Alongside these cooling processes, there is the possibility that the hot exciton may split into two or more lower energy excitons in what is termed carrier multiplication (CM). The fission of the hot exciton to form lower energy multiexcitons is in direct competition with the cooling processes, with the timescales for multiplication and cooling often overlapping strongly in many materials. Once CM has been achieved, the next challenge is to preserve the multiexcitons long enough to make use of the bonus carriers in the face of another competing process, non-radiative Auger recombination. However, it has been found that Auger recombination and the several possible cooling processes can be manipulated and usefully suppressed or retarded by engineering the nanoparticle shape, size or composition and by the use of heterostructures, along with different choices of surface treatments. This review surveys some of the work that has led to an understanding of the rich carrier dynamics in semiconductor nanoparticles, and that has started to guide materials researchers to nanostructures that can tilt the balance in favour of efficient CM with sustained multiexciton lifetimes. PMID:28927007

Assembling programmable FRET-based photonic networks using designer DNA scaffolds

PubMed Central

Buckhout-White, Susan; Spillmann, Christopher M; Algar, W. Russ; Khachatrian, Ani; Melinger, Joseph S.; Goldman, Ellen R.; Ancona, Mario G.; Medintz, Igor L.

2014-01-01

DNA demonstrates a remarkable capacity for creating designer nanostructures and devices. A growing number of these structures utilize Förster resonance energy transfer (FRET) as part of the device's functionality, readout or characterization, and, as device sophistication increases so do the concomitant FRET requirements. Here we create multi-dye FRET cascades and assess how well DNA can marshal organic dyes into nanoantennae that focus excitonic energy. We evaluate 36 increasingly complex designs including linear, bifurcated, Holliday junction, 8-arm star and dendrimers involving up to five different dyes engaging in four-consecutive FRET steps, while systematically varying fluorophore spacing by Förster distance (R0). Decreasing R0 while augmenting cross-sectional collection area with multiple donors significantly increases terminal exciton delivery efficiency within dendrimers compared with the first linear constructs. Förster modelling confirms that best results are obtained when there are multiple interacting FRET pathways rather than independent channels by which excitons travel from initial donor(s) to final acceptor. PMID:25504073

Highly Efficient Nondoped Green Organic Light-Emitting Diodes with Combination of High Photoluminescence and High Exciton Utilization.

PubMed

Wang, Chu; Li, Xianglong; Pan, Yuyu; Zhang, Shitong; Yao, Liang; Bai, Qing; Li, Weijun; Lu, Ping; Yang, Bing; Su, Shijian; Ma, Yuguang

2016-02-10

Photoluminescence (PL) efficiency and exciton utilization efficiency are two key parameters to harvest high-efficiency electroluminescence (EL) in organic light-emitting diodes (OLEDs). But it is not easy to simultaneously combine these two characteristics (high PL efficiency and high exciton utilization) into a fluorescent material. In this work, an efficient combination was achieved through two concepts of hybridized local and charge-transfer (CT) state (HLCT) and "hot exciton", in which the former is responsible for high PL efficiency while the latter contributes to high exciton utilization. On the basis of a tiny chemical modification in TPA-BZP, a green-light donor-acceptor molecule, we designed and synthesized CzP-BZP with this efficeient combination of high PL efficiency of η(PL) = 75% in the solid state and maximal exciton utilization efficiency up to 48% (especially, the internal quantum efficiency of η(IQE) = 35% substantially exceed 25% of spin statistics limit) in OLED. The nondoped OLED of CzP-BZP exhibited an excellent performance: a green emission with a CIE coordinate of (0.34, 0.60), a maximum current efficiency of 23.99 cd A(-1), and a maximum external quantum efficiency (EQE, η(EQE)) of 6.95%. This combined HLCT state and "hot exciton" strategy should be a practical way to design next-generation, low-cost, high-efficiency fluorescent OLED materials.

Estimation of exciton reverse transfer for variable spectra and high efficiency in interlayer-based organic light-emitting devices

NASA Astrophysics Data System (ADS)

Liu, Shengqiang; Zhao, Juan; Huang, Jiang; Yu, Junsheng

2016-12-01

Organic light-emitting devices (OLEDs) with three different exciton adjusting interlayers (EALs), which are inserted between two complementary blue and yellow emitting layers, are fabricated to demonstrate the relationship between the EAL and device performance. The results show that the variations of type and thickness of EAL have different adjusting capability and distribution control on excitons. However, we also find that the reverse Dexter transfer of triplet exciton from the light-emitting layer to the EAL is an energy loss path, which detrimentally affects electroluminescent (EL) spectral performance and device efficiency in different EAL-based devices. Based on exciton distribution and integration, an estimation of exciton reverse transfer is developed through a triplet energy level barrier to simulate the exciton behavior. Meanwhile, the estimation results also demonstrate the relationship between the EAL and device efficiency by a parameter of exciton reverse transfer probability. The estimation of exciton reverse transfer discloses a crucial role of the EALs in the interlayer-based OLEDs to achieve variable EL spectra and high efficiency.

Tailoring Quantum Dot Assemblies to Extend Exciton Coherence Times and Improve Exciton Transport

NASA Astrophysics Data System (ADS)

Seward, Kenton; Lin, Zhibin; Lusk, Mark

2012-02-01

The motion of excitons through nanostructured assemblies plays a central role in a wide range of physical phenomena including quantum computing, molecular electronics, photosynthetic processes, excitonic transistors and light emitting diodes. All of these technologies are severely handicapped, though, by quasi-particle lifetimes on the order of a nanosecond. The movement of excitons must therefore be as efficient as possible in order to move excitons meaningful distances. This is problematic for assemblies of small Si quantum dots (QDs), where excitons quickly localize and entangle with dot phonon modes. Ensuing exciton transport is then characterized by a classical random walk reduced to very short distances because of efficient recombination. We use a combination of master equation (Haken-Strobl) formalism and density functional theory to estimate the rate of decoherence in Si QD assemblies and its impact on exciton mobility. Exciton-phonon coupling and Coulomb interactions are calculated as a function of dot size, spacing and termination to minimize the rate of intra-dot phonon entanglement. This extends the time over which more efficient exciton transport, characterized by partial coherence, can be maintained.

Effect of co-crystallization on singlet fission efficiency in pentacene derivatives

NASA Astrophysics Data System (ADS)

Wang, Xiaopeng; Sanders, Samuel; Campos, Luis; Sfeir, Matthew; Marom, Noa

Singlet fission (SF), the conversion of one singlet exciton into two triplet excitons, may lead to a twofold increase in the efficiency of organic photovoltaics. Since SF has been observed in crystalline pentacene, this material has drawn interest both experimentally and theoretically. Recently, it has been shown that SF efficiency in rubrene may be improved by modifying the crystal packing. Here, we study the effect of co-crystallization with small molecule H-bond donors on SF efficiency in pentacene derivatives. Five co-crystals are synthetized and their photoluminescence (PL) and absorption spectra are measured. First-principles calculations based on many-body perturbation theory (MBPT) are then employed to study their excitonic properties. By combining experiment and theory, we demonsrate that excitonic properties, including singlet-triplet gaps, exciton binding energies, and exciton localization, are significantly modulated in pentacene co-crystals. Consequently, co-crystallization becomes an effective strategy for improving SF efficiency in molecular crystals of organic semiconductors.

Morphological and Compositional (S)TEM Analysis of Multiple Exciton Generation Solar Cells

NASA Astrophysics Data System (ADS)

Wisnivesky-Rocca-Rivarola, F.; Davis, N. J. L. K.; Bohm, M.; Ducati, C.

2015-10-01

Quantum confinement of charge carriers in semiconductor nanocrystals produces optical and electronic properties that have the potential to enhance the power conversion efficiency of solar cells. One of these properties is the efficient formation of more than one electron-hole pair from a single absorbed photon, in a process called multiple exciton generation (MEG). In this work we studied the morphology of nanocrystal multilayers of PbSe treated with CdCl2 using complementary imaging and spectroscopy techniques to characterise the chemical composition and morphology of full MEG devices made with PbSe nanorods (NRs). IN the scanning TEM (STEM), plan view images and chemical maps were obtained of the nanocrystal layers, which allowed for the analysis of crystal structure and orientation, as well as size distribution and aspect ratio. These results were complemented by cross-sectional images of full devices, which allowed accessing the structure of each layer that composes the device, including the nanorod packing in the active nanocrystal layer.

Charge transport through exciton shelves in cadmium chalcogenide quantum dot-DNA nano-bioelectronic thin films

NASA Astrophysics Data System (ADS)

Goodman, Samuel M.; Noh, Hyunwoo; Singh, Vivek; Cha, Jennifer N.; Nagpal, Prashant

2015-02-01

Quantum dot (QD), or semiconductor nanocrystal, thin films are being explored for making solution-processable devices due to their size- and shape-tunable bandgap and discrete higher energy electronic states. While DNA has been extensively used for the self-assembly of nanocrystals, it has not been investigated for the simultaneous conduction of multiple energy charges or excitons via exciton shelves (ES) formed in QD-DNA nano-bioelectronic thin films. Here, we present studies on charge conduction through exciton shelves, which are formed via chemically coupled QDs and DNA, between electronic states of the QDs and the HOMO-LUMO levels in the complementary DNA nucleobases. While several challenges need to be addressed in optimizing the formation of devices using QD-DNA thin films, a higher charge collection efficiency for hot-carriers and our detailed investigations of charge transport mechanism in these thin films highlight their potential for applications in nano-bioelectronic devices and biological transducers.

Excitonic energy transfer in light-harvesting complexes in purple bacteria

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

Ye Jun; Sun Kewei; Zhao Yang

Two distinct approaches, the Frenkel-Dirac time-dependent variation and the Haken-Strobl model, are adopted to study energy transfer dynamics in single-ring and double-ring light-harvesting (LH) systems in purple bacteria. It is found that the inclusion of long-range dipolar interactions in the two methods results in significant increase in intra- or inter-ring exciton transfer efficiency. The dependence of exciton transfer efficiency on trapping positions on single rings of LH2 (B850) and LH1 is similar to that in toy models with nearest-neighbor coupling only. However, owing to the symmetry breaking caused by the dimerization of BChls and dipolar couplings, such dependence has beenmore » largely suppressed. In the studies of coupled-ring systems, both methods reveal an interesting role of dipolar interactions in increasing energy transfer efficiency by introducing multiple intra/inter-ring transfer paths. Importantly, the time scale (4 ps) of inter-ring exciton transfer obtained from polaron dynamics is in good agreement with previous studies. In a double-ring LH2 system, non-nearest neighbor interactions can induce symmetry breaking, which leads to global and local minima of the average trapping time in the presence of a non-zero dephasing rate, suggesting that environment dephasing helps preserve quantum coherent energy transfer when the perfect circular symmetry in the hypothetic system is broken. This study reveals that dipolar coupling between chromophores may play an important role in the high energy transfer efficiency in the LH systems of purple bacteria and many other natural photosynthetic systems.« less

Effect of Annealing on Exciton Diffusion in a High Performance Small Molecule Organic Photovoltaic Material.

PubMed

Long, Yun; Hedley, Gordon J; Ruseckas, Arvydas; Chowdhury, Mithun; Roland, Thomas; Serrano, Luis A; Cooke, Graeme; Samuel, Ifor D W

2017-05-03

Singlet exciton diffusion was studied in the efficient organic photovoltaic electron donor material DTS(FBTTh 2 ) 2 . Three complementary time-resolved fluorescence measurements were performed: quenching in planar heterojunctions with an electron acceptor, exciton-exciton annihilation, and fluorescence depolarization. The average exciton diffusivity increases upon annealing from 1.6 × 10 -3 to 3.6 × 10 -3 cm 2 s -1 , resulting in an enhancement of the mean two-dimensional exciton diffusion length (L D = (4Dτ) 1/2 ) from 15 to 27 nm. About 30% of the excitons get trapped very quickly in as-cast films. The high exciton diffusion coefficient of the material leads to it being able to harvest excitons efficiently from large donor domains in bulk heterojunctions.

Effects of surface and interface traps on exciton and multi-exciton dynamics in core/shell quantum dots

NASA Astrophysics Data System (ADS)

Bozio, Renato; Righetto, Marcello; Minotto, Alessandro

2017-08-01

Exciton interactions and dynamics are the most important factors determining the exceptional photophysical properties of semiconductor quantum dots (QDs). In particular, best performances have been obtained for ingeniously engineered core/shell QDs. We have studied two factors entering in the exciton decay dynamics with adverse effects for the luminescence efficiency: exciton trapping at surface and interface traps, and non-radiative Auger recombination in QDs carrying either net charges or multiple excitons. In this work, we present a detailed study into the optical absorption, fluorescence dynamics and quantum yield, as well as ultrafast transient absorption properties of CdSe/CdS, CdSe/Cd0.5Zn0.5S, and CdSe/ZnS QDs as a function of shell thickness. It turns out that de-trapping processes play a pivotal role in determining steady state emission properties. By studying the excitation dependent photoluminescence quantum yields (PLQY) in different CdSe/CdxZn1-xS (x = 0, 0.5, 1) QDs, we demonstrate the different role played by hot and cold carrier trapping rates in determining fluorescence quantum yields. Finally, the use of global analysis allows us untangling the complex ultrafast transient absorption signals. Smoothing of interface potential, together with effective surface passivation, appear to be crucial factors in slowing down both Auger-based and exciton trapping recombination processes.

Triplet energy transfer and triplet exciton recycling in singlet fission sensitized organic heterojunctions

NASA Astrophysics Data System (ADS)

Hamid, Tasnuva; Yambem, Soniya D.; Crawford, Ross; Roberts, Jonathan; Pandey, Ajay K.

2017-08-01

Singlet exciton fission is a process where an excited singlet state splits into two triplets, thus leading to generation of multiple excitons per absorbed photon in organic semiconductors. Herein, we report a detailed exciton management approach for multiexciton harvesting over a broadband region of the solar spectrum in singlet fission sensitized organic photodiodes. Through systematic studies on the model cascade of pentacene/rubrene/C60, we found that efficient photocurrent generation from pentacene can still occur despite the presence of a >10nm thick interlayer of rubrene in between the pentacene/C60 heterojunction. Our results show that thin rubrene interlayers of thickness < 5 nm are effective in maintaining the delicate balance between two free charge generation channels that progress independently via the electron and hole transfer routes. The contribution to photocurrent from pentacene despite having a reasonably thick rubrene interlayer, that too with higher triplet energy (T1=1.12 eV) than pentacene (T1= 0.86 eV), makes its operation a rather interesting result. We discuss the role of rubrene interlayer film discontinuity, triplet exciton reflection from rubrene interlayer and triplet energy transfer from rubrene to pentacene layer followed by diffusion of triplet excitons through rubrene as plausible mechanisms that would enable triplet excitons from pentacene to generate significant photocurrent in a multilayer organic heterojunction.

Excessive Exoergicity Reduces Singlet Exciton Fission Efficiency of Heteroacenes in Solutions.

PubMed

Zhang, You-Dan; Wu, Yishi; Xu, Yanqing; Wang, Qiang; Liu, Ke; Chen, Jian-Wei; Cao, Jing-Jing; Zhang, Chunfeng; Fu, Hongbing; Zhang, Hao-Li

2016-06-01

The energy difference between a singlet exciton and twice of a triplet exciton, ΔESF, provides the thermodynamic driving force for singlet exciton fission (SF). This work reports a systematic investigation on the effect of ΔESF on SF efficiency of five heteroacenes in their solutions. The low-temperature, near-infrared phosphorescence spectra gave the energy levels of the triplet excitons, allowing us to identify the values of ΔESF, which are -0.58, -0.34, -0.31, -0.32, and -0.34 eV for the thiophene, benzene, pyridine, and two tetrafluorobenzene terminated molecules, respectively. Corresponding SF efficiencies of the five heteroacenes in 0.02 M solutions were determined via femtosecond transient absorption spectroscopy to be 117%, 124%, 140%, 132%, and 135%, respectively. This result reveals that higher ΔESF is not, as commonly expected, always beneficial for higher SF efficiency in solution phase. On the contrary, excessive exoergicity results in reduction of SF efficiency in the heteroacenes due to the promotion of other competitive exciton relaxation pathways. Therefore, it is important to optimize thermodynamic driving force when designing organic materials for high SF efficiency.

DNA-mediated excitonic upconversion FRET switching

DOE PAGES

Kellis, Donald L.; Rehn, Sarah M.; Cannon, Brittany L.; ...

2015-11-17

Excitonics is a rapidly expanding field of nanophotonics in which the harvesting of photons, ensuing creation and transport of excitons via Förster resonant energy transfer (FRET), and subsequent charge separation or photon emission has led to the demonstration of excitonic wires, switches, Boolean logic and light harvesting antennas for many applications. FRET funnels excitons down an energy gradient resulting in energy loss with each step along the pathway. Conversely, excitonic energy up conversion via up conversion nanoparticles (UCNPs), although currently inefficient, serves as an energy ratchet to boost the exciton energy. Although FRET-based up conversion has been demonstrated, it suffersmore » from low FRET efficiency and lacks the ability to modulate the FRET. We have engineered an up conversion FRET-based switch by combining lanthanide-doped UCNPs and fluorophores that demonstrates excitonic energy up conversion by nearly a factor of 2, an excited state donor to acceptor FRET efficiency of nearly 25%, and an acceptor fluorophore quantum efficiency that is close to unity. These findings offer a promising path for energy up conversion in nanophotonic applications including artificial light harvesting, excitonic circuits, photovoltaics, nanomedicine, and optoelectronics.« less

Exciton-dominant electroluminescence from a diode of monolayer MoS{sub 2}

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

Ye, Yu; Ye, Ziliang; Gharghi, Majid

2014-05-12

In two-dimensional monolayer MoS{sub 2}, excitons dominate the absorption and emission properties. However, the low electroluminescent efficiency and signal-to-noise ratio limit our understanding of the excitonic behavior of electroluminescence. Here, we study the microscopic origin of the electroluminescence from a diode of monolayer MoS{sub 2} fabricated on a heavily p-type doped silicon substrate. Direct and bound-exciton related recombination processes are identified from the electroluminescence. At a high electron-hole pair injection rate, Auger recombination of the exciton-exciton annihilation of the bound exciton emission is observed at room temperature. Moreover, the efficient electrical injection demonstrated here allows for the observation of amore » higher energy exciton peak of 2.255 eV in the monolayer MoS{sub 2} diode, attributed to the excited exciton state of a direct-exciton transition.« less

Organic-Inorganic Composites of Semiconductor Nanocrystals for Efficient Excitonics.

PubMed

Guzelturk, Burak; Demir, Hilmi Volkan

2015-06-18

Nanocomposites of colloidal semiconductor nanocrystals integrated into conjugated polymers are the key to soft-material hybrid optoelectronics, combining advantages of both plastics and particles. Synergic combination of the favorable properties in the hybrids of colloidal nanocrystals and conjugated polymers offers enhanced performance and new functionalities in light-generation and light-harvesting applications, where controlling and mastering the excitonic interactions at the nanoscale are essential. In this Perspective, we highlight and critically consider the excitonic interactions in the organic-inorganic nanocomposites to achieve highly efficient exciton transfer through rational design of the nanocomposites. The use of strong excitonic interactions in optoelectronic devices can trigger efficiency breakthroughs in hybrid optoelectronics.

Effect of Annealing on Exciton Diffusion in a High Performance Small Molecule Organic Photovoltaic Material

PubMed Central

2017-01-01

Singlet exciton diffusion was studied in the efficient organic photovoltaic electron donor material DTS(FBTTh2)2. Three complementary time-resolved fluorescence measurements were performed: quenching in planar heterojunctions with an electron acceptor, exciton–exciton annihilation, and fluorescence depolarization. The average exciton diffusivity increases upon annealing from 1.6 × 10–3 to 3.6 × 10–3 cm2 s–1, resulting in an enhancement of the mean two-dimensional exciton diffusion length (LD = (4Dτ)1/2) from 15 to 27 nm. About 30% of the excitons get trapped very quickly in as-cast films. The high exciton diffusion coefficient of the material leads to it being able to harvest excitons efficiently from large donor domains in bulk heterojunctions. PMID:28358189

Energy and Information Transfer Via Coherent Exciton Wave Packets

NASA Astrophysics Data System (ADS)

Zang, Xiaoning

Electronic excitons are bound electron-hole states that are generated when light interacts with matter. Such excitations typically entangle with phonons and rapidly decohere; the resulting electronic state dynamics become diffusive as a result. However, if the exciton-phonon coupling can be reduced, it may be possible to construct excitonic wave packets that offer a means of efficiently transmitting information and energy. This thesis is a combined theory/computation investigation to design condensed matter systems which support the requisite coherent transport. Under the idealizing assumption that exciton-phonon entanglement could be completely suppressed, the majority of this thesis focuses on the creation and manipulation of exciton wave packets in quasi-one-dimensional systems. While each site could be a silicon quantum dot, the actual implementation focused on organic molecular assemblies for the sake of computational simplicity, ease of experimental implementation, potential for coherent transport, and promise because of reduced structural uncertainty. A laser design was derived to create exciton wave packets with tunable shape and speed. Quantum interference was then exploited to manipulate these packets to block, pass, and even dissociate excitons based on their energies. These developments allow exciton packets to be considered within the arena of quantum information science. The concept of controllable excitonic wave packets was subsequently extended to consider molecular designs that allow photons with orbital angular momentum to be absorbed to create excitons with a quasi-angular momentum of their own. It was shown that a well-defined measure of topological charge is conserved in such light-matter interactions. Significantly, it was also discovered that such molecules allow photon angular momenta to be combined and later emitted. This amounts to a new way of up/down converting photonic angular momentum without relying on nonlinear optical materials. The associated excitations were dubbed twisted excitons. Twisted exciton packets can be manipulated as they travel down molecular chains, and this has applications in quantum information science as well. In each setting considered, exciton dynamics were initially studied using a simple tight-binding formalism. This misses the actual many-body interactions and multiple energy levels associated real systems. To remedy this, I adapted an existing time-domain Density Functional Theory code and applied it to study the dynamics of exciton wave packets on quasi-one-dimensional systems. This required the use of high-performance computing and the construction of a number of key auxiliary codes. Establishing the requisite methodology constituted a substantial part of the entire thesis. Surprisingly, this effort uncovered a computational issue associated with Rabi oscillations that had been incorrectly characterized in the literature. My research elucidated the actual problem and a solution was found. This new methodology was an integral part of the overall computational analysis. The thesis then takes up the a detailed consideration of the prospect for creating systems that support a strong measure of transport coherence. While physical implementations include molecular assemblies, solid-state superlattices, and even optical lattices, I decided to focus on assemblies of nanometer-sized silicon quantum dots. First principles computational analysis was used to quantify reorganization within individual dots and excitonic coupling between dots. Quantum dot functionalizations were identified that make it plausible to maintain a measure of excitonic coherence even at room temperatures. Attention was then turned to the use of covalently bonded bridge material to join quantum dots in a way that facilitates efficient exciton transfer. Both carbon and silicon structures were considered by considering the way in which subunits might be best brought together. This resulted in a set of design criteria which were then evaluated using first-principles, excited state analyses. It was found that efficient exciton transfer is indeed possible. When coupled to the previous quantum dot functionalizations, the notion that quantum dot materials could support partially coherent exciton wave packets was determined to be quite reasonable.

Extremely Low Roll-Off and High Efficiency Achieved by Strategic Exciton Management in Organic Light-Emitting Diodes with Simple Ultrathin Emitting Layer Structure.

PubMed

Zhang, Tianmu; Shi, Changsheng; Zhao, Chenyang; Wu, Zhongbin; Chen, Jiangshan; Xie, Zhiyuan; Ma, Dongge

2018-03-07

Phosphorescent organic light-emitting diodes (OLEDs) possess the property of high efficiency but have serious efficiency roll-off at high luminance. Herein, we manufactured high-efficiency phosphorescent OLEDs with extremely low roll-off by effectively locating the ultrathin emitting layer (UEML) away from the high-concentration exciton formation region. The strategic exciton management in this simple UEML architecture greatly suppressed the exciton annihilation due to the expansion of the exciton diffusion region; thus, this efficiency roll-off at high luminance was significantly improved. The resulting green phosphorescent OLEDs exhibited the maximum external quantum efficiency of 25.5%, current efficiency of 98.0 cd A -1 , and power efficiency of 85.4 lm W -1 and still had 25.1%, 94.9 cd A -1 , and 55.5 lm W -1 at 5000 cd m -2 luminance, and retained 24.3%, 92.7 cd A -1 , and 49.3 lm W -1 at 10 000 cd m -2 luminance, respectively. Compared with the usual structures, the improvement demonstrated in this work displays potential value in applications.

Efficient Carrier-to-Exciton Conversion in Field Emission Tunnel Diodes Based on MIS-Type van der Waals Heterostack.

PubMed

Wang, Shunfeng; Wang, Junyong; Zhao, Weijie; Giustiniano, Francesco; Chu, Leiqiang; Verzhbitskiy, Ivan; Zhou Yong, Justin; Eda, Goki

2017-08-09

We report on efficient carrier-to-exciton conversion and planar electroluminescence from tunnel diodes based on a metal-insulator-semiconductor (MIS) van der Waals heterostack consisting of few-layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer tungsten disulfide (WS 2 ). These devices exhibit excitonic electroluminescence with extremely low threshold current density of a few pA·μm -2 , which is several orders of magnitude lower compared to the previously reported values for the best planar EL devices. Using a reference dye, we estimate the EL quantum efficiency to be ∼1% at low current density limit, which is of the same order of magnitude as photoluminescence quantum yield at the equivalent excitation rate. Our observations reveal that the efficiency of our devices is not limited by carrier-to-exciton conversion efficiency but by the inherent exciton-to-photon yield of the material. The device characteristics indicate that the light emission is triggered by injection of hot minority carriers (holes) to n-doped WS 2 by Fowler-Nordheim tunneling and that hBN serves as an efficient hole-transport and electron-blocking layer. Our findings offer insight into the intelligent design of van der Waals heterostructures and avenues for realizing efficient excitonic devices.

Observation of rapid exciton-exciton annihilation in monolayer molybdenum disulfide.

PubMed

Sun, Dezheng; Rao, Yi; Reider, Georg A; Chen, Gugang; You, Yumeng; Brézin, Louis; Harutyunyan, Avetik R; Heinz, Tony F

2014-10-08

Monolayer MoS2 is a direct-gap two-dimensional semiconductor that exhibits strong electron-hole interactions, leading to the formation of stable excitons and trions. Here we report the existence of efficient exciton-exciton annihilation, a four-body interaction, in this material. Exciton-exciton annihilation was identified experimentally in ultrafast transient absorption measurements through the emergence of a decay channel varying quadratically with exciton density. The rate of exciton-exciton annihilation was determined to be (4.3 ± 1.1) × 10(-2) cm(2)/s at room temperature.

Exploring exciton relaxation and multiexciton generation in PbSe nanocrystals using hyperspectral near-IR probing.

PubMed

Gdor, Itay; Sachs, Hanan; Roitblat, Avishy; Strasfeld, David B; Bawendi, Moungi G; Ruhman, Sanford

2012-04-24

Hyperspectral femtosecond transient absorption spectroscopy is employed to record exciton relaxation and recombination in colloidal lead selenide (PbSe) nanocrystals in unprecedented detail. Results obtained with different pump wavelengths and fluences are scrutinized with regard to three issues: (1) early subpicosecond spectral features due to "hot" excitons are analyzed in terms of suggested underlying mechanisms; (2) global kinetic analysis facilitates separation of the transient difference spectra into single, double, and triple exciton state contributions, from which individual band assignments can be tested; and (3) the transient spectra are screened for signatures of multiexciton generation (MEG) by comparing experiments with excitation pulses both below and well above the theoretical threshold for multiplication. For the latter, a recently devised ultrafast pump-probe spectroscopic approach is employed. Scaling sample concentrations and pump pulse intensities inversely with the extinction coefficient at each excitation wavelength overcomes ambiguities due to direct multiphoton excitation, uncertainties of absolute absorption cross sections, and low signal levels. As observed in a recent application of this method to InAs core/shell/shell nanodots, no sign of MEG was detected in this sample up to photon energy 3.7 times the band gap. Accordingly, numerous reports of efficient MEG in other samples of PbSe suggest that the efficiency of this process varies from sample to sample and depends on factors yet to be determined.

Organic solar cells: understanding the role of Förster resonance energy transfer.

PubMed

Feron, Krishna; Belcher, Warwick J; Fell, Christopher J; Dastoor, Paul C

2012-12-12

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by F¨orster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of F¨orster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells.

Cascade exciton-pumping engines with manipulated speed and efficiency in light-harvesting porous π-network films

PubMed Central

Gu, Cheng; Huang, Ning; Xu, Fei; Gao, Jia; Jiang, Donglin

2015-01-01

Light-harvesting antennae are the machinery for exciton pumping in natural photosynthesis, whereas cascade energy transfer through chlorophyll is key to long-distance, efficient energy transduction. Numerous artificial antennae have been developed. However, they are limited in their cascade energy-transfer abilities because of a lack of control over complex chromophore aggregation processes, which has impeded their advancement. Here we report a viable approach for addressing this issue by using a light-harvesting porous polymer film in which a three-dimensional π-network serves as the antenna and micropores segregate multiple dyes to prevent aggregation. Cascade energy-transfer engines are integrated into the films; the rate and efficiency of the energy-funneling engines are precisely manipulated by tailoring the dye components and contents. The nanofilms allow accurate and versatile luminescence engineering, resulting in the production of thirty emission hues, including blue, green, red and white. This advance may open new pathways for realising photosynthesis and photoenergy conversion. PMID:25746459

Achieving Extreme Utilization of Excitons by an Efficient Sandwich-Type Emissive Layer Architecture for Reduced Efficiency Roll-Off and Improved Operational Stability in Organic Light-Emitting Diodes.

PubMed

Wu, Zhongbin; Sun, Ning; Zhu, Liping; Sun, Hengda; Wang, Jiaxiu; Yang, Dezhi; Qiao, Xianfeng; Chen, Jiangshan; Alshehri, Saad M; Ahamad, Tansir; Ma, Dongge

2016-02-10

It has been demonstrated that the efficiency roll-off is generally caused by the accumulation of excitons or charge carriers, which is intimately related to the emissive layer (EML) architecture in organic light-emitting diodes (OLEDs). In this article, an efficient sandwich-type EML structure with a mixed-host EML sandwiched between two single-host EMLs was designed to eliminate this accumulation, thus simultaneously achieving high efficiency, low efficiency roll-off and good operational stability in the resulting OLEDs. The devices show excellent electroluminescence performances, realizing a maximum external quantum efficiency (EQE) of 24.6% with a maximum power efficiency of 105.6 lm W(-1) and a maximum current efficiency of 93.5 cd A(-1). At the high brightness of 5,000 cd m(-2), they still remain as high as 23.3%, 71.1 lm W(-1), and 88.3 cd A(-1), respectively. And, the device lifetime is up to 2000 h at initial luminance of 1000 cd m(-2), which is significantly higher than that of compared devices with conventional EML structures. The improvement mechanism is systematically studied by the dependence of the exciton distribution in EML and the exciton quenching processes. It can be seen that the utilization of the efficient sandwich-type EML broadens the recombination zone width, thus greatly reducing the exciton quenching and increasing the probability of the exciton recombination. It is believed that the design concept provides a new avenue for us to achieve high-performance OLEDs.

Reducing exciton binding energy by increasing thin film permittivity: an effective approach to enhance exciton separation efficiency in organic solar cells.

PubMed

Leblebici, Sibel Y; Chen, Teresa L; Olalde-Velasco, Paul; Yang, Wanli; Ma, Biwu

2013-10-23

Photocurrent generation in organic solar cells requires that excitons, which are formed upon light absorption, dissociate into free carriers at the interface of electron acceptor and donor materials. The high exciton binding energy, arising from the low permittivity of organic semiconductor films, generally causes low exciton separation efficiency and subsequently low power conversion efficiency. We demonstrate here, for the first time, that the exciton binding energy in B,O-chelated azadipyrromethene (BO-ADPM) donor films is reduced by increasing the film permittivity by blending the BO-ADPM donor with a high dielectric constant small molecule, camphoric anhydride (CA). Various spectroscopic techniques, including impedance spectroscopy, photon absorption and emission spectroscopies, as well as X-ray spectroscopies, are applied to characterize the thin film electronic and photophysical properties. Planar heterojunction solar cells are fabricated with a BO-ADPM:CA film as the electron donor and C60 as the acceptor. With an increase in the dielectric constant of the donor film from ∼4.5 to ∼11, the exciton binding energy is reduced and the internal quantum efficiency of the photovoltaic cells improves across the entire spectrum, with an ∼30% improvement in the BO-ADPM photoactive region.

Engineered nanomaterials for solar energy conversion.

PubMed

Mlinar, Vladan

2013-02-01

Understanding how to engineer nanomaterials for targeted solar-cell applications is the key to improving their efficiency and could lead to breakthroughs in their design. Proposed mechanisms for the conversion of solar energy to electricity are those exploiting the particle nature of light in conventional photovoltaic cells, and those using the collective electromagnetic nature, where light is captured by antennas and rectified. In both cases, engineered nanomaterials form the crucial components. Examples include arrays of semiconductor nanostructures as an intermediate band (so called intermediate band solar cells), semiconductor nanocrystals for multiple exciton generation, or, in antenna-rectifier cells, nanomaterials for effective optical frequency rectification. Here, we discuss the state of the art in p-n junction, intermediate band, multiple exciton generation, and antenna-rectifier solar cells. We provide a summary of how engineered nanomaterials have been used in these systems and a discussion of the open questions.

Exciton size and binding energy limitations in one-dimensional organic materials.

PubMed

Kraner, S; Scholz, R; Plasser, F; Koerner, C; Leo, K

2015-12-28

In current organic photovoltaic devices, the loss in energy caused by the charge transfer step necessary for exciton dissociation leads to a low open circuit voltage, being one of the main reasons for rather low power conversion efficiencies. A possible approach to avoid these losses is to tune the exciton binding energy to a value of the order of thermal energy, which would lead to free charges upon absorption of a photon, and therefore increase the power conversion efficiency towards the Shockley-Queisser limit. We determine the size of the excitons for different organic molecules and polymers by time dependent density functional theory calculations. For optically relevant transitions, the exciton size saturates around 0.7 nm for one-dimensional molecules with a size longer than about 4 nm. For the ladder-type polymer poly(benzimidazobenzophenanthroline), we obtain an exciton binding energy of about 0.3 eV, serving as a lower limit of the exciton binding energy for the organic materials investigated. Furthermore, we show that charge transfer transitions increase the exciton size and thus identify possible routes towards a further decrease of the exciton binding energy.

Organic Solar Cells: Understanding the Role of Förster Resonance Energy Transfer

PubMed Central

Feron, Krishna; Belcher, Warwick J.; Fell, Christopher J.; Dastoor, Paul C.

2012-01-01

Organic solar cells have the potential to become a low-cost sustainable energy source. Understanding the photoconversion mechanism is key to the design of efficient organic solar cells. In this review, we discuss the processes involved in the photo-electron conversion mechanism, which may be subdivided into exciton harvesting, exciton transport, exciton dissociation, charge transport and extraction stages. In particular, we focus on the role of energy transfer as described by Förster resonance energy transfer (FRET) theory in the photoconversion mechanism. FRET plays a major role in exciton transport, harvesting and dissociation. The spectral absorption range of organic solar cells may be extended using sensitizers that efficiently transfer absorbed energy to the photoactive materials. The limitations of Förster theory to accurately calculate energy transfer rates are discussed. Energy transfer is the first step of an efficient two-step exciton dissociation process and may also be used to preferentially transport excitons to the heterointerface, where efficient exciton dissociation may occur. However, FRET also competes with charge transfer at the heterointerface turning it in a potential loss mechanism. An energy cascade comprising both energy transfer and charge transfer may aid in separating charges and is briefly discussed. Considering the extent to which the photo-electron conversion efficiency is governed by energy transfer, optimisation of this process offers the prospect of improved organic photovoltaic performance and thus aids in realising the potential of organic solar cells. PMID:23235328

A Versatile Molecular Design for High-Performance Nondoped OLEDs with ~100% Exciton Utilization and Negligible Efficiency Roll-Off.

PubMed

Liu, Huijun; Zeng, Jiajie; Guo, Jingjing; Nie, Han; Zhao, Zujin; Tang, Ben Zhong

2018-06-01

Nondoped organic light-emitting diodes (OLEDs) possess merits of higher stability and easier fabrication than doped devices. However, luminescent materials with high exciton utilization are generally unsuitable for nondoped OLEDs because of severe emission quenching and exciton annihilation in neat films. Herein, we wish to report a novel molecular design of integrating aggregation-induced delayed fluorescence (AIDF) moiety within host materials to explore efficient luminogens for nondoped OLEDs. By grafting 4-(phenoxazin-10-yl)benzoyl to common host materials, we develop a series of new luminescent materials with prominent AIDF property. Their neat films fluoresce strongly and can fully harvest both singlet and triplet excitons with suppressed exciton annihilation. Nondoped OLEDs of these AIDF luminogens exhibit excellent luminance (~100000 cd m-2), outstanding external quantum efficiencies (22.1-22.6%), negligible efficiency roll-off and improved operational stability. To the best of our knowledge, these are the most efficient nondoped OLEDs reported so far. This convenient and versatile molecular design is of high significance for the advance of nondoped OLEDs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coexistence of excitons and free carriers in Cd 1- xMn xTe/ZnTe multiple-quantum wells

NASA Astrophysics Data System (ADS)

Pittini, R.; Shen, J. X.; Takahashi, M.; Oka, Y.

2000-06-01

Optical pump-probe experiments were carried out in Cd 1- xMn xTe/ZnTe multiple-quantum wells to study the carrier dynamics and the exciton formation in these materials. Starting from 15 ps after the pump excitation, the bleaching of the absorption of the heavy-hole excitons in the wells yields a strong negative pump-probe signal. But before this occurs, the pump-probe signal has a completely different lineshape resembling a lying `S'. The time evolution of the pump-probe signal is understood to have arisen from a coexistence of carriers and excitons. We treated the excitons in the wells as Mahan excitons and obtained a good fit to the experimental data. The cooling of the carriers after the pump excitation can be monitored as an increasing Fermi energy of the `cold' carriers at the band edge. The Fermi sea is then depleted starting from 15 ps after the pump excitation due to the formation of excitons.

Efficient Interlayer Relaxation and Transition of Excitons in Epitaxial and Non-epitaxial MoS2/WS2 Heterostructures

DOE PAGES

Yu, Yifei; Hu, Shi; Su, Liqin; ...

2014-12-03

Semiconductor heterostructurs provide a powerful platform for the engineering of excitons. Here we report on the excitonic properties of two-dimensional (2D) heterostructures that consist of monolayer MoS2 and WS2 stacked epitaxially or non-epitaxially in the vertical direction. We find similarly efficient interlayer relaxation and transition of excitons in both the epitaxial and non-epitaxial heterostructures. This is manifested by a two orders of magnitude decrease in the photoluminescence and an extra absorption peak at low energy region of both heterostructures. The MoS2/WS2 heterostructures show weak interlayer coupling and essentially act as an atomic-scale heterojunction with the intrinsic band structures of themore » two monolayers largely preserved. They are particularly promising for the applications that request efficient dissociation of excitons and strong light absorption, including photovoltaics, solar fuels, photodetectors, and optical modulators. Our results also indicate that 2D heterostructures promise to provide capabilities to engineer excitons from the atomic level without concerns of interfacial imperfection.« less

Exploiting One-Dimensional Exciton-Phonon Coupling for Tunable and Efficient Single-Photon Generation with a Carbon Nanotube.

PubMed

Jeantet, A; Chassagneux, Y; Claude, T; Roussignol, P; Lauret, J S; Reichel, J; Voisin, C

2017-07-12

Condensed-matter emitters offer enriched cavity quantum electrodynamical effects due to the coupling to external degrees of freedom. In the case of carbon nanotubes, a very peculiar coupling between localized excitons and the one-dimensional acoustic phonon modes can be achieved, which gives rise to pronounced phonon wings in the luminescence spectrum. By coupling an individual nanotube to a tunable optical microcavity, we show that this peculiar exciton-phonon coupling is a valuable resource to enlarge the tuning range of the single-photon source while keeping an excellent exciton-photon coupling efficiency and spectral purity. Using the unique flexibility of our scanning fiber cavity, we are able to measure the efficiency spectrum of the very same nanotube in the Purcell regime for several mode volumes. Whereas this efficiency spectrum looks very much like the free-space luminescence spectrum when the Purcell factor is small (large mode volume), we show that the deformation of this spectrum at lower mode volumes can be traced back to the strength of the exciton-photon coupling. It shows an enhanced efficiency on the red wing that arises from the asymmetry of the incoherent energy exchange processes between the exciton and the cavity. This allows us to obtain a tuning range up to several hundred times the spectral width of the source.

Exciton size and binding energy limitations in one-dimensional organic materials

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

Kraner, S., E-mail: stefan.kraner@iapp.de; Koerner, C.; Leo, K.

2015-12-28

In current organic photovoltaic devices, the loss in energy caused by the charge transfer step necessary for exciton dissociation leads to a low open circuit voltage, being one of the main reasons for rather low power conversion efficiencies. A possible approach to avoid these losses is to tune the exciton binding energy to a value of the order of thermal energy, which would lead to free charges upon absorption of a photon, and therefore increase the power conversion efficiency towards the Shockley-Queisser limit. We determine the size of the excitons for different organic molecules and polymers by time dependent densitymore » functional theory calculations. For optically relevant transitions, the exciton size saturates around 0.7 nm for one-dimensional molecules with a size longer than about 4 nm. For the ladder-type polymer poly(benzimidazobenzophenanthroline), we obtain an exciton binding energy of about 0.3 eV, serving as a lower limit of the exciton binding energy for the organic materials investigated. Furthermore, we show that charge transfer transitions increase the exciton size and thus identify possible routes towards a further decrease of the exciton binding energy.« less

Heavy Atom Effect of Bromine Significantly Enhances Exciton Utilization of Delayed Fluorescence Luminogens.

PubMed

Gan, Shifeng; Hu, Shimin; Li, Xiang-Long; Zeng, Jiajie; Zhang, Dongdong; Huang, Tianyu; Luo, Wenwen; Zhao, Zujin; Duan, Lian; Su, Shi-Jian; Tang, Ben Zhong

2018-05-23

Raising triplet exciton utilization of pure organic luminescent materials is of significant importance for efficiency advancement of organic light-emitting diodes (OLEDs). Herein, by introducing bromine atom(s) onto a typical molecule (bis(carbazol-9-yl)-4,5-dicyanobenzene) with thermally activated delayed fluorescence, we demonstrate that the heavy atom effect of bromine can increase spin-orbit coupling and promote the reverse intersystem crossing, which endow the molecules with more distinct delayed fluorescence. In consequence, the triplet exciton utilization is improved greatly with the increase of bromine atoms, affording apparently advanced external quantum efficiencies of OLEDs. Utilizing the enhancement effect of bromine atoms on delayed fluorescence should be a simple and promising design concept for efficient organic luminogens with high exciton utilization.

Exciton management in organic photovoltaic multidonor energy cascades.

PubMed

Griffith, Olga L; Forrest, Stephen R

2014-05-14

Multilayer donor regions in organic photovoltaics show improved power conversion efficiency when arranged in decreasing exciton energy order from the anode to the acceptor interface. These so-called "energy cascades" drive exciton transfer from the anode to the dissociating interface while reducing exciton quenching and allowing improved overlap with the solar spectrum. Here we investigate the relative importance of exciton transfer and blocking in a donor cascade employing diphenyltetracene (D1), rubrene (D2), and tetraphenyldibenzoperiflanthene (D3) whose optical gaps monotonically decrease from D1 to D3. In this structure, D1 blocks excitons from quenching at the anode, D2 accepts transfer of excitons from D1 and blocks excitons at the interface between D2 and D3, and D3 contributes the most to the photocurrent due to its strong absorption at visible wavelengths, while also determining the open circuit voltage. We observe singlet exciton Förster transfer from D1 to D2 to D3 consistent with cascade operation. The power conversion efficiency of the optimized cascade OPV with a C60 acceptor layer is 7.1 ± 0.4%, which is significantly higher than bilayer devices made with only the individual donors. We develop a quantitative model to identify the dominant exciton processes that govern the photocurrent generation in multilayer organic structures.

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 .

Singlet exciton fission in polycrystalline pentacene: from photophysics toward devices.

PubMed

Wilson, Mark W B; Rao, Akshay; Ehrler, Bruno; Friend, Richard H

2013-06-18

Singlet exciton fission is the process in conjugated organic molecules bywhich a photogenerated singlet exciton couples to a nearby chromophore in the ground state, creating a pair of triplet excitons. Researchers first reported this phenomenon in the 1960s, an event that sparked further studies in the following decade. These investigations used fluorescence spectroscopy to establish that exciton fission occurred in single crystals of several acenes. However, research interest has been recently rekindled by the possibility that singlet fission could be used as a carrier multiplication technique to enhance the efficiency of photovoltaic cells. The most successful architecture to-date involves sensitizing a red-absorbing photoactive layer with a blue-absorbing material that undergoes fission, thereby generating additional photocurrent from higher-energy photons. The quest for improved solar cells has spurred a drive to better understand the fission process, which has received timely aid from modern techniques for time-resolved spectroscopy, quantum chemistry, and small-molecule device fabrication. However, the consensus interpretation of the initial studies using ultrafast transient absorption spectroscopy was that exciton fission was suppressed in polycrystalline thin films of pentacene, a material that would be otherwise expected to be an ideal model system, as well as a viable candidate for fission-sensitized photovoltaic devices. In this Account, we review the results of our recent transient absorption and device-based studies of polycrystalline pentacene. We address the controversy surrounding the assignment of spectroscopic features in transient absorption data, and illustrate how a consistent interpretation is possible. This work underpins our conclusion that singlet fission in pentacene is extraordinarily rapid (∼80 fs) and is thus the dominant decay channel for the photoexcited singlet exciton. Further, we discuss our demonstration that triplet excitons generated via singlet fission in pentacene can be dissociated at an interface with a suitable electron acceptor, such as fullerenes and infrared-absorbing inorganic semiconducting quantum dots. We highlight our recent reports of a pentacene/PbSe hybrid solar cell with a power conversion efficiency of 4.7% and of a pentacene/PbSe/amorphous silicon photovoltaic device. Although substantive challenges remain, both to better our understanding of the mechanism of singlet exciton fission and to optimize device performance, this realization of a solar cell where photocurrent is simultaneously contributed from a blue-absorbing fission-capable material and an infrared-absorbing conventional cell is an important step towards a dual-bandgap, single-junction, fission-enhanced photovoltaic device, which could one day surpass the Shockley-Queisser limit.

Analytical model for the photocurrent-voltage characteristics of bilayer MEH-PPV/TiO2 photovoltaic devices

PubMed Central

2011-01-01

The photocurrent in bilayer polymer photovoltaic cells is dominated by the exciton dissociation efficiency at donor/acceptor interface. An analytical model is developed for the photocurrent-voltage characteristics of the bilayer polymer/TiO2 photovoltaic cells. The model gives an analytical expression for the exciton dissociation efficiency at the interface, and explains the dependence of the photocurrent of the devices on the internal electric field, the polymer and TiO2 layer thicknesses. Bilayer polymer/TiO2 cells consisting of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and TiO2, with different thicknesses of the polymer and TiO2 films, were prepared for experimental purposes. The experimental results for the prepared bilayer MEH-PPV/TiO2 cells under different conditions are satisfactorily fitted to the model. Results show that increasing TiO2 or the polymer layer in thickness will reduce the exciton dissociation efficiency in the device and further the photocurrent. It is found that the photocurrent is determined by the competition between the exciton dissociation and charge recombination at the donor/acceptor interface, and the increase in photocurrent under a higher incident light intensity is due to the increased exciton density rather than the increase in the exciton dissociation efficiency. PMID:21711905

Excitons in Single-Walled Carbon Nanotubes and Their Dynamics

NASA Astrophysics Data System (ADS)

Amori, Amanda R.; Hou, Zhentao; Krauss, Todd D.

2018-04-01

Understanding exciton dynamics in single-walled carbon nanotubes (SWCNTs) is essential to unlocking the many potential applications of these materials. This review summarizes recent progress in understanding exciton photophysics and, in particular, exciton dynamics in SWCNTs. We outline the basic physical and electronic properties of SWCNTs, as well as bright and dark transitions within the framework of a strongly bound one-dimensional excitonic model. We discuss the many facets of ultrafast carrier dynamics in SWCNTs, including both single-exciton states (bright and dark) and multiple-exciton states. Photophysical properties that directly relate to excitons and their dynamics, including exciton diffusion lengths, chemical and structural defects, environmental effects, and photoluminescence photon statistics as observed through photon antibunching measurements, are also discussed. Finally, we identify a few key areas for advancing further research in the field of SWCNT excitons and photonics.

Exciton Dynamics, Transport, and Annihilation in Atomically Thin Two-Dimensional Semiconductors.

PubMed

Yuan, Long; Wang, Ti; Zhu, Tong; Zhou, Mingwei; Huang, Libai

2017-07-20

Large binding energy and unique exciton fine structure make the transition metal dichalcogenides (TMDCs) an ideal platform to study exciton behaviors in two-dimensional (2D) systems. While excitons in these systems have been extensively researched, there currently lacks a consensus on mechanisms that control dynamics. In this Perspective, we discuss extrinsic and intrinsic factors in exciton dynamics, transport, and annihilation in 2D TMDCs. Intrinsically, dark and bright exciton energy splitting is likely to play a key role in modulating the dynamics. Extrinsically, defect scattering is prevalent in single-layer TMDCs, which leads to rapid picosecond decay and limits exciton transport. The exciton-exciton annihilation process in single-layer TMDCs is highly efficient, playing an important role in the nonradiative recombination rate in the high exciton density regime. Future challenges and opportunities to control exciton dynamics are discussed.

Influences of Exciton Diffusion and Exciton-Exciton Annihilation on Photon Emission Statistics of Carbon Nanotubes.

PubMed

Ma, Xuedan; Roslyak, Oleskiy; Duque, Juan G; Pang, Xiaoying; Doorn, Stephen K; Piryatinski, Andrei; Dunlap, David H; Htoon, Han

2015-07-03

Pump-dependent photoluminescence imaging and second-order photon correlation studies have been performed on individual single-walled carbon nanotubes (SWCNTs) at room temperature. These studies enable the extraction of both the exciton diffusion constant and the Auger recombination coefficient. A linear correlation between these parameters is attributed to the effect of environmental disorder in setting the exciton mean free path and capture-limited Auger recombination at this length scale. A suppression of photon antibunching is attributed to the creation of multiple spatially nonoverlapping excitons in SWCNTs, whose diffusion length is shorter than the laser spot size. We conclude that complete antibunching at room temperature requires an enhancement of the exciton-exciton annihilation rate that may become realizable in SWCNTs allowing for strong exciton localization.

Cascaded plasmon-plasmon coupling mediated energy transfer across stratified metal-dielectric nanostructures

PubMed Central

Golmakaniyoon, Sepideh; Hernandez-Martinez, Pedro Ludwig; Demir, Hilmi Volkan; Sun, Xiao Wei

2016-01-01

Surface plasmon (SP) coupling has been successfully applied to nonradiative energy transfer via exciton-plasmon-exciton coupling in conventionally sandwiched donor-metal film-acceptor configurations. However, these structures lack the desired efficiency and suffer poor photoemission due to the high energy loss. Here, we show that the cascaded exciton-plasmon-plasmon-exciton coupling in stratified architecture enables an efficient energy transfer mechanism. The overlaps of the surface plasmon modes at the metal-dielectric and dielectric-metal interfaces allow for strong cross-coupling in comparison with the single metal film configuration. The proposed architecture has been demonstrated through the analytical modeling and numerical simulation of an oscillating dipole near the stratified nanostructure of metal-dielectric-metal-acceptor. Consistent with theoretical and numerical results, experimental measurements confirm at least 50% plasmon resonance energy transfer enhancement in the donor-metal-dielectric-metal-acceptor compared to the donor-metal-acceptor structure. Cascaded plasmon-plasmon coupling enables record high efficiency for exciton transfer through metallic structures. PMID:27698422

Optical nonlinearities of excitons in monolayer MoS2

NASA Astrophysics Data System (ADS)

Soh, Daniel B. S.; Rogers, Christopher; Gray, Dodd J.; Chatterjee, Eric; Mabuchi, Hideo

2018-04-01

We calculate linear and nonlinear optical susceptibilities arising from the excitonic states of monolayer MoS2 for in-plane light polarizations, using second-quantized bound and unbound exciton operators. Optical selection rules are critical for obtaining the susceptibilities. We derive the valley-chirality rule for the second-order harmonic generation in monolayer MoS2 and find that the third-order harmonic process is efficient only for linearly polarized input light while the third-order two-photon process (optical Kerr effect) is efficient for circularly polarized light using a higher order exciton state. The absence of linear absorption due to the band gap and the unusually strong two-photon third-order nonlinearity make the monolayer MoS2 excitonic structure a promising resource for coherent nonlinear photonics.

Directing energy transport in organic photovoltaic cells using interfacial exciton gates.

PubMed

Menke, S Matthew; Mullenbach, Tyler K; Holmes, Russell J

2015-04-28

Exciton transport in organic semiconductors is a critical, mediating process in many optoelectronic devices. Often, the diffusive and subdiffusive nature of excitons in these systems can limit device performance, motivating the development of strategies to direct exciton transport. In this work, directed exciton transport is achieved with the incorporation of exciton permeable interfaces. These interfaces introduce a symmetry-breaking imbalance in exciton energy transfer, leading to directed motion. Despite their obvious utility for enhanced exciton harvesting in organic photovoltaic cells (OPVs), the emergent properties of these interfaces are as yet uncharacterized. Here, directed exciton transport is conclusively demonstrated in both dilute donor and energy-cascade OPVs where judicious optimization of the interface allows exciton transport to the donor-acceptor heterojunction to occur considerably faster than when relying on simple diffusion. Generalized systems incorporating multiple exciton permeable interfaces are also explored, demonstrating the ability to further harness this phenomenon and expeditiously direct exciton motion, overcoming the diffusive limit.

Charge Generation and Recombination in Organic Materials for Photovoltaics

NASA Astrophysics Data System (ADS)

Ramirez, Jessica Jacklyn

Understanding the nature of molecular exciton states is critical for the design of organic photovoltaic materials that push current device efficiencies into the next realm. This thesis describes several research projects that have sought to further our understanding of the generation and recombination of charge carriers, facilitated by such excitonic states, in organic systems. We begin with fundamental studies on the excited-state dynamics of several fullerene derivatives. We also venture away from the traditional fullerene-based electron acceptors and consider several derivatized perylene diimides as alternate electron acceptors. We then report on the observation of a broad, structureless, emission emanating from charge-generating films comprised of perfluoroalkyl fullerene derivatives dilutely dispersed in polyfluorene hosts. We have determined that this red-shifted PL signature is the result of radiative recombination from a charge-transfer state that is populated initially as a precursor to charge generation, and may be repopulated upon charge recombination. Our data offers an observable link between charge-generation and charge-transfer emission that is kinetically associated with carrier recombination, and we utilize this link to probe the influence of driving force and polymer microstructure in the fundamental processes of charge generation and decay in small molecule/polymer heterojunctions. Thereafter, we sought to develop our understanding of a novel photophysical mechanism (known as energy pooling) which would allow for the energy of multiple excitons to be 'pooled' towards a central molecular moiety, where the individual exciton energies may add together to create a single highly excited excitonic state. This upconversion-like process would facilitate more efficient photocurrent generation in devices utilizing this mode of charge separation. The primary modes of inquiry utilized in this work come from the spectroscopic techniques of absorbance, steady-state and time-resolved photoluminescence, transient absorption and time-resolved microwave conductivity. Some secondary methods employed include cyclic voltammetry, X-ray diffraction and computational tools from density functional theory. This utilization of both experimental and theoretical methodologies provides a powerful approach to furthering our understanding of both the fundamental photophysics of the systems studied, as well as the charge generation and recombination pathways occurring at organic donor-acceptor interfaces, helping to guide the design of more efficient organic photovoltaics.

Decoupling degradation in exciton formation and recombination during lifetime testing of organic light-emitting devices

NASA Astrophysics Data System (ADS)

Hershey, Kyle W.; Suddard-Bangsund, John; Qian, Gang; Holmes, Russell J.

2017-09-01

The analysis of organic light-emitting device degradation is typically restricted to fitting the overall luminance loss as a function of time or the characterization of fully degraded devices. To develop a more complete understanding of degradation, additional specific data are needed as a function of luminance loss. The overall degradation in luminance during testing can be decoupled into a loss in emitter photoluminescence efficiency and a reduction in the exciton formation efficiency. Here, we demonstrate a method that permits separation of these component efficiencies, yielding the time evolution of two additional specific device parameters that can be used in interpreting and modeling degradation without modification to the device architecture or introduction of any additional post-degradation characterization steps. Here, devices based on the phosphor tris[2-phenylpyridinato-C2,N]iridium(III) (Ir(ppy)3) are characterized as a function of initial luminance and emissive layer thickness. The overall loss in device luminance is found to originate primarily from a reduction in the exciton formation efficiency which is exacerbated in devices with thinner emissive layers. Interestingly, the contribution to overall degradation from a reduction in the efficiency of exciton recombination (i.e., photoluminescence) is unaffected by thickness, suggesting a fixed exciton recombination zone width and degradation at an interface.

Controllable lasing performance in solution-processed organic-inorganic hybrid perovskites.

PubMed

Kao, Tsung Sheng; Chou, Yu-Hsun; Hong, Kuo-Bin; Huang, Jiong-Fu; Chou, Chun-Hsien; Kuo, Hao-Chung; Chen, Fang-Chung; Lu, Tien-Chang

2016-11-03

Solution-processed organic-inorganic perovskites are fascinating due to their remarkable photo-conversion efficiency and great potential in the cost-effective, versatile and large-scale manufacturing of optoelectronic devices. In this paper, we demonstrate that the perovskite nanocrystal sizes can be simply controlled by manipulating the precursor solution concentrations in a two-step sequential deposition process, thus achieving the feasible tunability of excitonic properties and lasing performance in hybrid metal-halide perovskites. The lasing threshold is at around 230 μJ cm -2 in this solution-processed organic-inorganic lead-halide material, which is comparable to the colloidal quantum dot lasers. The efficient stimulated emission originates from the multiple random scattering provided by the micro-meter scale rugged morphology and polycrystalline grain boundaries. Thus the excitonic properties in perovskites exhibit high correlation with the formed morphology of the perovskite nanocrystals. Compared to the conventional lasers normally serving as a coherent light source, the perovskite random lasers are promising in making low-cost thin-film lasing devices for flexible and speckle-free imaging applications.

Slow cooling and efficient extraction of C-exciton hot carriers in MoS2 monolayer

PubMed Central

Wang, Lei; Wang, Zhuo; Wang, Hai-Yu; Grinblat, Gustavo; Huang, Yu-Li; Wang, Dan; Ye, Xiao-Hui; Li, Xian-Bin; Bao, Qiaoliang; Wee, AndrewThye-Shen; Maier, Stefan A; Chen, Qi-Dai; Zhong, Min-Lin; Qiu, Cheng-Wei; Sun, Hong-Bo

2017-01-01

In emerging optoelectronic applications, such as water photolysis, exciton fission and novel photovoltaics involving low-dimensional nanomaterials, hot-carrier relaxation and extraction mechanisms play an indispensable and intriguing role in their photo-electron conversion processes. Two-dimensional transition metal dichalcogenides have attracted much attention in above fields recently; however, insight into the relaxation mechanism of hot electron-hole pairs in the band nesting region denoted as C-excitons, remains elusive. Using MoS2 monolayers as a model two-dimensional transition metal dichalcogenide system, here we report a slower hot-carrier cooling for C-excitons, in comparison with band-edge excitons. We deduce that this effect arises from the favourable band alignment and transient excited-state Coulomb environment, rather than solely on quantum confinement in two-dimension systems. We identify the screening-sensitive bandgap renormalization for MoS2 monolayer/graphene heterostructures, and confirm the initial hot-carrier extraction for the C-exciton state with an unprecedented efficiency of 80%, accompanied by a twofold reduction in the exciton binding energy. PMID:28054546

Is there any Exciton (bottleneck) in an Excitonic Solar Cell: Revisiting the Prospects of Single-Semiconductor OPV

NASA Astrophysics Data System (ADS)

Alam, Muhammad

2014-03-01

The discovery dye sensitized and bulk heterojunction (BHJ) solar cells in early 1990s introduced a new class of PV technology that rely on (i) distributed photogeneration of excitons, (ii) dissociation of excitons into free carriers by the heterojunction between two organic semiconductors (OSC), and (iii) collection of free carriers through electron and hole transport layers. The success of the approach is undisputed: the highest efficiency OPV cells have all relied on variants of BHJ approach. Yet, three concerns related to the use of a pair of OSCs, namely, low Voc, process sensitivity, and reliability, suggest that the technology may never achieve efficiency-variability-reliability metrics comparable to inorganic solar cells. This encourages a reconsideration of the prospects of Single semiconductor OPV (SS-OPV), a system presumably doomed by the exciton bottleneck. In this talk, we use an inverted SS-OPV to demonstrate how the historical SS-OPV experiments may have been misinterpreted. No one disputes the signature of excitons in polymer under narrowband excitation, but our experiments show that exciton dissociation need not be a bottleneck for OPV under broadband solar illumination. We demonstrate that an alternate collection-limited theory consistently interprets the classical and new experiments, resolves puzzles such as efficiency loss with increasing light intensity, and voltage-dependent reverse photo-current, etc. The theory and experiments suggest a new ``perovskite-like'' strategy to efficiency-variability-reliability of organic solar cells. The work was supported by the Columbia DOE-EFRC (DE-SC0001085) and NSF-NCN (EEC-0228390).

Surface modification and multiple exciton generation studies of lead(II) sulfide nanoparticles

NASA Astrophysics Data System (ADS)

Zemke, Jennifer M.

2011-12-01

Solar energy is a green alternative to fossil fuels but solar technologies to date have been plagued by low conversion efficiencies and high input costs making solar power inaccessible to much of the developing world. Semiconductor nanoparticles (NPs) may provide a route to efficient, economical solar devices through a phenomenon called multiple exciton generation (MEG). Through MEG, semiconductor NPs use a high-energy input photon to create more than one exciton (electron-hole pair) per photon absorbed, thereby exhibiting large photoconversion efficiencies. While MEG has been studied in many NP systems, and we understand some of the factors that affect MEG, a rigorous analysis of the NP-ligand interface with respect to MEG is missing. This dissertation describes how the NP ligand shell directly affects MEG and subsequent charge carrier recombination. Chapter I describes the motivation for studying MEG with respect to NP surface chemistry. Chapter II provides an in-depth overview of the transient absorption experiment used to measure MEG in the NP samples. Chapter III highlights the effect of oleic acid and sodium 2, 3-dimercaptopropane sulfonate on MEG in PbS NPs. The differences in carrier recombination were accounted for by two differences between these ligands: the coordinating atom and/or the secondary structure of the ligand. Because of these hypotheses, experiments were designed to elucidate the origin of these effects by controlling the NP ligand shell. Chapter IV details a viable synthetic route to thiol and amine-capped PbS NPs using sodium 3-mercaptopropane sulfonate as an intermediate ligand. With the versatile ligand exchange described in Chapter IV, the MEG yield and carrier recombination was investigated for ligands with varying headgroups but the same secondary structure. The correlation of ligand donor atom to MEG is outlined in Chapter V. Finally, Chapter VI discusses the conclusions and future outlook of the research reported in this dissertation. This dissertation includes previously published and unpublished co-authored material.

Efficient Generation of Long-Lived Triplet Excitons in 2D Hybrid Perovskite.

PubMed

Younts, Robert; Duan, Hsin-Sheng; Gautam, Bhoj; Saparov, Bayrammurad; Liu, Jie; Mongin, Cedric; Castellano, Felix N; Mitzi, David B; Gundogdu, Kenan

2017-03-01

Triplet excitons form in quasi-2D hybrid inorganic-organic perovskites and diffuse over 100 nm before radiating with >11% photoluminescence quantum efficiency (PLQE) at low temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exciton diffusion in disordered small molecules for organic photovoltaics: insights from first-principles simulations.

PubMed

Li, Z; Zhang, X; Lu, G

2014-05-07

Exciton diffusion in small molecules 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione [DPP(TBFu)2] is studied using first-principles simulations. We have examined dependence of exciton diffusion on structure disorder, temperature and exciton energy. We find that exciton diffusion length and diffusivity increase with structural order, temperature and the initial exciton energy. Compared to conjugated polymer poly(3-hexylthiophene) (P3HT), DPP(TBFu)2 small molecules exhibit a much higher exciton diffusivity, but a shorter lifetime. The exciton diffusion length in DPP(TBFu)2 is 50% longer than that in P3HT, yielding a higher exciton harvesting efficiency; the physical origin behind these differences is discussed. The time evolutions of exciton energy, electron-hole distance, and exciton localization are explored, and the widely speculated exciton diffusion mechanism is confirmed theoretically. The connection between exciton diffusion and carrier mobilities is also studied. Finally we point out the possibility to estimate exciton diffusivity by measuring carrier mobilities under AC electric fields.

Influence of intra-pigment vibrations on dynamics of photosynthetic exciton.

PubMed

Sato, Yoshihiro; Doolittle, Brian

2014-11-14

We have numerically investigated the effect of an underdamped intra-pigment vibrational mode on an exciton's quantum coherence and energy transfer efficiency. Our model describes a bacteriochlorophyll a pigment-protein dimer under the conditions at which photosynthetic energy transfer occurs. The dimer is modeled using a theoretical treatment of a vibronic exciton, and its dynamics are numerically analyzed using a non-Markovian and non-perturbative method. We examined the system's response to various values of the Huang-Rhys factor, site energy difference, reorganization energy, and reorganization energy difference. We found that the inclusion of the intra-pigment vibronic mode allows for long-lived oscillatory quantum coherences to occur. This excitonic coherence is robust against static site-energy disorder. The vibrational mode also promotes exciton transfer along the site-energy landscape thus improving the overall energy transfer efficiency.

Effect of a Phonon Bottleneck on Exciton and Spin Generation in Self-Assembled In1 -xGaxAs Quantum Dots

NASA Astrophysics Data System (ADS)

Huang, Y. Q.; Buyanova, I. A.; Yang, X. J.; Murayama, A.; Chen, W. M.

2018-04-01

We provide direct experimental evidence for the effect of a phonon bottleneck on exciton and spin generation in self-assembled In0.5Ga0.5As quantum dots (QDs). With the aid of tunable laser spectroscopy, we resolve and identify efficient exciton generation channels in the QDs mediated by longitudinal-optical (LO) phonons from an otherwise inhomogeneously broadened QD emission background that suffers from the phonon bottleneck effect in exciton generation. Spin-generation efficiency is found to be enhanced under the LO-assisted excitation condition due to suppressed spin relaxation accompanying accelerated exciton generation. These findings underline the importance of fine-tuning QD energy levels that will benefit potential spin-optoelectronic applications of QDs by reducing spin loss due to the phonon bottleneck.

Exciton Transport Simulations in Phenyl Cored Thiophene Dendrimers

NASA Astrophysics Data System (ADS)

Kim, Kwiseon; Erkan Kose, Muhammet; Graf, Peter; Kopidakis, Nikos; Rumbles, Garry; Shaheen, Sean E.

2009-03-01

Phenyl cored 3-arm and 4-arm thiophene dendrimers are promising materials for use in photovoltaic devices. It is important to understand the energy transfer mechanisms in these molecules to guide the synthesis of novel dendrimers with improved efficiency. A method is developed to estimate the exciton diffusion lengths for the dendrimers and similar chromophores in amorphous films. The approach exploits Fermi's Golden Rule to estimate the energy transfer rates for an ensemble of bimolecular complexes in random orientations. Using Poisson's equation to evaluate Coulomb integrals led to efficient calculation of excitonic couplings between the transition densities. Monte-Carlo simulations revealed the dynamics of energy transport in the dendrimers. Experimental exciton diffusion lengths of the dendrimers range 10 ˜ 20 nm, increasing with the size of the dendrimer. Simulated diffusion lengths correlate well with experiments. The chemical structure of the chromophore, the shape of the transition densities and the exciton lifetime are found to be the most important factors that determine the exciton diffusion length in amorphous films.

Observation of Tunable Charged Exciton Polaritons in Hybrid Monolayer WS2-Plasmonic Nanoantenna System.

PubMed

Cuadra, Jorge; Baranov, Denis G; Wersäll, Martin; Verre, Ruggero; Antosiewicz, Tomasz J; Shegai, Timur

2018-03-14

Formation of dressed light-matter states in optical structures, manifested as Rabi splitting of the eigen energies of a coupled system, is one of the key effects in quantum optics. In pursuing this regime with semiconductors, light is usually made to interact with excitons, electrically neutral quasiparticles of semiconductors; meanwhile interactions with charged three-particle states, trions, have received little attention. Here, we report on strong interaction between localized surface plasmons in silver nanoprisms and excitons and trions in monolayer tungsten disulfide (WS 2 ). We show that the plasmon-exciton interactions in this system can be efficiently tuned by controlling the charged versus neutral exciton contribution to the coupling process. In particular, we show that a stable trion state emerges and couples efficiently to the plasmon resonance at low temperature by forming three bright intermixed plasmon-exciton-trion polariton states. Our findings open up a possibility to exploit electrically charged polaritons at the single nanoparticle level.

Effects of molecular packing in organic crystals on singlet fission with ab initio many body perturbation theory

NASA Astrophysics Data System (ADS)

Haber, Jonah; Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G.; Neaton, Jeffrey B.

Multi-exciton generation processes, in which multiple charge carriers are generated from a single photon, are mechanisms of significant interest for achieving efficiencies beyond the Shockley-Queisser limit of conventional p-n junction solar cells. One well-studied multiexciton process is singlet fission, whereby a singlet decays into two spin-correlated triplet excitons. Here, we use a newly developed computational approach to calculate singlet-fission coupling terms and rates with an ab initio Green's function formalism based on many-body perturbation theory (MBPT) within the GW approximation and the Bethe-Salpeter equation approach. We compare results for crystalline pentacene and TIPS-pentacene and explore the effect of molecular packing on the singlet fission mechanism. This work is supported by the Department of Energy.

Influence of Energetic Disorder on Exciton Lifetime and Photoluminescence Efficiency in Conjugated Polymers.

PubMed

Rörich, Irina; Mikhnenko, Oleksandr V; Gehrig, Dominik; Blom, Paul W M; Crăciun, N Irina

2017-02-16

Using time-resolved photoluminescence (TRPL) spectroscopy the exciton lifetime in a range of conjugated polymers is investigated. For poly(p-phenylenevinylene) (PPV)-based derivatives and a polyspirobifluorene copolymer (PSBF) we find that the exciton lifetime is correlated with the energetic disorder. Better ordered polymers exhibit a single exponential PL decay with exciton lifetimes of a few hundred picoseconds, whereas polymers with a larger degree of disorder show multiexponential PL decays with exciton lifetimes in the nanosecond regime. These observations are consistent with diffusion-limited exciton quenching at nonradiative recombination centers. The measured PL decay time reflects the time that excitons need to diffuse toward these quenching sites. Conjugated polymers with large energetic disorder and thus longer exciton lifetime also exhibit a higher photoluminescence quantum yield due to the slower exciton diffusion toward nonradiative quenching sites.

Efficient cascade multiple heterojunction organic solar cells with inverted structure

NASA Astrophysics Data System (ADS)

Guo, Tingting; Li, Mingtao; Qiao, Zhenfang; Yu, Leiming; Zhao, Jianhong; Feng, Nianjun; Shi, Peiguang; Wang, Xiaoyan; Pu, Xiaoyun; Wang, Hai

2018-05-01

In this work, we demonstrate an efficient cascade multiple heterojunction organic solar cell with inverted structure. By using two donor materials, poly(3-hexylthiosphene) (P3HT) and titanyl phthalocyanine (TiOPc), as well as two acceptor materials, [6,6]-phenyl C61 butyric acid methyl ester (PCBM) and C60, the cascade multiple heterojunctions of P3HT:PCBM/TiOPc:C60/C60 have been constructed. Applying the optimized inverted configuration of FTO/Zinc Tin Oxide (ZTO)/C60 (30 nm)/TiOPc:C60 (1:1.5, 25 nm)/P3HT:PCBM (1:0.8, 100 nm)/MoO3 (4 nm)/Ag, the considerably enhanced open circuit voltage (VOC) and short circuit current (JSC) can be harvested together, and the power conversion efficiency (PCE) is three times higher than that of the control cell with conventional structure. The significant improvements of the inverted cell are mostly due to the broadened spectral absorption and high efficient multi-interface exciton dissociation in the cascade multiple heterojunctions, indicating that the optimized cascade heterojunctions match the inverted structure well.

Impact of Molecular Organization on Exciton Diffusion in Photosensitive Single-Crystal Halogenated Perylenediimides Charge Transfer Interfaces.

PubMed

Pinto, Rui M; Gouveia, Wilson; Maçôas, Ermelinda M S; Santos, Isabel C; Raja, Sebastian; Baleizão, Carlos; Alves, Helena

2015-12-23

The efficiency of organic photodetectors and optoelectronic devices is strongly limited by exciton diffusion, in particular for acceptor materials. Although mechanisms for exciton diffusion are well established, their correlation to molecular organization in real systems has received far less attention. In this report, organic single-crystals interfaces were probed with wavelength-dependent photocurrent spectroscopy and their crystal structure resolved using X-ray diffraction. All systems present a dynamic photoresponse, faster than 500 ms, up to 650 nm. A relationship between molecular organization and favorable exciton diffusion in substituted butyl-perylenediimides (PDIB) is established. This is demonstrated by a set of PDIBs with different intra- and interstack distances and short contacts and their impact on photoresponse. Given the short packing distances between PDIs cores along the same stacking direction (3.4-3.7 Å), and across parallel stacks (2.5 Å), singlet exciton in these PDIBs can follow both Förster and Dexter exciton diffusion, with the Dexter-type mechanism assuming special relevance for interstack exciton diffusion. Yet, the response is maximized in substituted PDIBs, where a 2D percolation network is formed through strong interstack contacts, allowing for PDIBs primary excitons to reach with great efficiency the splitting interface with crystalline rubrene. The importance of short contacts and molecular distances, which is often overlooked as a parameter to consider and optimize when choosing materials for excitonic devices, is emphasized.

Study of Exciton Hopping Transport in PbS Colloidal Quantum Dot Thin Films Using Frequency- and Temperature-Scanned Photocarrier Radiometry

NASA Astrophysics Data System (ADS)

Hu, Lilei; Mandelis, Andreas; Melnikov, Alexander; Lan, Xinzheng; Hoogland, Sjoerd; Sargent, Edward H.

2017-01-01

Solution-processed colloidal quantum dots (CQDs) are promising materials for realizing low-cost, large-area, and flexible photovoltaic devices. The study of charge carrier transport in quantum dot solids is essential for understanding energy conversion mechanisms. Recently, solution-processed two-layer oleic-acid-capped PbS CQD solar cells with one layer treated with tetrabutylammonium iodide (TBAI) serving as the main light-absorbing layer and the other treated with 1,2-ethanedithiol (EDT) acting as an electron-blocking/hole-extraction layer were reported. These solar cells demonstrated a significant improvement in power conversion efficiency of 8.55% and long-term air stability. Coupled with photocarrier radiometry measurements, this work used a new trap-state mediated exciton hopping transport model, specifically for CQD thin films, to unveil and quantify exciton transport mechanisms through the extraction of hopping transport parameters including exciton lifetimes, hopping diffusivity, exciton detrapping time, and trap-state density. It is shown that PbS-TBAI has higher trap-state density than PbS-EDT that results in higher PbS-EDT exciton lifetimes. Hopping diffusivities of both CQD thin film types show similar temperature dependence, particularly higher temperatures yield higher hopping diffusivity. The higher diffusivity of PbS-TBAI compared with PbS-EDT indicates that PbS-TBAI is a much better photovoltaic material than PbS-EDT. Furthermore, PCR temperature spectra and deep-level photothermal spectroscopy provided additional insights to CQD surface trap states: PbS-TBAI thin films exhibit a single dominant trap level, while PbS-EDT films with lower trap-state densities show multiple trap levels.

Size-Independent Exciton Localization Efficiency in Colloidal CdSe/CdS Core/Crown Nanosheet Type-I Heterostructures.

PubMed

Li, Qiuyang; Wu, Kaifeng; Chen, Jinquan; Chen, Zheyuan; McBride, James R; Lian, Tianquan

2016-03-22

CdSe/CdS core/crown nanoplatelet type I heterostructures are a class of two-dimensional materials with atomically precise thickness and many potential optoelectronic applications. It remains unclear how the precise thickness and lack of energy disorder affect the properties of exciton transport in these materials. By steady-state photoluminescence excitation spectroscopy and ultrafast transient absorption spectroscopy, we show that in five CdSe/CdS core/crown structures with the same core and increasing crown size (with thickness of ∼1.8 nm, width of ∼11 nm, and length from 20 to 40 nm), the crown-to-core exciton localization efficiency is independent of crown size and increases with photon energy above the band edge (from 70% at 400 nm to ∼100% at 370 nm), while the localization time increases with the crown size. These observations can be understood by a model that accounts for the competition of in-plane exciton diffusion and selective hole trapping at the core/crown interface. Our findings suggest that the exciton localization efficiency can be further improved by reducing interfacial defects.

Multi-exciton emission from solitary dopant states of carbon nanotubes.

PubMed

Ma, Xuedan; Hartmann, Nicolai F; Velizhanin, Kirill A; Baldwin, Jon K S; Adamska, Lyudmyla; Tretiak, Sergei; Doorn, Stephen K; Htoon, Han

2017-11-02

By separating the photons from slow and fast decays of single and multi-exciton states in a time gated 2 nd order photon correlation experiment, we show that solitary oxygen dopant states of single-walled carbon nanotubes (SWCNTs) allow emission of photon pairs with efficiencies as high as 44% of single exciton emission. Our pump dependent time resolved photoluminescence (PL) studies further reveal diffusion-limited exciton-exciton annihilation as the key process that limits the emission of multi-excitons at high pump fluences. We further postulate that creation of additional permanent exciton quenching sites occurring under intense laser irradiation leads to permanent PL quenching. With this work, we bring out multi-excitonic processes of solitary dopant states as a new area to be explored for potential applications in lasing and entangled photon generation.

Charge Separation and Exciton Dynamics at Polymer/ZnO Interface from First-Principles Simulations.

PubMed

Wu, Guangfen; Li, Zi; Zhang, Xu; Lu, Gang

2014-08-07

Charge separation and exciton dynamics play a crucial role in determining the performance of excitonic photovoltaics. Using time-dependent density functional theory with a range-separated exchange-correlation functional as well as nonadiabatic ab initio molecular dynamics, we have studied the formation and dynamics of charge-transfer (CT) excitons at polymer/ZnO interface. The interfacial atomic structure, exciton density of states and conversions between exciton species are examined from first-principles. The exciton dynamics exhibits both adiabatic and nonadiabatic characters. While the adiabatic transitions are facilitated by C═C vibrations along the polymer (P3HT) backbone, the nonadiabatic transitions are realized by exciton hopping between the excited states. We find that the localized ZnO surface states lead to localized low-energy CT states and poor charge separation. In contrast, the surface states of crystalline C60 are indistinguishable from the bulk states, resulting in delocalized CT states and efficient charge separation in polymer/fullerene (P3HT/PCBM) heterojunctions. The hot CT states are found to cool down in an ultrafast time scale and may not play a major role in charge separation of P3HT/ZnO. Finally we suggest that the dimensions of nanostructured acceptors can be tuned to obtain both efficient charge separation and high open circuit voltages.

Enabling valley selective exciton scattering in monolayer WSe2 through upconversion

PubMed Central

Manca, M.; Glazov, M. M.; Robert, C.; Cadiz, F.; Taniguchi, T.; Watanabe, K.; Courtade, E.; Amand, T.; Renucci, P.; Marie, X.; Wang, G.; Urbaszek, B.

2017-01-01

Excitons, Coulomb bound electron–hole pairs, are composite bosons and their interactions in traditional semiconductors lead to condensation and light amplification. The much stronger Coulomb interaction in transition metal dichalcogenides such as WSe2 monolayers combined with the presence of the valley degree of freedom is expected to provide new opportunities for controlling excitonic effects. But so far the bosonic character of exciton scattering processes remains largely unexplored in these two-dimensional materials. Here we show that scattering between B-excitons and A-excitons preferably happens within the same valley in momentum space. This leads to power dependent, negative polarization of the hot B-exciton emission. We use a selective upconversion technique for efficient generation of B-excitons in the presence of resonantly excited A-excitons at lower energy; we also observe the excited A-excitons state 2s. Detuning of the continuous wave, low-power laser excitation outside the A-exciton resonance (with a full width at half maximum of 4 meV) results in vanishing upconversion signal. PMID:28367962

Spatial exciton allocation strategy with reduced energy loss for high-efficiency fluorescent/phosphorescent hybrid white organic light-emitting diodes

DOE PAGES

Zhao, Fangchao; Wei, Ying; Xu, Hui; ...

2017-05-17

Due to the poor operational lifetime of blue phosphorescent dopants and blue thermally activated delayed fluorescent (TADF) materials, hybrid white organic light-emitting diodes (WOLEDs) with conventional blue fluorescent emitters are still preferred for commercial applications in general lighting. However, the improvement in the overall efficiency of hybrid WOLEDs has been limited due to energy losses during the energy transfer process and exciton quenching after the spatial separation of the singlet and triplet excitons. Here we demonstrate the development of a Spatial Exciton Allocation Strategy (SEAS) to achieve close to 100% internal quantum efficiency (IQE) in blue-yellow complementary color hybrid WOLEDs.more » The employed blue fluorophore not only has a resonant triplet level with the yellow phosphor to reduce energy loss during energy transfer processes and triplet–triplet annihilation (TTA), but also has a resonant singlet level with the electron transport layer to extend singlet exciton distribution and enhance both singlet and triplet exciton utilization. Thus, the resulting hybrid WOLEDs exhibited 104 lm W -1 efficacy at 100 cd m -2 and 74 lm W -1 at 1000 cd m -2 with CIE coordinates of (0.42, 0.44) which is warm white and suitable for indoor lighting.« less

Spatial exciton allocation strategy with reduced energy loss for high-efficiency fluorescent/phosphorescent hybrid white organic light-emitting diodes

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

Zhao, Fangchao; Wei, Ying; Xu, Hui

Due to the poor operational lifetime of blue phosphorescent dopants and blue thermally activated delayed fluorescent (TADF) materials, hybrid white organic light-emitting diodes (WOLEDs) with conventional blue fluorescent emitters are still preferred for commercial applications in general lighting. However, the improvement in the overall efficiency of hybrid WOLEDs has been limited due to energy losses during the energy transfer process and exciton quenching after the spatial separation of the singlet and triplet excitons. Here we demonstrate the development of a Spatial Exciton Allocation Strategy (SEAS) to achieve close to 100% internal quantum efficiency (IQE) in blue-yellow complementary color hybrid WOLEDs.more » The employed blue fluorophore not only has a resonant triplet level with the yellow phosphor to reduce energy loss during energy transfer processes and triplet–triplet annihilation (TTA), but also has a resonant singlet level with the electron transport layer to extend singlet exciton distribution and enhance both singlet and triplet exciton utilization. Thus, the resulting hybrid WOLEDs exhibited 104 lm W -1 efficacy at 100 cd m -2 and 74 lm W -1 at 1000 cd m -2 with CIE coordinates of (0.42, 0.44) which is warm white and suitable for indoor lighting.« less

An efficient descriptor model for designing materials for solar cells

NASA Astrophysics Data System (ADS)

Alharbi, Fahhad H.; Rashkeev, Sergey N.; El-Mellouhi, Fedwa; Lüthi, Hans P.; Tabet, Nouar; Kais, Sabre

2015-11-01

An efficient descriptor model for fast screening of potential materials for solar cell applications is presented. It works for both excitonic and non-excitonic solar cells materials, and in addition to the energy gap it includes the absorption spectrum (α(E)) of the material. The charge transport properties of the explored materials are modelled using the characteristic diffusion length (Ld) determined for the respective family of compounds. The presented model surpasses the widely used Scharber model developed for bulk heterojunction solar cells. Using published experimental data, we show that the presented model is more accurate in predicting the achievable efficiencies. To model both excitonic and non-excitonic systems, two different sets of parameters are used to account for the different modes of operation. The analysis of the presented descriptor model clearly shows the benefit of including α(E) and Ld in view of improved screening results.

Electrical control of optical orientation of neutral and negatively charged excitons in an n -type semiconductor quantum well

NASA Astrophysics Data System (ADS)

Dzhioev, R. I.; Korenev, V. L.; Lazarev, M. V.; Sapega, V. F.; Gammon, D.; Bracker, A. S.

2007-01-01

We report electric field induced increase of spin orientation of negatively charged excitons (trions) localized in n -type GaAs/AlGaAs quantum well. Under resonant excitation of free neutral heavy-hole excitons, the polarization of trions increases dramatically with electrical injection of electrons. The polarization enhancement correlates strongly with trion/exciton luminescence intensity ratio. This effect results from a very efficient trapping of free neutral excitons by the quantum well interfacial fluctuations (“natural” quantum dots) containing resident electrons.

A Comparison Between Magnetic Field Effects in Excitonic and Exciplex Organic Light-Emitting Diodes

NASA Astrophysics Data System (ADS)

Sahin Tiras, Kevser; Wang, Yifei; Harmon, Nicholas J.; Wohlgenannt, Markus; Flatte, Michael E.

In flat-panel displays and lighting applications, organic light emitting diodes (OLEDs) have been widely used because of their efficient light emission, low-cost manufacturing and flexibility. The electrons and holes injected from the anode and cathode, respectively, form a tightly bound exciton as they meet at a molecule in organic layer. Excitons occur as spin singlets or triplets and the ratio between singlet and triplet excitons formed is 1:3 based on spin degeneracy. The internal quantum efficiency (IQE) of fluorescent-based OLEDs is limited 25% because only singlet excitons contribute the light emission. To overcome this limitation, thermally activated delayed fluorescent (TADF) materials have been introduced in the field of OLEDs. The exchange splitting between the singlet and triplet states of two-component exciplex systems is comparable to the thermal energy in TADF materials, whereas it is usually much larger in excitons. Reverse intersystem crossing occurs from triplet to singlet exciplex state, and this improves the IQE. An applied small magnetic field can change the spin dynamics of recombination in TADF blends. In this study, magnetic field effects on both excitonic and exciplex OLEDs will be presented and comparison similarities and differences will be made.

Unexpectedly Fast Phonon-Assisted Exciton Hopping between Carbon Nanotubes

DOE PAGES

Davoody, A. H.; Karimi, F.; Arnold, M. S.; ...

2017-06-05

Carbon-nanotube (CNT) aggregates are promising light-absorbing materials for photovoltaics. The hopping rate of excitons between CNTs directly affects the efficiency of these devices. We theoretically investigate phonon-assisted exciton hopping, where excitons scatter with phonons into a same-tube transition state, followed by intertube Coulomb scattering into the final state. Second-order hopping between bright excitonic states is as fast as the first-order process (~1 ps). For perpendicular CNTs, the high rate stems from the high density of phononic states; for parallel CNTs, the reason lies in relaxed selection rules. Moreover, second-order exciton transfer between dark and bright states, facilitated by phonons withmore » large angular momentum, has rates comparable to bright-to-bright transfer, so dark excitons provide an additional pathway for energy transfer in CNT composites. Furthermore, as dark excitons are difficult to probe in experiment, predictive theory is critical for understanding exciton dynamics in CNT composites.« less

Unexpectedly Fast Phonon-Assisted Exciton Hopping between Carbon Nanotubes

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

Davoody, A. H.; Karimi, F.; Arnold, M. S.

Carbon-nanotube (CNT) aggregates are promising light-absorbing materials for photovoltaics. The hopping rate of excitons between CNTs directly affects the efficiency of these devices. We theoretically investigate phonon-assisted exciton hopping, where excitons scatter with phonons into a same-tube transition state, followed by intertube Coulomb scattering into the final state. Second-order hopping between bright excitonic states is as fast as the first-order process (~1 ps). For perpendicular CNTs, the high rate stems from the high density of phononic states; for parallel CNTs, the reason lies in relaxed selection rules. Moreover, second-order exciton transfer between dark and bright states, facilitated by phonons withmore » large angular momentum, has rates comparable to bright-to-bright transfer, so dark excitons provide an additional pathway for energy transfer in CNT composites. Furthermore, as dark excitons are difficult to probe in experiment, predictive theory is critical for understanding exciton dynamics in CNT composites.« less

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.

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.

Electrically driven plasmon-exciton coupled random lasing in ZnO metal-semiconductor-metal devices

NASA Astrophysics Data System (ADS)

Suja, Mohammad; Debnath, Bishwajit; Bashar, Sunayna B.; Su, Longxing; Lake, Roger; Liu, Jianlin

2018-05-01

Electrically driven plasmon-exciton coupled random lasing is demonstrated by incorporating Ag nanoparticles on Cu-doped ZnO metal-semiconductor-metal (MSM) devices. Both photoluminescence and electroluminescence studies show that emission efficiencies have been enhanced significantly due to coupling between ZnO excitons and Ag surface plasmons. With the incorporation of Ag nanoparticles on ZnO MSM structures, internal quantum efficiency up to 6 times is demonstrated. Threshold current for lasing is decreased by as much as 30% while the output power is increased up to 350% at an injection current of 40 mA. A numerical simulation study reveals that hole carriers are generated in the ZnO MSM devices from impact ionization processes for subsequent plasmon-exciton coupled lasing.

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.

Excitonic effects and related properties in semiconductor nanostructures: roles of size and dimensionality

NASA Astrophysics Data System (ADS)

Wu, Shudong; Cheng, Liwen; Wang, Qiang

2017-08-01

The size- and dimensionality-dependence of excitonic effects and related properties in semiconductor nanostructures are theoretically studied in detail within the effective-mass approximation. When nanostructure sizes become smaller than the bulk exciton Bohr radius, excitonic effects are significantly enhanced with reducing size or dimensionality. This is as a result of quantum confinement in more directions leading to larger exciton binding energies and normalized exciton oscillator strengths. These excitonic effects originate from electron-hole Coulombic interactions, which strongly enhance the oscillator strength between the electron and hole. It is also established that the universal scaling of exciton binding energy versus the inverse of the exciton Bohr radius follows a linear scaling law. Herein, we propose a stretched exponential law for the size scaling of optical gap, which is in good agreement with the calculated data. Due to differences in the confinement dimensionality, the radiative lifetime of low-dimensional excitons becomes shorter than that of bulk excitons. The size dependence of the exciton radiative lifetimes is in good agreement with available experimental data. This strongly enhanced electron-hole exchange interaction is expected in low-dimensional structures due to enriched excitonic effects. The main difference in nanostructures compared to the bulk can be interpreted in terms of the enhanced excitonic effects induced by exciton localization. The enhanced excitonic effects are expected to be of importance in developing stable and high-efficiency nanoscale excitonic optoelectronic devices.

Exciton-exciton annihilation in a disordered molecular system by direct and multistep Förster transfer

NASA Astrophysics Data System (ADS)

Fennel, Franziska; Lochbrunner, Stefan

2015-10-01

Exciton annihilation dynamics in a disordered organic model system is investigated by ultrafast absorption spectroscopy. We show that the temporal evolution of the exciton density can be quantitatively understood by applying Förster energy transfer theory to describe the diffusion of the excitons as well as the annihilation step itself. To this end, previous formulations of Förster theory are extended to account for the inhomogeneous distribution of the S0-S1 transition energies resulting in an effective exciton diffusion constant. Two annihilation pathways are considered, the direct transfer of an exciton between two excited molecules and diffusive motion by multiple transfer steps towards a second exciton preceding the annihilation event. One pathway can be emphasized with respect to the other by tuning the exciton diffusion constant via the chromophore concentration. The investigated system allows one to extract all relevant parameters for the description and provides in this way a proof that the annihilation dynamics can be entirely understood and modeled by Förster energy transfer.

Highly efficient phosphorescence from organic light-emitting devices with an exciton-block layer

NASA Astrophysics Data System (ADS)

Ikai, Masamichi; Tokito, Shizuo; Sakamoto, Youichi; Suzuki, Toshiyasu; Taga, Yasunori

2001-07-01

One of the keys to highly efficient phosphorescent emission in organic light-emitting devices is to confine triplet excitons generated within the emitting layer. We employ "starburst" perfluorinated phenylenes (C60F42) as a both hole- and exciton-block layer, and a hole-transport material 4,4',4″-tri(N-carbazolyl) triphenylamine as a host for the phosphorescent dopant dye in the emitting layer. A maximum external quantum efficiency reaches to 19.2%, and keeps over 15% even at high current densities of 10-20 mA/cm2, providing several times the brightness of fluorescent tubes for lighting. The onset voltage of the electroluminescence is as low as 2.4 V and the peak power efficiency is 70-72 lm/W, promising for low-power display devices.

Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes

NASA Astrophysics Data System (ADS)

Cho, Himchan; Jeong, Su-Hun; Park, Min-Ho; Kim, Young-Hoon; Wolf, Christoph; Lee, Chang-Lyoul; Heo, Jin Hyuck; Sadhanala, Aditya; Myoung, NoSoung; Yoo, Seunghyup; Im, Sang Hyuk; Friend, Richard H.; Lee, Tae-Woo

2015-12-01

Organic-inorganic hybrid perovskites are emerging low-cost emitters with very high color purity, but their low luminescent efficiency is a critical drawback. We boosted the current efficiency (CE) of perovskite light-emitting diodes with a simple bilayer structure to 42.9 candela per ampere, similar to the CE of phosphorescent organic light-emitting diodes, with two modifications: We prevented the formation of metallic lead (Pb) atoms that cause strong exciton quenching through a small increase in methylammonium bromide (MABr) molar proportion, and we spatially confined the exciton in uniform MAPbBr3 nanograins (average diameter = 99.7 nanometers) formed by a nanocrystal pinning process and concomitant reduction of exciton diffusion length to 67 nanometers. These changes caused substantial increases in steady-state photoluminescence intensity and efficiency of MAPbBr3 nanograin layers.

Intrinsic exciton-state mixing and nonlinear optical properties in transition metal dichalcogenide monolayers

NASA Astrophysics Data System (ADS)

Glazov, M. M.; Golub, L. E.; Wang, G.; Marie, X.; Amand, T.; Urbaszek, B.

2017-01-01

Optical properties of transition metal dichalcogenides monolayers are controlled by Wannier-Mott excitons forming a series of 1 s ,2 s ,2 p ,... hydrogen-like states. We develop the theory of the excited excitonic states energy spectrum fine structure. We predict that p - and s -shell excitons are mixed due to the specific D3 h point symmetry of the transition metal dichalcogenide monolayers. Hence, both s - and p -shell excitons are active in both single- and two-photon processes, providing an efficient mechanism of second harmonic generation. The corresponding contribution to the nonlinear susceptibility is calculated.

Probing Exciton Diffusion and Dissociation in Single-Walled Carbon Nanotube-C60 Heterojunctions

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

Dowgiallo, Anne-Marie; Mistry, Kevin S.; Johnson, Justin C.

The efficiency of thin-film organic photovoltaic (OPV) devices relies heavily upon the transport of excitons to type-II heterojunction interfaces, where there is sufficient driving force for exciton dissociation and ultimately the formation of charge carriers. Semiconducting single-walled carbon nanotubes (SWCNTs) are strong near-infrared absorbers that form type-II heterojunctions with fullerenes such as C60. Although the efficiencies of SWCNT-fullerene OPV devices have climbed over the past few years, questions remain regarding the fundamental factors that currently limit their performance. In this study, we determine the exciton diffusion length in the C60 layer of SWCNT-C60 bilayer active layers using femtosecond transient absorptionmore » measurements. We demonstrate that hole transfer from photoexcited C60 molecules to SWCNTs can be tracked by the growth of narrow spectroscopic signatures of holes in the SWCNT 'reporter layer'. In bilayers with thick C60 layers, the SWCNT charge-related signatures display a slow rise over hundreds of picoseconds, reflecting exciton diffusion through the C60 layer to the interface. A model based on exciton diffusion with a Beer-Lambert excitation profile, as well as Monte Carlo simulations, gives the best fit to the data as a function of C60 layer thickness using an exciton diffusion length of approximately 5 nm.« less

Probing Exciton Diffusion and Dissociation in Single-Walled Carbon Nanotube-C(60) Heterojunctions.

PubMed

Dowgiallo, Anne-Marie; Mistry, Kevin S; Johnson, Justin C; Reid, Obadiah G; Blackburn, Jeffrey L

2016-05-19

The efficiency of thin-film organic photovoltaic (OPV) devices relies heavily upon the transport of excitons to type-II heterojunction interfaces, where there is sufficient driving force for exciton dissociation and ultimately the formation of charge carriers. Semiconducting single-walled carbon nanotubes (SWCNTs) are strong near-infrared absorbers that form type-II heterojunctions with fullerenes such as C60. Although the efficiencies of SWCNT-fullerene OPV devices have climbed over the past few years, questions remain regarding the fundamental factors that currently limit their performance. In this study, we determine the exciton diffusion length in the C60 layer of SWCNT-C60 bilayer active layers using femtosecond transient absorption measurements. We demonstrate that hole transfer from photoexcited C60 molecules to SWCNTs can be tracked by the growth of narrow spectroscopic signatures of holes in the SWCNT "reporter layer". In bilayers with thick C60 layers, the SWCNT charge-related signatures display a slow rise over hundreds of picoseconds, reflecting exciton diffusion through the C60 layer to the interface. A model based on exciton diffusion with a Beer-Lambert excitation profile, as well as Monte Carlo simulations, gives the best fit to the data as a function of C60 layer thickness using an exciton diffusion length of approximately 5 nm.

Optimization of hybrid blue organic light-emitting diodes based on singlet and triplet exciton diffusion length

NASA Astrophysics Data System (ADS)

Lee, Song Eun; Lee, Ho Won; Lee, Jae Woo; Hwang, Kyo Min; Park, Soo Na; Yoon, Seung Soo; Kim, Young Kwan

2015-06-01

The hybrid blue organic light-emitting diodes (HB OLEDs) with triplet harvesting (TH) structures within an emitting layer (EML) are fabricated with fluorescent and phosphorescent EMLs. The TH is to transfer triplet excitons from fluorescence to phosphorescence, where they can decay radiatively. Remarkably, the half-decay lifetime of a hybrid blue device with fluorescent and phosphorescent EML thickness of 5 and 25 nm, measured at an initial luminance of 500 cd/m2, has improved twice than that of using a conventional structure. Additionally, the blue device’s efficiency improved. We attribute this improvement to the efficient triplet excitons energy transfer and the optimized distribution of the EML which depends on singlet and triplet excitons diffusion length that occurs within each the EML.

Energy-cascade organic photovoltaic devices incorporating a host-guest architecture.

PubMed

Menke, S Matthew; Holmes, Russell J

2015-02-04

In planar heterojunction organic photovoltaic devices (OPVs), broad spectral coverage can be realized by incorporating multiple molecular absorbers in an energy-cascade architecture. Here, this approach is combined with a host-guest donor layer architecture previously shown to optimize exciton transport for the fluorescent organic semiconductor boron subphthalocyanine chloride (SubPc) when diluted in an optically transparent host. In order to maximize the absorption efficiency, energy-cascade OPVs that utilize both photoactive host and guest donor materials are examined using the pairing of SubPc and boron subnaphthalocyanine chloride (SubNc), respectively. In a planar heterojunction architecture, excitons generated on the SubPc host rapidly energy transfer to the SubNc guest, where they may migrate toward the dissociating, donor-acceptor interface. Overall, the incorporation of a photoactive host leads to a 13% enhancement in the short-circuit current density and a 20% enhancement in the power conversion efficiency relative to an optimized host-guest OPV combining SubNc with a nonabsorbing host. This work underscores the potential for further design refinements in planar heterojunction OPVs and demonstrates progress toward the effective separation of functionality between constituent OPV materials.

Photoexcited emission efficiencies of zinc oxide

NASA Astrophysics Data System (ADS)

Foreman, John Vincent

Optoelectronic properties of the II-VI semiconductor zinc oxide (ZnO) have been studied scientifically for almost 60 years; however, many fundamental questions remain unanswered about its two primary emission bands--the exciton-related luminescence in the ultraviolet and the defect-related emission band centered in the green portion of the visible spectrum. The work in this dissertation was motivated by the surprising optical properties of a ZnO nanowire sample grown by the group of Prof. Jie Liu, Department of Chemistry, Duke University. We found that this nanowire sample exhibited defect-related green/white emission of unprecedented intensity relative to near-band-edge luminescence. The experimental work comprising this dissertation was designed to explain the optical properties of this ZnO nanowire sample. Understanding the physics underlying such exceptional intensity of green emission addresses many of the open questions of ZnO research and assesses the possibility of using ZnO nanostructures as an ultraviolet-excited, broadband visible phosphor. The goal of this dissertation is to provide insight into what factors influence the radiative and nonradiative recombination efficiencies of ZnO by characterizing simultaneously the optical properties of the near-band-edge ultraviolet and the defect-related green emission bands. Specifically, we seek to understand the mechanisms of ultraviolet and green emission, the mechanism of energy transfer between them, and the evolution of their emission efficiencies with parameters such as excitation density and sample temperature. These fundamental but unanswered questions of ZnO emission are addressed here by using a novel combination of ultrafast spectroscopic techniques in conjunction with a systematic set of ZnO samples. Through this systematic investigation, ZnO may be realistically assessed as a potential green/white light phosphor. Photoluminescence techniques are used to characterize the thermal quenching behavior of both emission bands in micrometer-scale ZnO powders. Green luminescence quenching is described by activation energies associated with bound excitons. We find that green luminescence efficiency is maximized when excitons are localized in the vicinity of green-emitting defects. Subsequent photoluminescence excitation measurements performed at multiple temperatures independently verified that green band photoluminescence intensity directly correlates with the photogenerated exciton population. The spatial distributions of green-emitting defects and nonradiative traps are elucidated by an innovative combination of quantum efficiency and time-integrated/resolved photoluminescence measurements. By combining these techniques for the first time, we take advantage of the drastically different absorption coefficients for one- and two-photon excitations to provide details about the types and concentrations of surface and bulk defects and to demonstrate the non-negligible effects of reabsorption. A comparison of results for unannealed and annealed ZnO powders indicates that the annealing process creates a high density of green-emitting defects near the surface of the sample while simultaneously reducing the density of bulk nonradiative traps. These experimental results are discussed in the context of a simple rate equation model that accounts for the quantum efficiencies of both emission bands. For both femtosecond pulsed and continuous-wave excitations, the green band efficiency is found to decrease with increasing excitation density--from 35% to 5% for pulsed excitation spanning 1-1000 muJ/cm--2, and from 60% to 5% for continuous excitation in the range 0.01-10 W/cm --2. On the other hand, near-band-edge emission efficiency increases from 0.4% to 25% for increasing pulsed excitation density and from 0.1% to 0.6% for continuous excitation. It is shown experimentally that these changes in efficiency correspond to a reduction in exciton formation efficiency. The differences in efficiencies for pulsed versus continuous-wave excitation are described by changes in the relative rates of exciton luminescence and exciton capture at green defects based on an extended rate equation model that accounts for the excitation density dependence of both luminescence bands. In using a systematic set of ZnO samples and a novel combination of optical techniques to characterize them, this body of work presents a comprehensive and detailed physical picture of recombination mechanisms in ZnO. The insight provided by these results has immediate implications for material growth/processing techniques and should help material growers control the relative efficiencies of ultraviolet, green/visible, and nonradiative recombination channels in ZnO.

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

Coherent Exciton Dynamics in the Presence of Underdamped Vibrations

DOE PAGES

Dijkstra, Arend G.; Wang, Chen; Cao, Jianshu; ...

2015-01-22

Recent ultrafast optical experiments show that excitons in large biological light-harvesting complexes are coupled to molecular vibration modes. These high-frequency vibrations will not only affect the optical response, but also drive the exciton transport. Here, using a model dimer system, the frequency of the underdamped vibration is shown to have a strong effect on the exciton dynamics such that quantum coherent oscillations in the system can be present even in the case of strong noise. Two mechanisms are identified to be responsible for the enhanced transport efficiency: critical damping due to the tunable effective strength of the coupling to themore » bath, and resonance coupling where the vibrational frequency coincides with the energy gap in the system. The interplay of these two mechanisms determines parameters responsible for the most efficient transport, and these optimal control parameters are comparable to those in realistic light-harvesting complexes. Interestingly, oscillations in the excitonic coherence at resonance are suppressed in comparison to the case of an off-resonant vibration.« less

Intensity and temperature-dependent photoluminescence of tris (8-hydroxyquinoline) aluminum films

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

Ajward, A. M.; Wang, X.; Wagner, H. P.

2013-12-04

We investigate the recombination of excitons in tris (8-hydroxyquinoline) aluminum films by intensity and temperature dependent time-resolved photoluminescence (PL). At low temperature (15 K) and elevated excitation intensity the radiative emission is quenched by singlet-singlet annihilation processes. With rising temperature the PL quenching is strongly reduced resulting in a PL efficiency maximum at ∼170 K. The reduced exciton annihilation is attributed to thermally activated occupation of non-quenchable trapped exciton states. Above 170 K the PL efficiency decreases due to thermal de-trapping of radiative states and subsequent migration to non-radiative centers.

Electronic Two-Transition-Induced Enhancement of Emission Efficiency in Polymer Light-Emitting Diodes

PubMed Central

Chen, Ren-Ai; Wang, Cong; Li, Sheng; George, Thomas F.

2013-01-01

With the development of experimental techniques, effective injection and transportation of electrons is proven as a way to obtain polymer light-emitting diodes (PLEDs) with high quantum efficiency. This paper reveals a valid mechanism for the enhancement of quantum efficiency in PLEDs. When an external electric field is applied, the interaction between a negative polaron and triplet exciton leads to an electronic two-transition process, which induces the exciton to emit light and thus improve the emission efficiency of PLEDs. PMID:28809346

Exciton fission in monolayer transition metal dichalcogenide semiconductors.

PubMed

Steinhoff, A; Florian, M; Rösner, M; Schönhoff, G; Wehling, T O; Jahnke, F

2017-10-27

When electron-hole pairs are excited in a semiconductor, it is a priori not clear if they form a plasma of unbound fermionic particles or a gas of composite bosons called excitons. Usually, the exciton phase is associated with low temperatures. In atomically thin transition metal dichalcogenide semiconductors, excitons are particularly important even at room temperature due to strong Coulomb interaction and a large exciton density of states. Using state-of-the-art many-body theory, we show that the thermodynamic fission-fusion balance of excitons and electron-hole plasma can be efficiently tuned via the dielectric environment as well as charge carrier doping. We propose the observation of these effects by studying exciton satellites in photoemission and tunneling spectroscopy, which present direct solid-state counterparts of high-energy collider experiments on the induced fission of composite particles.

Color-tunable and high-efficiency organic light-emitting diode by adjusting exciton bilateral migration zone

NASA Astrophysics Data System (ADS)

Liu, Shengqiang; Wu, Ruofan; Huang, Jiang; Yu, Junsheng

2013-09-01

A voltage-controlled color-tunable and high-efficiency organic light-emitting diode (OLED) by inserting 16-nm N,N'-dicarbazolyl-3,5-benzene (mCP) interlayer between two complementary emitting layers (EMLs) was fabricated. The OLED emitted multicolor ranging from blue (77.4 cd/A @ 6 V), white (70.4 cd/A @ 7 V), to yellow (33.7 cd/A @ 9 V) with voltage variation. An equivalent model was proposed to reveal the color-tunable and high-efficiency emission of OLEDs, resulting from the swing of exciton bilateral migration zone near mCP/blue-EML interface. Also, the model was verified with a theoretical arithmetic using single-EML OLEDs to disclose the crucial role of mCP exciton adjusting layer.

Optical studies of native defects in π-conjugated donor-acceptor copolymers

NASA Astrophysics Data System (ADS)

Baniya, Sangita; Khanal, Dipak; Lafalce, Evan; You, Wei; Valy Vardeny, Z.

2018-04-01

We used multiple spectroscopies such as photoinduced absorption (PIA), magneto photoinduced absorption, and doping induced absorption for studying native defects in π-conjugated donor-acceptor copolymer chains of benzodithio-phene fluorinated benzotriazole. The PIA spectrum contains characteristic photoinduced absorption bands that are due to polarons and triplet exciton species, whose strengths have different dependencies on the modulation frequency, temperature, and laser excitation, as well as magnetic field response. We found that the native defects in the copolymer chains serve as efficient traps that ionize the photoexcited excitons, thereby generating charge carriers whose characteristic optical properties are similar, but not equal to those of intrachain polarons formed by doping. The native defects density is of the order of 1017 cm-3 indicating that most of the copolymer chains contain native defects upon synthesis; however, this does not preclude their used-for photovoltaic applications.

Singlet-to-triplet intermediates and triplet exciton dynamics in pentacene thinfilms

NASA Astrophysics Data System (ADS)

Thorsmolle, Verner; Korber, Michael; Obergfell, Emanuel; Kuhlman, Thomas; Campbell, Ian; Crone, Brian; Taylor, Antoinette; Averitt, Richard; Demsar, Jure

Singlet-to-triplet fission in organic semiconductors is a spin-conserving multiexciton process in which one spin-zero singlet excitation is converted into two spin-one triplet excitations on an ultrafast timescale. Current scientific interest into this carrier multiplication process is largely driven by prospects of enhancing the efficiency in photovoltaic applications by generating two long-lived triplet excitons by one photon. The fission process is known to involve intermediate states, known as correlated triplet pairs, with an overall singlet character, before being interchanged into uncorrelated triplets. Here we use broadband femtosecond real-time spectroscopy to study the excited state dynamics in pentacene thin films, elucidating the fission process and the role of intermediate triplet states. VKT and AJT acknowledge support by the LDRD program at Los Alamos National Laboratory and the Department of Energy, Grant No. DE-FG02-04ER118. MK, MO and JD acknowledge support by the Alexander von Humboldt Foundation.

Atomistic absorption spectra and non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model

NASA Astrophysics Data System (ADS)

Glowacki, David

Recently, we outlined an efficient multi-tiered parallel excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground/excited state energies and gradients of large supramolecular complexes in atomistic detail. In this paper, we apply our ab initioexciton framework to the 27 coupled bacteriocholorophyll-a chromophores which make up the LH2 complex, using it to compute linear absorption spectra and short-time, on-the-fly nonadiabatic surface-hopping (SH) dynamics of electronically excited LH2. Our ab initio exciton model includes two key parameters whose values are determined by fitting to experiment: d, which is added to the diagonal elements, corrects for the error in TDDFT vertical excitation energies on a single chromophore; and e, which occurs on the off-diagonal matrix elements, describes the average dielectric screening of the inter-chromophore transition-dipole coupling. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, best-fit values of both d and e were obtained by fitting to the thermally broadened experimental absorption spectrum within the Frank-Condon approximation, providing a linear absorption spectrum that agrees reasonably well with the experimental observations. We follow the nonadiabatic dynamics using surface hopping to construct time-resolved visualizations of the EET dynamics in the sub-picosecond regime following photoexcitation. This provides some qualitative insight into the excitonic energy transfer (EET) that results from atomically resolved vibrational fluctuations of the chromophores. The dynamical picture that emerges is one of rapidly fluctuating eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the underlying chromophore vibrational dynamics. The eigenstate fluctuations arise from disorder in both the diagonal chromophore site energies and the off-diagonal inter-chromophore couplings. The scalability of our excitonic computational framework across massively parallel architectures opens up the possibility of addressing a wide range of questions, including how specific dynamical motions impact both the pathways and efficiency of electronic energy-transfer within large supramolecular systems.

Novel Polymers for High Efficiency Renewable and Portable Power Applications

DTIC Science & Technology

2015-07-30

photoelectric, thermoelectric , energy conversions, charge transfer, energy transfer, photoluminescence (PL). REPORT DOCUMENTATION PAGE 11. SPONSOR...of polymer/dye interface of photo generated excitons in the covalent system resulting in more efficient exciton dissociations. 4) For thermoelectric ...studies, it appears the thermoelectric charge carrier generations of the four conjugated polymers doped with iodine at room temperature are in the

Many-body effects in nonlinear optical responses of 2D layered semiconductors

DOE PAGES

Aivazian, Grant; Yu, Hongyi; Wu, Sanfeng; ...

2017-01-05

We performed ultrafast degenerate pump-probe spectroscopy on monolayer WSe2 near its exciton resonance. The observed differential reflectance signals exhibit signatures of strong many-body interactions including the exciton-exciton interaction and free carrier induced band gap renormalization. The exciton-exciton interaction results in a resonance blue shift which lasts for the exciton lifetime (several ps), while the band gap renormalization manifests as a resonance red shift with several tens ps lifetime. Our model based on the many-body interactions for the nonlinear optical susceptibility ts well the experimental observations. The power dependence of the spectra shows that with the increase of pump power, themore » exciton population increases linearly and then saturates, while the free carrier density increases superlinearly, implying that exciton Auger recombination could be the origin of these free carriers. Our model demonstrates a simple but efficient method for quantitatively analyzing the spectra, and indicates the important role of Coulomb interactions in nonlinear optical responses of such 2D materials.« less

Many-body effects in nonlinear optical responses of 2D layered semiconductors

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

Aivazian, Grant; Yu, Hongyi; Wu, Sanfeng

We performed ultrafast degenerate pump-probe spectroscopy on monolayer WSe2 near its exciton resonance. The observed differential reflectance signals exhibit signatures of strong many-body interactions including the exciton-exciton interaction and free carrier induced band gap renormalization. The exciton-exciton interaction results in a resonance blue shift which lasts for the exciton lifetime (several ps), while the band gap renormalization manifests as a resonance red shift with several tens ps lifetime. Our model based on the many-body interactions for the nonlinear optical susceptibility ts well the experimental observations. The power dependence of the spectra shows that with the increase of pump power, themore » exciton population increases linearly and then saturates, while the free carrier density increases superlinearly, implying that exciton Auger recombination could be the origin of these free carriers. Our model demonstrates a simple but efficient method for quantitatively analyzing the spectra, and indicates the important role of Coulomb interactions in nonlinear optical responses of such 2D materials.« less

Orientation-Dependent Exciton-Plasmon Coupling in Embedded Organic/Metal Nanowire Heterostructures.

PubMed

Li, Yong Jun; Hong, Yan; Peng, Qian; Yao, Jiannian; Zhao, Yong Sheng

2017-10-24

The excitation of surface plasmons by optical emitters based on exciton-plasmon coupling is important for plasmonic devices with active optical properties. It has been theoretically demonstrated that the orientation of exciton dipole can significantly influence the coupling strength, yet systematic study of the coupling process in nanostructures is still hindered by the lack of proper material systems. In this work, we have experimentally investigated the orientation-dependent exciton-plasmon coupling in a rationally designed organic/metal nanowire heterostructure system. The heterostructures were prepared by inserting silver nanowires into crystalline organic waveguides during the self-assembly of dye molecules. Structures with different exciton orientations exhibited varying coupling efficiencies. The near-field exciton-plasmon coupling facilitates the design of nanophotonic devices based on the directional surface plasmon polariton propagations.

Exciton Level Structure and Dynamics in Tubular Porphyrin Aggregates

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

Wan, Yan; Stradomska, Anna; Fong, Sarah

2014-10-30

We present an account of the optical properties of the Frenkel excitons in self-assembled porphyrin tubular aggregates that represent an analog to natural photosynthetic antennae. Using a combination of ultrafast optical spectroscopy and stochastic exciton modeling, we address both linear and nonlinear exciton absorption, relaxation pathways, and the role of disorder. The static disorder-dominated absorption and fluorescence line widths show little temperature dependence for the lowest excitons (Q band), which we successfully simulate using a model of exciton scattering on acoustic phonons in the host matrix. Temperature-dependent transient absorption of and fluorescence from the excitons in the tubular aggregates aremore » marked by nonexponential decays with time scales ranging from a few picoseconds to a few nanoseconds, reflecting complex relaxation mechanisms. Combined experimental and theoretical investigations indicate that nonradiative pathways induced by traps and defects dominate the relaxation of excitons in the tubular aggregates. We model the pumpprobe spectra and ascribe the excited-state absorption to transitions from one-exciton states to a manifold of mixed one- and two-exciton states. Our results demonstrate that while the delocalized Frenkel excitons (over 208 (1036) molecules for the optically dominant excitons in the Q (B) band) resulting from strong intermolecular coupling in these aggregates could potentially facilitate efficient energy transfer, fast relaxation due to defects and disorder probably present a major limitation for exciton transport over large distances.« less

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

Abbaszadeh, D.; Wetzelaer, G. A. H.; Dutch Polymer Institute, P.O. Box 902, 5600 AX, Eindhoven

The quenching of excitons at the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) anode in blue polyalkoxyspirobifluorene-arylamine polymer light-emitting diodes is investigated. Due to the combination of a higher electron mobility and the presence of electron traps, the recombination zone shifts from the cathode to the anode with increasing voltage. The exciton quenching at the anode at higher voltages leads to an efficiency roll-off. The voltage dependence of the luminous efficiency is reproduced by a drift-diffusion model under the condition that quenching of excitons at the PEDOT:PSS anode and metallic cathode is of equal strength. Experimentally, the efficiency roll-off at high voltages due tomore » anode quenching is eliminated by the use of an electron-blocking layer between the anode and the light-emitting polymer.« less

Method to analyze the ability of bulk heterojunctions of organic and hybrid solar cells to dissociate photogenerated excitons and collect free carriers

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

Basta, M.; Dusza, M.; Palewicz, M.

2014-05-07

We have developed a model to predict and analyze the photocurrent generation and resulting charge carrier Dissociation and Collection Efficiency (DCE) through reflectivity and quantum efficiency spectra. The DCE is regarded as a function of the morphology and exciton transport properties of the bulk heterojunction and is therefore a way to investigate the final properties of photoactive layer in a solar cell. Method proposed allows determination of the efficiency at which photogenerated excitons are dissociated in a working device with respect to the position in the cell at which the generation occurs. The method is tested on our results asmore » well as on a number of results already present in the literature.« less

Basic aspects for improving the energy conversion efficiency of hetero-junction organic photovoltaic cells.

PubMed

Ryuzaki, Sou; Onoe, Jun

2013-01-01

Hetero-junction organic photovoltaic (OPV) cells consisting of donor (D) and acceptor (A) layers have been regarded as next-generation PV cells, because of their fascinating advantages, such as lightweight, low fabrication cost, resource free, and flexibility, when compared to those of conventional PV cells based on silicon and semiconductor compounds. However, the power conversion efficiency (η) of the OPV cells has been still around 8%, though more than 10% efficiency has been required for their practical use. To fully optimize these OPV cells, it is necessary that the low mobility of carriers/excitons in the OPV cells and the open circuit voltage (V OC), of which origin has not been understood well, should be improved. In this review, we address an improvement of the mobility of carriers/excitons by controlling the crystal structure of a donor layer and address how to increase the V OC for zinc octaethylporphyrin [Zn(OEP)]/C60 hetero-junction OPV cells [ITO/Zn(OEP)/C60/Al]. It was found that crystallization of Zn(OEP) films increases the number of inter-molecular charge transfer (IMCT) excitons and enlarges the mobility of carriers and IMCT excitons, thus significantly improving the external quantum efficiency (EQE) under illumination of the photoabsorption band due to the IMCT excitons. Conversely, charge accumulation of photo-generated carriers in the vicinity of the donor/acceptor (D/A) interface was found to play a key role in determining the V OC for the OPV cells.

Basic aspects for improving the energy conversion efficiency of hetero-junction organic photovoltaic cells

PubMed Central

Ryuzaki, Sou; Onoe, Jun

2013-01-01

Hetero-junction organic photovoltaic (OPV) cells consisting of donor (D) and acceptor (A) layers have been regarded as next-generation PV cells, because of their fascinating advantages, such as lightweight, low fabrication cost, resource free, and flexibility, when compared to those of conventional PV cells based on silicon and semiconductor compounds. However, the power conversion efficiency (η) of the OPV cells has been still around 8%, though more than 10% efficiency has been required for their practical use. To fully optimize these OPV cells, it is necessary that the low mobility of carriers/excitons in the OPV cells and the open circuit voltage (V OC), of which origin has not been understood well, should be improved. In this review, we address an improvement of the mobility of carriers/excitons by controlling the crystal structure of a donor layer and address how to increase the V OC for zinc octaethylporphyrin [Zn(OEP)]/C60 hetero-junction OPV cells [ITO/Zn(OEP)/C60/Al]. It was found that crystallization of Zn(OEP) films increases the number of inter-molecular charge transfer (IMCT) excitons and enlarges the mobility of carriers and IMCT excitons, thus significantly improving the external quantum efficiency (EQE) under illumination of the photoabsorption band due to the IMCT excitons. Conversely, charge accumulation of photo-generated carriers in the vicinity of the donor/acceptor (D/A) interface was found to play a key role in determining the V OC for the OPV cells. PMID:23853702

Exciton effects in the index of refraction of multiple quantum wells and superlattices

NASA Technical Reports Server (NTRS)

Kahen, K. B.; Leburton, J. P.

1986-01-01

Theoretical calculations of the index of refraction of multiple quantum wells and superlattices are presented. The model incorporates both the bound and continuum exciton contributions for the gamma region transitions. In addition, the electronic band structure model has both superlattice and bulk alloy properties. The results indicate that large light-hole masses, i.e., of about 0.23, produced by band mixing effects, are required to account for the experimental data. Furthermore, it is shown that superlattice effects rapidly decrease for energies greater than the confining potential barriers. Overall, the theoretical results are in very good agreement with the experimental data and show the importance of including exciton effects in the index of refraction.

Robust excitons inhabit soft supramolecular nanotubes

PubMed Central

Eisele, Dörthe M.; Arias, Dylan H.; Fu, Xiaofeng; Bloemsma, Erik A.; Steiner, Colby P.; Jensen, Russell A.; Rebentrost, Patrick; Eisele, Holger; Tokmakoff, Andrei; Lloyd, Seth; Nelson, Keith A.; Nicastro, Daniela; Knoester, Jasper; Bawendi, Moungi G.

2014-01-01

Nature's highly efficient light-harvesting antennae, such as those found in green sulfur bacteria, consist of supramolecular building blocks that self-assemble into a hierarchy of close-packed structures. In an effort to mimic the fundamental processes that govern nature’s efficient systems, it is important to elucidate the role of each level of hierarchy: from molecule, to supramolecular building block, to close-packed building blocks. Here, we study the impact of hierarchical structure. We present a model system that mirrors nature’s complexity: cylinders self-assembled from cyanine-dye molecules. Our work reveals that even though close-packing may alter the cylinders’ soft mesoscopic structure, robust delocalized excitons are retained: Internal order and strong excitation-transfer interactions—prerequisites for efficient energy transport—are both maintained. Our results suggest that the cylindrical geometry strongly favors robust excitons; it presents a rational design that is potentially key to nature’s high efficiency, allowing construction of efficient light-harvesting devices even from soft, supramolecular materials. PMID:25092336

Exploiting Fast Exciton Diffusion in Dye-Doped Polymer Nanoparticles to Engineer Efficient Photoswitching.

PubMed

Trofymchuk, Kateryna; Prodi, Luca; Reisch, Andreas; Mély, Yves; Altenhöner, Kai; Mattay, Jochen; Klymchenko, Andrey S

2015-06-18

Photoswitching of bright fluorescent nanoparticles opens new possibilities for bioimaging with superior temporal and spatial resolution. However, efficient photoswitching of nanoparticles is hard to achieve using Förster resonance energy transfer (FRET) to a photochromic dye, because the particle size is usually larger than the Förster radius. Here, we propose to exploit the exciton diffusion within the FRET donor dyes to boost photoswitching efficiency in dye-doped polymer nanoparticles. To this end, we utilized bulky hydrophobic counterions that prevent self-quenching and favor communication of octadecyl rhodamine B dyes inside a polymer matrix of poly(D,L-lactide-co-glycolide). Among tested counterions, only perfluorinated tetraphenylborate that favors the exciton diffusion enables high photoswitching efficiency (on/off ratio ∼20). The switching improves with donor dye loading and requires only 0.1-0.3 wt % of a diphenylethene photochromic dye. Our nanoparticles were validated both in solution and at the single-particle level. The proposed concept paves the way to new efficient photoswitchable nanomaterials.

Quantitative Analysis of the Efficiency of OLEDs.

PubMed

Sim, Bomi; Moon, Chang-Ki; Kim, Kwon-Hyeon; Kim, Jang-Joo

2016-12-07

We present a comprehensive model for the quantitative analysis of factors influencing the efficiency of organic light-emitting diodes (OLEDs) as a function of the current density. The model takes into account the contribution made by the charge carrier imbalance, quenching processes, and optical design loss of the device arising from various optical effects including the cavity structure, location and profile of the excitons, effective radiative quantum efficiency, and out-coupling efficiency. Quantitative analysis of the efficiency can be performed with an optical simulation using material parameters and experimental measurements of the exciton profile in the emission layer and the lifetime of the exciton as a function of the current density. This method was applied to three phosphorescent OLEDs based on a single host, mixed host, and exciplex-forming cohost. The three factors (charge carrier imbalance, quenching processes, and optical design loss) were influential in different ways, depending on the device. The proposed model can potentially be used to optimize OLED configurations on the basis of an analysis of the underlying physical processes.

Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model.

PubMed

Sisto, Aaron; Stross, Clem; van der Kamp, Marc W; O'Connor, Michael; McIntosh-Smith, Simon; Johnson, Graham T; Hohenstein, Edward G; Manby, Fred R; Glowacki, David R; Martinez, Todd J

2017-06-14

We recently outlined an efficient multi-tiered parallel ab initio excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground and excited state energies and gradients of large supramolecular complexes in atomistic detail - enabling us to undertake non-adiabatic simulations which explicitly account for the coupled anharmonic vibrational motion of all the constituent atoms in a supramolecular system. Here we apply that framework to the 27 coupled bacterio-chlorophyll-a chromophores which make up the LH2 complex, using it to compute an on-the-fly nonadiabatic surface-hopping (SH) trajectory of electronically excited LH2. Part one of this article is focussed on calibrating our ab initio exciton Hamiltonian using two key parameters: a shift δ, which corrects for the error in TDDFT vertical excitation energies; and an effective dielectric constant ε, which describes the average screening of the transition-dipole coupling between chromophores. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, we tune the values of both δ and ε through fitting to the thermally broadened experimental absorption spectrum, giving a linear absorption spectrum that agrees reasonably well with experiment. In part two of this article, we construct a time-resolved picture of the coupled vibrational and excitation energy transfer (EET) dynamics in the sub-picosecond regime following photo-excitation. Assuming Franck-Condon excitation of a narrow eigenstate band centred at 800 nm, we use surface hopping to follow a single nonadiabatic dynamics trajectory within the full eigenstate manifold. Consistent with experimental data, this trajectory gives timescales for B800→B850 population transfer (τ B800→B850 ) between 650-1050 fs, and B800 population decay (τ 800→ ) between 10-50 fs. The dynamical picture that emerges is one of rapidly fluctuating LH2 eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the atomic vibrations of the constituent chromophores. The eigenstate fluctuations arise from disorder that is driven by vibrational dynamics with multiple characteristic timescales. The scalability of our ab initio excitonic computational framework across massively parallel architectures opens up the possibility of addressing a wide range of questions, including how specific dynamical motions impact both the pathways and efficiency of electronic energy-transfer within large supramolecular systems.

Enhancing energy transport in conjugated polymers

NASA Astrophysics Data System (ADS)

Holmes, Russell J.

2018-05-01

The conversion of light into usable chemical energy by plants is enabled by the precise spatial arrangement of light-absorbing photosynthetic systems and associated molecular complexes (1). In organic solar cells, there is also the need to control intermolecular spacing and molecular orientation, as well as thin-film crystallinity and morphology, so as to enable efficient energy migration and photoconversion (2). In an organic solar cell, light absorption creates excitons, tightly bound electron-hole pairs that must be efficiently dissociated into their component charge carriers in order to create an electrical current. Thus, long-range exciton migration must occur from the point of photogeneration to a dissociating site. On page 897 of this issue, Jin et al. (3) report on a conjugated polymer nanofiber system that yields exciton diffusion lengths greater than 200 nm. In comparison, organic solar cells are typically constructed with materials having exciton diffusion lengths one order of magnitude smaller than this value, which limits device thickness and optical absorption. Their approach exploits a sequential synthesis method that enables measurement of this long exciton diffusion length (see the figure).

A transferable model for singlet-fission kinetics.

PubMed

Yost, Shane R; Lee, Jiye; Wilson, Mark W B; Wu, Tony; McMahon, David P; Parkhurst, Rebecca R; Thompson, Nicholas J; Congreve, Daniel N; Rao, Akshay; Johnson, Kerr; Sfeir, Matthew Y; Bawendi, Moungi G; Swager, Timothy M; Friend, Richard H; Baldo, Marc A; Van Voorhis, Troy

2014-06-01

Exciton fission is a process that occurs in certain organic materials whereby one singlet exciton splits into two independent triplets. In photovoltaic devices these two triplet excitons can each generate an electron, producing quantum yields per photon of >100% and potentially enabling single-junction power efficiencies above 40%. Here, we measure fission dynamics using ultrafast photoinduced absorption and present a first-principles expression that successfully reproduces the fission rate in materials with vastly different structures. Fission is non-adiabatic and Marcus-like in weakly interacting systems, becoming adiabatic and coupling-independent at larger interaction strengths. In neat films, we demonstrate fission yields near unity even when monomers are separated by >5 Å. For efficient solar cells, however, we show that fission must outcompete charge generation from the singlet exciton. This work lays the foundation for tailoring molecular properties like solubility and energy level alignment while maintaining the high fission yield required for photovoltaic applications.

Excitons emissions and Raman scattering of ZnO nanoparticles embedded in BaF2 matrices by reactive magnetron sputtering.

PubMed

Zang, C H; Su, J F; Liu, Y C; Tang, C J; Fang, S J; Zhang, D M; Zhang, Y S

2011-11-01

ZnO nanoparticles embedded in BaF2 matrix were fabricated by rf magnetic sputtering technology. The optical properties of high quality ZnO nanoparticles, thermally post treated in a N2 atmosphere, were investigated by temperature-dependence photoluminescence measurement. Free exciton and localized exciton were observed at the low temperature. Free exciton peak was at 3.374 eV and localized exciton peak was at 3.420 eV, dominating the PL spectrum at 77 K. Free exciton transition was observed at 3.310 eV at room temperature, whereas the localized exciton transition was at 3.378 eV. The multiple-phonon Raman scattering spectrum showed that ZnO nanoparticles embedded in BaF2 matrix had a large deformation energy originated from lattice mismatch between ZnO and BaF2 matrix. Analysis of the fitting results from the temperature dependence of FWHM of ZnO exciton illustrated that the large value of gamma(ph) was good qualitative agreement with the large deformation potential.

Mapping the nanoscale energetic landscape in conductive polymer films with spatially super-resolved exciton dynamics

NASA Astrophysics Data System (ADS)

Ginsberg, Naomi

2015-03-01

The migration of Frenkel excitons, tightly-bound electron-hole pairs, in polymeric organic semiconducting films is critical to the efficiency of bulk heterojunction solar cells. While these materials exhibit a high degree of structural heterogeneity on the nanoscale, traditional measurements of exciton diffusion lengths are performed on bulk samples. Since both the characteristic length scales of structural heterogeneity and the reported bulk diffusion lengths are smaller than the optical diffraction limit, we adapt far-field super-resolution fluorescence imaging to uncover the correlations between the structural and energetic landscapes that the excitons explore.

Understanding the free energy barrier and multiple timescale dynamics of charge separation in organic photovoltaic cells.

PubMed

Yan, Yaming; Song, Linze; Shi, Qiang

2018-02-28

By employing several lattice model systems, we investigate the free energy barrier and real-time dynamics of charge separation in organic photovoltaic (OPV) cells. It is found that the combined effects of the external electric field, entropy, and charge delocalization reduce the free energy barrier significantly. The dynamic disorder reduces charge carrier delocalization and results in the increased charge separation barrier, while the effect of static disorder is more complicated. Simulation of the real-time dynamics indicates that the free charge generation process involves multiple time scales, including an ultrafast component within hundreds of femtoseconds, an intermediate component related to the relaxation of the hot charge transfer (CT) state, and a slow component on the time scale of tens of picoseconds from the thermally equilibrated CT state. Effects of hot exciton dissociation as well as its dependence on the energy offset between the Frenkel exciton and the CT state are also analyzed. The current results indicate that only a small energy offset between the band gap and the lowest energy CT state is needed to achieve efficient free charge generation in OPV devices, which agrees with recent experimental findings.

Understanding the free energy barrier and multiple timescale dynamics of charge separation in organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Yan, Yaming; Song, Linze; Shi, Qiang

2018-02-01

By employing several lattice model systems, we investigate the free energy barrier and real-time dynamics of charge separation in organic photovoltaic (OPV) cells. It is found that the combined effects of the external electric field, entropy, and charge delocalization reduce the free energy barrier significantly. The dynamic disorder reduces charge carrier delocalization and results in the increased charge separation barrier, while the effect of static disorder is more complicated. Simulation of the real-time dynamics indicates that the free charge generation process involves multiple time scales, including an ultrafast component within hundreds of femtoseconds, an intermediate component related to the relaxation of the hot charge transfer (CT) state, and a slow component on the time scale of tens of picoseconds from the thermally equilibrated CT state. Effects of hot exciton dissociation as well as its dependence on the energy offset between the Frenkel exciton and the CT state are also analyzed. The current results indicate that only a small energy offset between the band gap and the lowest energy CT state is needed to achieve efficient free charge generation in OPV devices, which agrees with recent experimental findings.

Harvesting Triplet Excitons with Exciplex Thermally Activated Delayed Fluorescence Emitters toward High Performance Heterostructured Organic Light-Emitting Field Effect Transistors.

PubMed

Song, Li; Hu, Yongsheng; Liu, Zheqin; Lv, Ying; Guo, Xiaoyang; Liu, Xingyuan

2017-01-25

The utilization of triplet excitons plays a key role in obtaining high emission efficiency for organic electroluminescent devices. However, to date, only phosphorescent materials have been implemented to harvest the triplet excitons in the organic light-emitting field effect transistors (OLEFETs). In this work, we report the first incorporation of exciplex thermally activated delayed fluorescence (TADF) emitters in heterostructured OLEFETs to harvest the triplet excitons. By developing a new kind of exciplex TADF emitter constituted by m-MTDATA (4,4',4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine) as the donor and OXD-7 (1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene) as the acceptor, an exciton utilization efficiency of 74.3% for the devices was achieved. It is found that the injection barrier between hole transport layer and emission layer as well as the ratio between donor and acceptor would influence the external quantum efficiency (EQE) significantly. Devices with a maximum EQE of 3.76% which is far exceeding the reported results for devices with conventional fluorescent emitters were successfully demonstrated. Moreover, the EQE at high brightness even outperformed the result for organic light-emitting diode based on the same emitter. Our results demonstrate that the exciplex TADF emitters can be promising candidates to develop OLEFETs with high performance.

4P-NPD ultra-thin films as efficient exciton blocking layers in DBP/C70 based organic solar cells

NASA Astrophysics Data System (ADS)

Patil, Bhushan R.; Liu, Yiming; Qamar, Talha; Rubahn, Horst-Günter; Madsen, Morten

2017-09-01

Exciton blocking effects from ultra-thin layers of N,N‧-di-1-naphthalenyl-N,N‧-diphenyl [1,1‧:4‧,1″:4″,1‴-quaterphenyl]-4,4‴-diamine (4P-NPD) were investigated in small molecule-based inverted organic solar cells (OSCs) using tetraphenyldibenzoperiflanthene as the electron donor material and fullerene (C70) as the electron acceptor material. The short-circuit current density (J SC) and power conversion efficiency (PCE) of the optimized OSCs with 0.7 nm thick 4P-NPD were approximately 16% and 24% higher, respectively, compared to reference devices without exciton blocking layers (EBLs). Drift diffusion-based device modeling was conducted to model the full current density-voltage (JV) characteristics and external quantum efficiency spectrum of the OSCs, and photoluminescence measurements were conducted to investigate the exciton blocking effects with increasing thicknesses of the 4P-NPD layer. Importantly, coupled optical and electrical modeling studies of the device behaviors and exciton generation rates and densities in the active layer for different 4P-NPD layer thicknesses were conducted, in order to gain a complete understanding of the observed increase in PCE for 4P-NPD layer thicknesses up to 1 nm, and the observed decrease in PCE for layer thicknesses beyond 1 nm. This work demonstrates a route for guiding the integration of EBLs in OSC devices.

Direct Imaging of Exciton Transport in Tubular Porphyrin Aggregates by Ultrafast Microscopy.

PubMed

Wan, Yan; Stradomska, Anna; Knoester, Jasper; Huang, Libai

2017-05-31

Long-range exciton transport is a key challenge in achieving efficient solar energy harvesting in both organic solar cells and photosynthetic systems. Self-assembled molecular aggregates provide the potential for attaining long-range exciton transport through strong intermolecular coupling. However, there currently lacks an experimental tool to directly characterize exciton transport in space and in time to elucidate mechanisms. Here we report a direct visualization of exciton diffusion in tubular molecular aggregates by transient absorption microscopy with ∼200 fs time resolution and ∼50 nm spatial precision. These direct measurements provide exciton diffusion constants of 3-6 cm 2 s -1 for the tubular molecular aggregates, which are 3-5 times higher than a theoretical lower bound obtained by assuming incoherent hopping. These results suggest that coherent effects play a role, despite the fact that exciton states near the band bottom crucial for transport are only weakly delocalized (over <10 molecules). The methods presented here establish a direct approach for unraveling the mechanisms and main parameters underlying exciton transport in large molecular assemblies.

Excitonic luminescence upconversion in a two-dimensional semiconductor

DOE PAGES

Jones, Aaron M.; Yu, Hongyi; Schaibley, John R.; ...

2015-12-21

Photon upconversion is an elementary light-matter interaction process in which an absorbed photon is re-emitted at higher frequency after extracting energy from the medium. Furthermore, this phenomenon lies at the heart of optical refrigeration in solids(1), where upconversion relies on anti-Stokes processes enabled either by rare-earth impurities(2) or exciton-phonon coupling(3). We demonstrate a luminescence upconversion process from a negatively charged exciton to a neutral exciton resonance in monolayer WSe2, producing spontaneous anti-Stokes emission with an energy gain of 30 meV. Polarization-resolved measurements find this process to be valley selective, unique to monolayer semiconductors(4). Since the charged exciton binding energy(5) closelymore » matches the 31 meV A(1)' optical phonon(6-9), we ascribe the spontaneous excitonic anti-Stokes to doubly resonant Raman scattering, where the incident and outgoing photons are in resonance with the charged and neutral excitons, respectively. Additionally, we resolve a charged exciton doublet with a 7 meV splitting, probably induced by exchange interactions, and show that anti-Stokes scattering is efficient only when exciting the doublet peak resonant with the phonon, further confirming the excitonic doubly resonant picture.« less

Subnanosecond control of excitons in coupled quantum well nanostructures: Photonic storage and Exciton Conveyer devices

NASA Astrophysics Data System (ADS)

Winbow, Alexander Graham

Indirect excitons in GaAs coupled quantum well nanostructures are a versatile system for fundamental study of cold neutral bosonic gases and demonstration of novel optoelectronic devices based on excitons --- a bound electron--hole pair --- rather than electrons. Indirect exciton lifetimes range from nanoseconds to microseconds and cool rapidly after photoexcitation to the lattice temperature. Lithographically-patterned electrodes enable design of potential energy landscapes, and both energy and lifetime can be controlled in situ, rapidly, on timescales much shorter than the exciton lifetime. Such intrinsically optoelectronic devices can operate at speeds relevant to optical networks, and later be fabricated in other semiconductors for higher-temperature operation. Two different kinds of devices are demonstrated: Photon storage --- an optical memory --- with 250 ps rise time of the readout optical signal and storage time reaching microseconds was implemented with indirect excitons in CQW. The storage and release of photons was controlled by the gate voltage pulse, and the transient processes in the CQW studied by measuring the kinetics of the exciton emission spectra. This control of excitons on timescales much shorter than the exciton lifetime demonstrates the feasibility of studying excitons in in situ controlled electrostatic traps. The Exciton Conveyer is a laterally moving electrostatic lattice potential for actively transporting excitons. Generated by laterally modulated electrodes, the potential velocity and depth are controlled in situ by frequency and voltage. We observed exciton transport characterized by average exciton cloud spatial extension over several tens of microns, and observed dynamical localization--delocalization transitions for the excitons in the conveyer: In the localization regime of deeper potentials and moderate exciton density, excitons are moved by the conveyer; in the delocalized regime of shallower lattice potential or high exciton density, excitons do not follow the conveyer motion. We explore conveyer velocities both slower and faster than phonon velocities. Realizing subnanosecond manipulations of exciton energy and lifetime required versatile control of pulsed and multiple AC RF electrical signals in optical, liquid helium cryogenic systems. Considerable detail is presented of design, construction, and test of flexible experimental apparatus.

Energy harvesting of non-emissive triplet excitons in tetracene by emissive PbS nanocrystals

NASA Astrophysics Data System (ADS)

Thompson, Nicholas J.; Wilson, Mark W. B.; Congreve, Daniel N.; Brown, Patrick R.; Scherer, Jennifer M.; Bischof, Thomas S.; Wu, Mengfei; Geva, Nadav; Welborn, Matthew; Voorhis, Troy Van; Bulović, Vladimir; Bawendi, Moungi G.; Baldo, Marc A.

2014-11-01

Triplet excitons are ubiquitous in organic optoelectronics, but they are often an undesirable energy sink because they are spin-forbidden from emitting light and their high binding energy hinders the generation of free electron-hole pairs. Harvesting their energy is consequently an important technological challenge. Here, we demonstrate direct excitonic energy transfer from ‘dark’ triplets in the organic semiconductor tetracene to colloidal PbS nanocrystals, thereby successfully harnessing molecular triplet excitons in the near infrared. Steady-state excitation spectra, supported by transient photoluminescence studies, demonstrate that the transfer efficiency is at least (90 ± 13)%. The mechanism is a Dexter hopping process consisting of the simultaneous exchange of two electrons. Triplet exciton transfer to nanocrystals is expected to be broadly applicable in solar and near-infrared light-emitting applications, where effective molecular phosphors are lacking at present. In particular, this route to ‘brighten’ low-energy molecular triplet excitons may permit singlet exciton fission sensitization of conventional silicon solar cells.

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

Makarov, Nikolay S.; Lin, Qianglu; Pietryga, Jeffrey M.

One source of efficiency losses in photovoltaic cells is their transparency toward solar photons with energies below the band gap of the absorbing layer. This loss can be reduced using a process of up-conversion whereby two or more sub-band-gap photons generate a single above-gap exciton. Traditional approaches to up-conversion, such as nonlinear two-photon absorption (2PA) or triplet fusion, suffer from low efficiency at solar light intensities, a narrow absorption bandwidth, nonoptimal absorption energies, and difficulties for implementing in practical devices. We show that these deficiencies can be alleviated using the effect of Auger up-conversion in thick-shell PbSe/CdSe quantum dots. Thismore » process relies on Auger recombination whereby two low-energy, core-based excitons are converted into a single higher-energy, shell-based exciton. When compared to their monocomponent counterparts, the tailored PbSe/CdSe heterostructures feature enhanced absorption cross-sections, a higher efficiency of the “productive” Auger pathway involving re-excitation of a hole, and longer lifetimes of both core- and shell-localized excitons. These features lead to effective up-conversion cross-sections that are more than 6 orders of magnitude higher than for standard nonlinear 2PA, which allows for efficient up-conversion of continuous wave infrared light at intensities as low as a few watts per square centimeter.« less

Design of Organic Solar Cells as a Function of Radiative Quantum Efficiency

NASA Astrophysics Data System (ADS)

Godefroid, Blaise; Kozyreff, Gregory

2017-09-01

We study the radiative decay, or fluorescence, of excitons in organic solar cells as a function of its geometrical parameters. Contrary to their nonradiative counterpart, fluorescence losses strongly depend on the environment. By properly tuning the thicknesses of the buffer layers between the active regions of the cell and the electrodes, the exciton lifetime and, hence, the exciton diffusion length can be increased. The importance of this phenomenon depends on the radiative quantum efficiency, which is the fraction of the exciton decay that is intrinsically due to fluorescence. Besides this effect, interferences within the cell control the efficiency of sunlight injection into the active layers. The optimal cell design must rely on a consideration of these two aspects. By properly managing fluorescence losses, one can significantly improve the cell performance. To demonstrate this fact, we use realistic material parameters inspired from literature data and obtain an increase of power-conversion efficiency from 11.3% to 12.7%. Conversely, not to take into account the strong dependence of fluorescence on the environment may lead to a suboptimal cell design and a degradation of cell performance. The presence of radiative losses, however small, significantly changes the optimal set of thicknesses. We illustrate the latter situation with experimental material data.

Nanocrystal sensitized photovoltaics and photodetectors with performance enhanced using ligand engineering

NASA Astrophysics Data System (ADS)

Schut, David M.; Williams, George M., Jr.; Arteaga, Stefan; Allen, Thomas L.; Novet, Thomas

2011-06-01

Nanocrystal quantum dot photovoltaics and photodetectors with performance optimized by engineering the nanocrystals size and the optoelectronic properties of the nanocrystal's chemical coating are reported. Due to the large surface-to-volume ratio inherent to nanocrystals, the surface effects of ligands used to chemically coat and passivate nanocrystals play a significant role in device performance. However, the optoelectronic properties of ligands are difficult to ascertain, as the band structure of the ligand-capped nanoparticle system is complex and difficult to model. Using density-of-states measurements, we demonstrate that modeling of electropositive and electronegative substituents and use of the Hammett equation, are useful tools in optimizing nanocrystal detector performance. A new particle, the Janus-II nanoparticles, developed using 'charge-donating' and 'charge-withdrawing' ligands distributed over opposite surfaces of the nanocrystal, is described. The polarizing ligands of the Janus-II nanoparticle form a degeneracy-splitting dipole, which reduces the overlap integral between excitonic states, and thus reduces the probability of carrier recombination, allowing carrier extraction to take place more efficiently. This is shown to allow increased photodetection efficiencies and to allow the capture of multiple exciton events in working photodetectors.

Tensor network methods for the simulation of open quantum dynamics in multichromophore systems: Application to singlet fission in novel pentacene dimers

NASA Astrophysics Data System (ADS)

Chin, Alex

Singlet fission (SF) is an ultrafast process in which a singlet exciton spontaneously converts into a pair of entangled triplet excitons on neighbouring organic molecules. As a mechanism of multiple exciton generation, it has been suggested as a way to increase the efficiency of organic photovoltaic devices, and its underlying photophysics across a wide range of molecules and materials has attracted significant theoretical attention. Recently, a number of studies using ultrafast nonlinear optics have underscored the importance of intramolecular vibrational dynamics in efficient SF systems, prompting a need for methods capable of simulating open quantum dynamics in the presence of highly structured and strongly coupled environments. Here, a combination of ab initio electronic structure techniques and a new tensor-network methodology for simulating open vibronic dynamics is presented and applied to a recently synthesised dimer of pentacene (DP-Mes). We show that ultrafast (300 fs) SF in this system is driven entirely by symmetry breaking vibrations, and our many-body approach enables the real-time identification and tracking of the ''functional' vibrational dynamics and the role of the ''bath''-like parts of the environment. Deeper analysis of the emerging wave functions points to interesting links between the time at which parts of the environment become relevant to the SF process and the optimal topology of the tensor networks, highlighting the additional insight provided by moving the problem into the natural language of correlated quantum states and how this could lead to simulations of much larger multichromophore systems Supported by The Winton Programme for the Physics of Sustainability.

Resolving ultrafast exciton migration in organic solids at the nanoscale

NASA Astrophysics Data System (ADS)

Ginsberg, Naomi

The migration of Frenkel excitons, tightly-bound electron-hole pairs, in photosynthesis and in organic semiconducting films is critical to the efficiency of natural and artificial light harvesting. While these materials exhibit a high degree of structural heterogeneity on the nanoscale, traditional measurements of exciton migration lengths are performed on bulk samples. Since both the characteristic length scales of structural heterogeneity and the reported bulk diffusion lengths are smaller than the optical diffraction limit, we adapt far-field super-resolution fluorescence imaging to uncover the correlations between the structural and energetic landscapes that the excitons explore. By combining the ultrafast super-resolved measurements with exciton hopping simulations we furthermore specify the nature (in addition to the extent) of exciton migration as a function of the intrinsic and ensemble chromophore energy scales that determine a spatio-energetic landscape for migration. In collaboration with: Samuel Penwell, Lucas Ginsberg, University of California, Berkeley and Rodrigo Noriega University of Utah.

Excitons in Cuprous Oxide: Photoionization and Other Multiphoton Processes

NASA Astrophysics Data System (ADS)

Frazer, Nicholas Laszlo

In cuprous oxide (Cu2O), momentum from the absorption of two infrared photons to make an orthoexciton is conserved and detected through the photon component of a resulting mixed exciton/photon (quadrupole exciton polariton) state. I demonstrated that this process, which actually makes the photon momentum more precisely defined, is disrupted by photoionization of excitons. Some processes are known to affect exciton propagation in both the pump and exciton stages, such as phonon emission, exciton-exciton (Auger) scattering, and third harmonic generation. These processes alone were not able to explain all observed losses of excitons or all detected scattering products, which lead me to design an optical pump-probe experiment to measure the exciton photoionization cross section, which is (3.9+/-0.2) x 10-22 m2. This dissertation describes the synthesis of cuprous oxide crystals using oxidation of copper, crystallization from melt with the optical floating zone method, and annealing. The cuprous oxide crystals were characterized using time and space resolved luminescence, leading to the discovery of new defect properties. Selection rules and overall efficiency of third harmonic generation in these crystals were characterized. Exciton photoionization was demonstrated through the depletion of polariton luminescence by an optical probe, the production of phonon linked luminescence as a scattering product, temporal delay of the probe, and time resolved luminescence. The results are integrated with the traditional dynamical model of exciton densities. An additional investigation of copper/cuprous oxide/gold photovoltaic devices is appended.

Electron Transfer as a Probe of the Interfacial Quantum Dot-Organic Molecule Interaction

NASA Astrophysics Data System (ADS)

Peterson, Mark D.

This dissertation describes a set of experimental and theoretical studies of the interaction between small organic molecules and the surfaces of semiconductor nanoparticles, also called quantum dots (QDs). Chapter 1 reviews the literature on the influence of ligands on exciton relaxation dynamics following photoexcitation of semiconductor QDs, and describes how ligands promote or inhibit processes such as emission, nonradiative relaxation, and charge transfer to redox active adsorbates. Chapter 2 investigates the specific interaction of alkylcarboxylated viologen derivatives with CdS QDs, and shows how a combination of steady-state photoluminescence (PL) and transient absorption (TA) experiments can be used to reveal the specific binding geometry of redox active organic molecules on QD surfaces. Chapter 3 expands on Chapter 2 by using PL and TA to provide information about the mechanisms through which methyl viologen (MV 2+) associates with CdS QDs to form a stable QD/MV2+ complex, suggesting two chemically distinct reactions. We use our understanding of the QD/molecule interaction to design a drug delivery system in Chapter 4, which employs PL and TA experiments to show that conformational changes in a redox active adsorbate may follow electron transfer, "activating" a biologically inert Schiff base to a protein inhibitor form. The protein inhibitor limits cell motility and may be used to prevent tumor metastasis in cancer patients. Chapter 5 discusses future applications of QD/molecule redox couples with an emphasis on efficient multiple charge-transfer reactions -- a process facilitated by the high degeneracy of band-edge states in QDs. These multiple charge-transfer reactions may potentially increase the thermodynamic efficiency of solar cells, and may also facilitate the splitting of water into fuel. Multiple exciton generation procedures, multi-electron transfer experiments, and future directions are discussed.

Coherent transport and energy flow patterns in photosynthesis under incoherent excitation.

PubMed

Pelzer, Kenley M; Can, Tankut; Gray, Stephen K; Morr, Dirk K; Engel, Gregory S

2014-03-13

Long-lived coherences have been observed in photosynthetic complexes after laser excitation, inspiring new theories regarding the extreme quantum efficiency of photosynthetic energy transfer. Whether coherent (ballistic) transport occurs in nature and whether it improves photosynthetic efficiency remain topics of debate. Here, we use a nonequilibrium Green's function analysis to model exciton transport after excitation from an incoherent source (as opposed to coherent laser excitation). We find that even with an incoherent source, the rate of environmental dephasing strongly affects exciton transport efficiency, suggesting that the relationship between dephasing and efficiency is not an artifact of coherent excitation. The Green's function analysis provides a clear view of both the pattern of excitonic fluxes among chromophores and the multidirectionality of energy transfer that is a feature of coherent transport. We see that even in the presence of an incoherent source, transport occurs by qualitatively different mechanisms as dephasing increases. Our approach can be generalized to complex synthetic systems and may provide a new tool for optimizing synthetic light harvesting materials.

Hyperspectral Probing of Exciton dynamics and Multiplication in PbSe Nanocrystals

NASA Astrophysics Data System (ADS)

Gdor, I.; Sachs, H.; Roitblat, A.; Strasfeld, D.; Bawendi, M. G.; Ruhman, S.

2013-03-01

Height time hyperspectral near IR probing providing broad-band coverage is employed on PbSe nanocrystals, uncovering spectral evolution following high energy photo-excitation due to hot exciton relaxation and recombination. Separation of single, double and triple exciton state contributions to these spectra is demonstrated, and the mechanisms underlying the course of spectral evolution are investigated. In addition no sign of MEG was detected in this sample up to a photon energy 3.7 times that of the band gap.

Disturbing the coherent dynamics of an excitonic polarization with strong terahertz fields

NASA Astrophysics Data System (ADS)

Drexler, M. J.; Woscholski, R.; Lippert, S.; Stolz, W.; Rahimi-Iman, A.; Koch, M.

2014-11-01

We present a paper based on combining four-wave mixing and strong fields in the terahertz frequency range to monitor the time evolution of a disturbed excitonic polarization in a multiple quantum well system. Our findings not only confirm a lower field-dependent ionization threshold for higher excitonic states, but furthermore provide experimental evidence for intraexcitonic Rabi flopping in the time domain. These measurements correspond to the picture of a reversible and irreversible transfer as previously predicted by a microscopic theory.

Measurement of Exciton Binding Energy of Monolayer WS2

NASA Astrophysics Data System (ADS)

Chen, Xi; Zhu, Bairen; Cui, Xiaodong

Excitonic effects are prominent in monolayer crystal of transition metal dichalcogenides (TMDCs) because of spatial confinement and reduced Coulomb screening. Here we use linear differential transmission spectroscopy and two-photon photoluminescence excitation spectroscopy (TP-PLE) to measure the exciton binding energy of monolayer WS2. Peaks for excitonic absorptions of the direct gap located at K valley of the Brillouin zone and transitions from multiple points near Γ point of the Brillouin zone, as well as trion side band are shown in the linear absorption spectra of WS2. But there is no gap between distinct excitons and the continuum of the interband transitions. Strong electron-phonon scattering, overlap of excitons around Γ point and the transfer of the oscillator strength from interband continuum to exciton states make it difficult to resolve the electronic interband transition edge even down to 10K. The gap between excited states of the band-edge exciton and the single-particle band is probed by TP-PLE measurements. And the energy difference between 1s exciton and the single-particle gap gives the exciton binding energy of monolayer WS2 to be about 0.71eV. The work is supported by Area of excellency (AoE/P-04/08), CRF of Hong Kong Research Grant Council (HKU9/CRF/13G) and SRT on New Materials of The University of Hong Kong.

Lead Telluride Quantum Dot Solar Cells Displaying External Quantum Efficiencies Exceeding 120%

PubMed Central

2015-01-01

Multiple exciton generation (MEG) in semiconducting quantum dots is a process that produces multiple charge-carrier pairs from a single excitation. MEG is a possible route to bypass the Shockley-Queisser limit in single-junction solar cells but it remains challenging to harvest charge-carrier pairs generated by MEG in working photovoltaic devices. Initial yields of additional carrier pairs may be reduced due to ultrafast intraband relaxation processes that compete with MEG at early times. Quantum dots of materials that display reduced carrier cooling rates (e.g., PbTe) are therefore promising candidates to increase the impact of MEG in photovoltaic devices. Here we demonstrate PbTe quantum dot-based solar cells, which produce extractable charge carrier pairs with an external quantum efficiency above 120%, and we estimate an internal quantum efficiency exceeding 150%. Resolving the charge carrier kinetics on the ultrafast time scale with pump–probe transient absorption and pump–push–photocurrent measurements, we identify a delayed cooling effect above the threshold energy for MEG. PMID:26488847

Bose-Einstein condensation and indirect excitons: a review.

PubMed

Combescot, Monique; Combescot, Roland; Dubin, François

2017-06-01

We review recent progress on Bose-Einstein condensation (BEC) of semiconductor excitons. The first part deals with theory, the second part with experiments. This Review is written at a time where the problem of exciton Bose-Einstein condensation has just been revived by the understanding that the exciton condensate must be dark because the exciton ground state is not coupled to light. Here, we theoretically discuss this missed understanding before providing its experimental support through experiments that scrutinize indirect excitons made of spatially separated electrons and holes. The theoretical part first discusses condensation of elementary bosons. In particular, the necessary inhibition of condensate fragmentation by exchange interaction is stressed, before extending the discussion to interacting bosons with spin degrees of freedom. The theoretical part then considers composite bosons made of two fermions like semiconductor excitons. The spin structure of the excitons is detailed, with emphasis on the crucial fact that ground-state excitons are dark: indeed, this imposes the exciton Bose-Einstein condensate to be not coupled to light in the dilute regime. Condensate fragmentations are then reconsidered. In particular, it is shown that while at low density, the exciton condensate is fully dark, it acquires a bright component, coherent with the dark one, beyond a density threshold: in this regime, the exciton condensate is 'gray'. The experimental part first discusses optical creation of indirect excitons in quantum wells, and the detection of their photoluminescence. Exciton thermalisation is also addressed, as well as available approaches to estimate the exciton density. We then switch to specific experiments where indirect excitons form a macroscopic fragmented ring. We show that such ring provides efficient electrostatic trapping in the region of the fragments where an essentially-dark exciton Bose-Einstein condensate is formed at sub-Kelvin bath temperatures. The macroscopic spatial coherence of the photoluminescence observed in this essentially dark region confirms this conclusion.

Understanding Singlet and Triplet Excitons in Acene Crystals from First Principles

NASA Astrophysics Data System (ADS)

Rangel Gordillo, Tonatiuh; Sharifzadeh, Sahar; Kronik, Leeor; Neaton, Jeffrey

2014-03-01

Singlet fission, a process in which two triplet excitons are formed from a singlet exciton, has the potential to increase the solar cell efficiencies above 100%. Efficient singlet fission has been reported in larger acene crystals, such as tetracene and pentacene, in part attributable to their low-lying triplet energies. In this work, we use many-body perturbation theory within the GW approximation and the Bethe-Salpeter equation approach to compute quasiparticle gaps, low-lying singlet and and triplet excitations, and optical absorption spectra across the entire acene family of crystals, from benzene to hexacene. We closely examine the degree of localization and charge-transfer character of the low-lying singlets and triplets, and their sensitivity to crystal environment, and discuss implications for the efficiency of singlet fission in this systems. This work supported by DOE and computational resources provided by NERSC.

Direct Observation of Electron-Phonon Coupling and Slow Vibrational Relaxation in Organic-Inorganic Hybrid Perovskites.

PubMed

Straus, Daniel B; Hurtado Parra, Sebastian; Iotov, Natasha; Gebhardt, Julian; Rappe, Andrew M; Subotnik, Joseph E; Kikkawa, James M; Kagan, Cherie R

2016-10-05

Quantum and dielectric confinement effects in 2D hybrid perovskites create excitons with a binding energy exceeding 150 meV. We exploit the large exciton binding energy to study exciton and carrier dynamics as well as electron-phonon coupling in hybrid perovskites using absorption and photoluminescence (PL) spectroscopies. At temperatures below 75 K, we resolve splitting of the excitonic absorption and PL into multiple regularly-spaced resonances every 40-46 meV, consistent with electron-phonon coupling to phonons located on the organic cation. We also resolve resonances with a 14 meV spacing, in accord with coupling to phonons with mixed organic and inorganic character, and these assignments are supported by density-functional theory calculations. Hot exciton PL and time-resolved PL measurements show that vibrational relaxation occurs on a picosecond timescale competitive with that for PL. At temperatures above 75 K, excitonic absorption and PL exhibit homogeneous broadening. While absorption remains homogeneous, PL becomes inhomogeneous below 75K, which we speculate is caused by the formation and subsequent dynamics of a polaronic exciton.

Topologically protected excitons in porphyrin thin films

NASA Astrophysics Data System (ADS)

Yuen-Zhou, Joel; Saikin, Semion K.; Yao, Norman Y.; Aspuru-Guzik, Alán

2014-11-01

The control of exciton transport in organic materials is of fundamental importance for the development of efficient light-harvesting systems. This transport is easily deteriorated by traps in the disordered energy landscape. Here, we propose and analyse a system that supports topological Frenkel exciton edge states. Backscattering of these chiral Frenkel excitons is prohibited by symmetry, ensuring that the transport properties of such a system are robust against disorder. To implement our idea, we propose a two-dimensional periodic array of tilted porphyrins interacting with a homogeneous magnetic field. This field serves to break time-reversal symmetry and results in lattice fluxes that mimic the Aharonov-Bohm phase acquired by electrons. Our proposal is the first blueprint for realizing topological phases of matter in molecular aggregates and suggests a paradigm for engineering novel excitonic materials.

Topologically protected excitons in porphyrin thin films.

PubMed

Yuen-Zhou, Joel; Saikin, Semion K; Yao, Norman Y; Aspuru-Guzik, Alán

2014-11-01

The control of exciton transport in organic materials is of fundamental importance for the development of efficient light-harvesting systems. This transport is easily deteriorated by traps in the disordered energy landscape. Here, we propose and analyse a system that supports topological Frenkel exciton edge states. Backscattering of these chiral Frenkel excitons is prohibited by symmetry, ensuring that the transport properties of such a system are robust against disorder. To implement our idea, we propose a two-dimensional periodic array of tilted porphyrins interacting with a homogeneous magnetic field. This field serves to break time-reversal symmetry and results in lattice fluxes that mimic the Aharonov-Bohm phase acquired by electrons. Our proposal is the first blueprint for realizing topological phases of matter in molecular aggregates and suggests a paradigm for engineering novel excitonic materials.

Effect of horizontal molecular orientation on triplet-exciton diffusion in amorphous organic films

NASA Astrophysics Data System (ADS)

Sawabe, T.; Takasu, I.; Yonehara, T.; Ono, T.; Yoshida, J.; Enomoto, S.; Amemiya, I.; Adachi, C.

2012-09-01

Triplet harvesting is a candidate technology for highly efficient and long-life white OLEDs, where green or red phosphorescent emitters are activated by the triplet-excitons diffused from blue fluorescent emitters. We examined two oxadiazole-based electron transport materials with different horizontal molecular orientation as a triplet-exciton diffusion layer (TDL) in triplet-harvesting OLEDs. The device characteristics and the transient electroluminescent analyses of the red phosphorescent emitter showed that the triplet-exciton diffusion was more effective in the highly oriented TDL. The results are ascribed to the strong orbital overlap between the oriented molecules, which provides rapid electron exchange (Dexter energy transfer) in the TDL.

Trapping time of excitons in Si nanocrystals embedded in a SiO2 matrix

NASA Astrophysics Data System (ADS)

de Jong, E. M. L. D.; de Boer, W. D. A. M.; Yassievich, I. N.; Gregorkiewicz, T.

2017-05-01

Silicon (Si) nanocrystals (NCs) are of great interest for many applications, ranging from photovoltaics to optoelectonics. The photoluminescence quantum yield of Si NCs dispersed in SiO2 is limited, suggesting the existence of very efficient processes of nonradiative recombination, among which the formation of a self-trapped exciton state on the surface of the NC. In order to improve the external quantum efficiency of these systems, the carrier relaxation and recombination need to be understood more thoroughly. For that purpose, we perform transient-induced absorption spectroscopy on Si NCs embedded in a SiO2 matrix over a broad probe range for NCs of average sizes from 2.5 to 5.5 nm. The self-trapping of free excitons on surface-related states is experimentally and theoretically discussed and found to be dependent on the NC size. These results offer more insight into the self-trapped exciton state and are important to increase the optical performance of Si NCs.

Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering.

PubMed

Lukman, Steven; Chen, Kai; Hodgkiss, Justin M; Turban, David H P; Hine, Nicholas D M; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C; Musser, Andrew J

2016-12-07

Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.

Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering

PubMed Central

Lukman, Steven; Chen, Kai; Hodgkiss, Justin M.; Turban, David H. P.; Hine, Nicholas D. M.; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C.; Musser, Andrew J.

2016-01-01

Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics. PMID:27924819

The Dual Role of Disorder on the Dissociation of Interfacial Charge Transfer Excitons

NASA Astrophysics Data System (ADS)

Shi, Liang; Lee, Chee-Kong; Willard, Adam

In organic-based photovoltaics (OPV), dissociation of neutral photo-excitations (i.e., Frenkel excitons) into free charge carriers requires the excitons to overcome binding energy that can significantly exceed thermal energies. The inability of bound charges to overcome this large binding energy has been implicated as a primary source of efficiency loss in OPVs. Despite the potential impact on the performance of organic solar cells much remains to be understood about the microscopic mechanism of exciton dissociation in OPV materials. Here we explore the role of static molecular disorder in mediating this charge dissociation process. Using a simple lattice model of exciton dynamics we demonstrate that random spatial variations in the energetic landscape can mitigate the effects of the exciton binding energy by lowering the free energy barrier. By considering the competition between this thermodynamic effect and the disorder-induced slowing of dissociation kinetics we demonstrate that exciton dissociation yields are expected to depend non-monotonically on the degree of static disorder. We conclude that a certain amount of molecular-scale disorder is desirable in order to optimize the performance of organic photovoltaic materials.

Auger Up-Conversion of Low-Intensity Infrared Light in Engineered Quantum Dots

DOE PAGES

Makarov, Nikolay S.; Lin, Qianglu; Pietryga, Jeffrey M.; ...

2016-11-29

One source of efficiency losses in photovoltaic cells is their transparency toward solar photons with energies below the band gap of the absorbing layer. This loss can be reduced using a process of up-conversion whereby two or more sub-band-gap photons generate a single above-gap exciton. Traditional approaches to up-conversion, such as nonlinear two-photon absorption (2PA) or triplet fusion, suffer from low efficiency at solar light intensities, a narrow absorption bandwidth, nonoptimal absorption energies, and difficulties for implementing in practical devices. We show that these deficiencies can be alleviated using the effect of Auger up-conversion in thick-shell PbSe/CdSe quantum dots. Thismore » process relies on Auger recombination whereby two low-energy, core-based excitons are converted into a single higher-energy, shell-based exciton. When compared to their monocomponent counterparts, the tailored PbSe/CdSe heterostructures feature enhanced absorption cross-sections, a higher efficiency of the “productive” Auger pathway involving re-excitation of a hole, and longer lifetimes of both core- and shell-localized excitons. These features lead to effective up-conversion cross-sections that are more than 6 orders of magnitude higher than for standard nonlinear 2PA, which allows for efficient up-conversion of continuous wave infrared light at intensities as low as a few watts per square centimeter.« less

Structural tunability and switchable exciton emission in inorganic-organic hybrids with mixed halides

NASA Astrophysics Data System (ADS)

Ahmad, Shahab; Baumberg, Jeremy J.; Vijaya Prakash, G.

2013-12-01

Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C12H25NH3)2PbI4(1-y)Br4y (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed to the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices.

A Study of Charge Transport: Correlated Energetic Disorder in Organic Semiconductors, and the Fragment Hamiltonian

NASA Astrophysics Data System (ADS)

Allen, Jonathan Robert

This dissertation details work done on two different descriptions of charge transport. The first topic is energetic disorder in organic semiconductors, and its effect on charge transport. This is motivated primarily by solar cells, which can be broadly classified as either inorganic or organic. The inorganic class of solar cells is older, and more well-developed, with the most common type being constructed from crystalline silicon. The large silicon crystals required for these cells are expensive to manufacture, which gave rise to interest in photovoltaic cells made from much less costly organic polymers. These organic materials are also less efficient than their silicon counterparts, due to a large degree of spatial and energetic disorder. In this document, the sources and structure of energetic disorder in organic semiconductors are explored, with an emphasis on spatial correlations in energetic disorder. In order for an organic photovoltaic device to function, there must be photogeneration of an exciton (a bound electron-hole pair), exciton transport, exciton dissociation, and transport of the individual charges to their respective terminals. In the case of this thesis, the main focus is exciton dissociation. The effects of correlation on exciton dissociation are examined through computer simulation, and compared to the theory and simulations of previous researchers. We conclude that energetic disorder in organic semiconductors is spatially correlated, and that this correlation improves the ability of excitons to dissociate. The second topic of this dissertation is the Fragment Hamiltonian model. This is a model currently in development as a means of describing charge transport across a range of systems. Currently there are many different systems which exhibit various charge transport behaviors, which are described by several different models. The overarching goal of the Fragment Hamiltonian model is to construct a description of charge transport which accurately describes the behavior of multiple different materials (i.e. metallic conductors or ceramic insulators) in the appropriate limits. The Fragment Hamiltonian model is explored in the context of the tight-binding model, and properties such as the conductivity of several different systems are deduced.

Theoretical study on the cooperative exciton dissociation process based on dimensional and hot charge-transfer state effects in an organic photocell

NASA Astrophysics Data System (ADS)

Shimazaki, Tomomi; Nakajima, Takahito

2016-06-01

This paper discusses the exciton dissociation process at the donor-acceptor interface in organic photocells. In our previous study, we introduced a local temperature to handle the hot charge-transfer (CT) state and calculated the exciton dissociation probability based on the 1D organic semiconductor model [T. Shimazaki and T. Nakajima, Phys. Chem. Chem. Phys. 17, 12538 (2015)]. Although the hot CT state plays an essential role in exciton dissociations, the probabilities calculated are not high enough to efficiently separate bound electron-hole pairs. This paper focuses on the dimensional (entropy) effect together with the hot CT state effect and shows that cooperative behavior between both effects can improve the exciton dissociation process. In addition, we discuss cooperative effects with site-disorders and external-electric-fields.

Enhanced photoelectrochemical aptasensing platform based on exciton energy transfer between CdSeTe alloyed quantum dots and SiO2@Au nanocomposites.

PubMed

Fan, Gao-Chao; Zhu, Hua; Shen, Qingming; Han, Li; Zhao, Ming; Zhang, Jian-Rong; Zhu, Jun-Jie

2015-04-25

High-efficient exciton energy transfer between CdSeTe alloyed quantum dots and SiO2@Au nanocomposites was applied to develop an enhanced photoelectrochemical aptasensing platform with ultrahigh sensitivity, good selectivity, reproducibility and stability.

Near-infrared exciton-polaritons in strongly coupled single-walled carbon nanotube microcavities

NASA Astrophysics Data System (ADS)

Graf, Arko; Tropf, Laura; Zakharko, Yuriy; Zaumseil, Jana; Gather, Malte C.

2016-10-01

Exciton-polaritons form upon strong coupling between electronic excitations of a material and photonic states of a surrounding microcavity. In organic semiconductors the special nature of excited states leads to particularly strong coupling and facilitates condensation of exciton-polaritons at room temperature, which may lead to electrically pumped organic polariton lasers. However, charge carrier mobility and photo-stability in currently used materials is limited and exciton-polariton emission so far has been restricted to visible wavelengths. Here, we demonstrate strong light-matter coupling in the near infrared using single-walled carbon nanotubes (SWCNTs) in a polymer matrix and a planar metal-clad cavity. By exploiting the exceptional oscillator strength and sharp excitonic transition of (6,5) SWCNTs, we achieve large Rabi splitting (>110 meV), efficient polariton relaxation and narrow band emission (<15 meV). Given their high charge carrier mobility and excellent photostability, SWCNTs represent a promising new avenue towards practical exciton-polariton devices operating at telecommunication wavelengths.

Impact of the glass transition on exciton dynamics in polymer thin films

NASA Astrophysics Data System (ADS)

Ehrenreich, Philipp; Proepper, Daniel; Graf, Alexander; Jores, Stefan; Boris, Alexander V.; Schmidt-Mende, Lukas

2017-11-01

In the development of organic electronics, unlimited design possibilities of conjugated polymers offer a wide variety of mechanical and electronic properties. Thereby, it is crucially important to reveal universal physical characteristics that allow efficient and forward developments of new chemical compounds. In particular for organic solar cells, a deeper understanding of exciton dynamics in polymer films can help to improve the charge generation process further. For this purpose, poly(3-hexylthiophene) (P3HT) is commonly used as a model system, although exciton decay kinetics have found different interpretations. Using temperature-dependent time-resolved photoluminescence spectroscopy in combination with low-temperature spectroscopic ellipsometry, we can show that P3HT is indeed a model system in which excitons follow a simple diffusion/hopping model. Based on our results we can exclude the relevance of hot-exciton emission as well as a dynamic torsional relaxation upon photoexcitation on a ps time scale. Instead, we depict the glass transition temperature of polymers to strongly affect exciton dynamics.

Quantifying exciton hopping in disordered media with quenching sites: Application to arrays of quantum dots

NASA Astrophysics Data System (ADS)

Miyazaki, Jun

2013-10-01

We present an analytical method for quantifying exciton hopping in an energetically disordered system with quenching sites. The method is subsequently used to provide a quantitative understanding of exciton hopping in a quantum dot (QD) array. Several statistical quantities that characterize the dynamics (survival probability, average number of distinct sites visited, average hopping distance, and average hopping rate in the initial stage) are obtained experimentally by measuring time-resolved fluorescence intensities at various temperatures. The time evolution of these quantities suggests in a quantitative way that at low temperature an exciton tends to be trapped at a local low-energy site, while at room temperature, exciton hopping occurs repeatedly, leading to a large hopping distance. This method will serve to facilitate highly efficient optoelectronic devices using QDs such as photovoltaic cells and light-emitting diodes, since exciton hopping is considered to strongly influence their operational parameters. The presence of a dark QD (quenching site) that exhibits fast decay is also quantified.

The Role of FRET in Non-Fullerene Organic Solar Cells: Implications for Molecular Design.

PubMed

Gautam, Bhoj R; Younts, Robert; Carpenter, Joshua; Ade, Harald; Gundogdu, Kenan

2018-04-19

Non-fullerene acceptors (NFAs) have been demonstrated to be promising candidates for highly efficient organic photovoltaic (OPV) devices. The tunability of absorption characteristics of NFAs can be used to make OPVs with complementary donor-acceptor absorption to cover a broad range of the solar spectrum. However, both charge transfer from donor to acceptor moieties and energy (energy) transfer from high-bandgap to low-bandgap materials are possible in such structures. Here, we show that when charge transfer and exciton transfer processes are both present, the coexistence of excitons in both domains can cause a loss mechanism. Charge separation of excitons in a low-bandgap material is hindered due to exciton population in the larger bandgap acceptor domains. Our results further show that excitons in low-bandgap material should have a relatively long lifetime compared to the transfer time of excitons from higher bandgap material in order to contribute to the charge separation. These observations provide significant guidance for design and development of new materials in OPV applications.

Organic photovoltaic cell incorporating electron conducting exciton blocking layers

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

Forrest, Stephen R.; Lassiter, Brian E.

2014-08-26

The present disclosure relates to photosensitive optoelectronic devices including a compound blocking layer located between an acceptor material and a cathode, the compound blocking layer including: at least one electron conducting material, and at least one wide-gap electron conducting exciton blocking layer. For example, 3,4,9,10 perylenetetracarboxylic bisbenzimidazole (PTCBI) and 1,4,5,8-napthalene-tetracarboxylic-dianhydride (NTCDA) function as electron conducting and exciton blocking layers when interposed between the acceptor layer and cathode. Both materials serve as efficient electron conductors, leading to a fill factor as high as 0.70. By using an NTCDA/PTCBI compound blocking layer structure increased power conversion efficiency is achieved, compared to anmore » analogous device using a conventional blocking layers shown to conduct electrons via damage-induced midgap states.« less

Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model

DOE PAGES

Sisto, Aaron; Stross, Clem; van der Kamp, Marc W.; ...

2017-03-28

We recently outlined an efficient multi-tiered parallel ab initio excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground and excited state energies and gradients of large supramolecular complexes in atomistic detail – enabling us to undertake non-adiabatic simulations which explicitly account for the coupled anharmonic vibrational motion of all the constituent atoms in a supramolecular system. Here we apply that framework to the 27 coupled bacterio-chlorophyll-a chromophores which make up the LH2 complex, using it to compute an on-the-fly nonadiabatic surface-hopping (SH) trajectory of electronically excited LH2. Part one of this article is focussed on calibratingmore » our ab initio exciton Hamiltonian using two key parameters: a shift δ, which corrects for the error in TDDFT vertical excitation energies; and an effective dielectric constant ε, which describes the average screening of the transition-dipole coupling between chromophores. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, we tune the values of both δ and ε through fitting to the thermally broadened experimental absorption spectrum, giving a linear absorption spectrum that agrees reasonably well with experiment. In part two of this article, we construct a time-resolved picture of the coupled vibrational and excitation energy transfer (EET) dynamics in the sub-picosecond regime following photo-excitation. Assuming Franck–Condon excitation of a narrow eigenstate band centred at 800 nm, we use surface hopping to follow a single nonadiabatic dynamics trajectory within the full eigenstate manifold. Consistent with experimental data, this trajectory gives timescales for B800→B850 population transfer (τ B800→B850) between 650–1050 fs, and B800 population decay (τ 800→) between 10–50 fs. The dynamical picture that emerges is one of rapidly fluctuating LH2 eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the atomic vibrations of the constituent chromophores. The eigenstate fluctuations arise from disorder that is driven by vibrational dynamics with multiple characteristic timescales. The scalability of our ab initio excitonic computational framework across massively parallel architectures opens up the possibility of addressing a wide range of questions, including how specific dynamical motions impact both the pathways and efficiency of electronic energy-transfer within large supramolecular systems.« less

Effects of Molecular Stresses on Energy Transfer Pathways in Opto- and Electro-Excited Conjugated Polymers for High-Efficiency Optoelectronic Devices

DTIC Science & Technology

2014-10-20

unless it hops, and lead to obstructed recombination for PL or charge separation for solar cells and the reduced quantum efficiencies of the...excitons (Fig. 1a and 1b). For the free-moving delocalized states of the Wannier-Mott excitons, the binding energy in silicon , for example, is around...typically encompass many unit cells and typically exist in materials of small bandgap and large dielectric constant. In converse, the the tightly

Coherent dynamics of localized excitons and trions in ZnO/(Zn,Mg)O quantum wells studied by photon echoes

NASA Astrophysics Data System (ADS)

Solovev, I. A.; Poltavtsev, S. V.; Kapitonov, Yu. V.; Akimov, I. A.; Sadofev, S.; Puls, J.; Yakovlev, D. R.; Bayer, M.

2018-06-01

We study optically the coherent evolution of trions and excitons in a δ -doped 3.5-nm-thick ZnO/Zn0.91Mg0.09O multiple quantum well by means of time-resolved four-wave mixing at a temperature of 1.5 K. Employing spectrally narrow picosecond laser pulses in the χ(3 ) regime allows us to address differently localized trion and exciton states, thereby avoiding many-body interactions and excitation-induced dephasing. The signal in the form of photon echoes from the negatively charged A excitons (TA, trions) decays with coherence times varying from 8 up to 60 ps, depending on the trion energy: more strongly localized trions reveal longer coherence dynamics. The localized neutral excitons decay on the picosecond time scale with coherence times up to T2=4.5 ps. The coherent dynamics of the XB exciton and TB trion are very short (T2<1 ps), which is attributed to the fast energy relaxation from the trion and exciton B states to the respective A states. The trion population dynamics is characterized by the decay time T1, rising from 30 to 100 ps with decreasing trion energy.

Spatially and temporally resolved exciton dynamics and transport in single nanostructures and assemblies

NASA Astrophysics Data System (ADS)

Huang, Libai

2015-03-01

The frontier in solar energy conversion now lies in learning how to integrate functional entities across multiple length scales to create optimal devices. To address this new frontier, I will discuss our recent efforts on elucidating multi-scale energy transfer, migration, and dissipation processes with simultaneous femtosecond temporal resolution and nanometer spatial resolution. We have developed ultrafast microscopy that combines ultrafast spectroscopy with optical microscopy to map exciton dynamics and transport with simultaneous ultrafast time resolution and diffraction-limited spatial resolution. We have employed pump-probe transient absorption microscopy to elucidate morphology and structure dependent exciton dynamics and transport in single nanostructures and molecular assemblies. More specifically, (1) We have applied transient absorption microscopy (TAM) to probe environmental and structure dependent exciton relaxation pathways in sing-walled carbon nanotubes (SWNTs) by mapping dynamics in individual pristine SWNTs with known structures. (2) We have systematically measured and modeled the optical properties of the Frenkel excitons in self-assembled porphyrin tubular aggregates that represent an analog to natural photosynthetic antennae. Using a combination of ultrafast optical microscopy and stochastic exciton modeling, we address exciton transport and relaxation pathways, especially those related to disorder.

Efficient Blue Electroluminescence Using Quantum-Confined Two-Dimensional Perovskites.

PubMed

Kumar, Sudhir; Jagielski, Jakub; Yakunin, Sergii; Rice, Peter; Chiu, Yu-Cheng; Wang, Mingchao; Nedelcu, Georgian; Kim, Yeongin; Lin, Shangchao; Santos, Elton J G; Kovalenko, Maksym V; Shih, Chih-Jen

2016-10-03

Solution-processed hybrid organic-inorganic lead halide perovskites are emerging as one of the most promising candidates for low-cost light-emitting diodes (LEDs). However, due to a small exciton binding energy, it is not yet possible to achieve an efficient electroluminescence within the blue wavelength region at room temperature, as is necessary for full-spectrum light sources. Here, we demonstrate efficient blue LEDs based on the colloidal, quantum-confined 2D perovskites, with precisely controlled stacking down to one-unit-cell thickness (n = 1). A variety of low-k organic host compounds are used to disperse the 2D perovskites, effectively creating a matrix of the dielectric quantum wells, which significantly boosts the exciton binding energy by the dielectric confinement effect. Through the Förster resonance energy transfer, the excitons down-convert and recombine radiatively in the 2D perovskites. We report room-temperature pure green (n = 7-10), sky blue (n = 5), pure blue (n = 3), and deep blue (n = 1) electroluminescence, with record-high external quantum efficiencies in the green-to-blue wavelength region.

Single photon generation through exciton-exciton annihilation in air-suspended carbon nanotubes

NASA Astrophysics Data System (ADS)

Ishii, Akihiro; Uda, Takushi; Kato, Yuichiro K.

Carbon nanotubes have great potential for single photon sources as they have stable exciton states even at room temperature and their emission wavelengths cover the telecommunication bands. In recent years, single photon emission from carbon nanotubes has been achieved by creating localized states of excitons. In contrast to such an approach, here we utilize mobile excitons and show that single photons can be generated in air-suspended carbon nanotubes, where exciton diffusion length is as long as several hundred nanometers and exciton-exciton annihilation is efficient. We perform photoluminescence microscopy on as-grown air-suspended carbon nanotubes in order to determine their chirality and suspended length. Photon correlation measurements are performed on nanotube emission at room temperature using a Hanbury-Brown-Twiss setup with InGaAs/InP single photon detectors. We observe antibunching with a clear excitation power dependence, where we obtain g (2) (0) value less than 0.5 at low excitation powers, indicating single photon generation. We show such g (2) (0) data with different chiralities and suspended lengths, and the effects of exciton diffusion on single photon generation processes are discussed. Work supported by KAKENHI (26610080, 16H05962), The Canon Foundation, and MEXT (Photon Frontier Network Program, Nanotechnology Platform). A.I. is supported by MERIT and JSPS Research Fellowship, and T.U. is supported by ALPS.

Efficient triplet harvesting of hybrid white organic light-emitting diodes using thermally activated delayed fluorescence green emitter

NASA Astrophysics Data System (ADS)

Lee, Song Eun; Lee, Ho Won; Baek, Hyun Jung; Yun, Tae Jun; Yun, Geum Jae; Kim, Woo Young; Kim, Young Kwan

2016-10-01

Hybrid white organic light-emitting diodes (WOLEDs) were fabricated by applying triplet harvesting (TH) using a green thermally activated delayed fluorescence (TADF) emitter. The triplet exciton of the green TADF emitter can be upconverted to its singlet state. The TH involved energy transfer of triplet exciton from a blue fluorescent emitter to a green TADF and red phosphorescent emitters, where they can decay radiatively. In addition, the triplet exciton of the green TADF emitter was energy transferred to its singlet state for a reverse intersystem crossing by green emission. Enhanced hybrid WOLEDs were demonstrated using an efficient green TADF emitter combined with red phosphorescent and blue fluorescent emitters. Hybrid WOLEDs were fabricated with various hole-electron recombination zones as changing blue emitting layer thicknesses. Among these, hybrid WOLEDs showed a maximum external quantum efficiency of 11.23%, luminous efficiency of 29.20 cd/A, and a power efficiency of 26.21 lm/W. Moreover, the WOLED exhibited electroluminescence spectra with Commission International de L'Éclairage chromaticity of (0.38, 0.36) at 1000 cd/m2 and a color rendering index of 82 at a practical brightness of 20,000 cd/m2.

Crystalline Nanoporous Frameworks: a Nanolaboratory for Probing Excitonic Device Concepts.

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

Allendorf, Mark D.; Azoulay, Jason; Ford, Alexandra Caroline

2014-09-01

Electro-optical organic materials hold great promise for the development of high-efficiency devices based on exciton formation and dissociation, such as organic photovoltaics (OPV) and organic light-emitting devices (OLEDs). However, the external quantum efficiency (EQE) of both OPV and OLEDs must be improved to make these technologies economical. Efficiency rolloff in OLEDs and inability to control morphology at key OPV interfaces both reduce EQE. Only by creating materials that allow manipulation and control of the intimate assembly and communication between various nanoscale excitonic components can we hope to first understand and then engineer the system to allow these materials to reachmore » their potential. The aims of this proposal are to: 1) develop a paradigm-changing platform for probing excitonic processes composed of Crystalline Nanoporous Frameworks (CNFs) infiltrated with secondary materials (such as a complimentary semiconductor); 2) use them to probe fundamental aspects of excitonic processes; and 3) create prototype OPVs and OLEDs using infiltrated CNF as active device components. These functional platforms will allow detailed control of key interactions at the nanoscale, overcoming the disorder and limited synthetic control inherent in conventional organic materials. CNFs are revolutionary inorganic-organic hybrid materials boasting unmatched synthetic flexibility that allow tuning of chemical, geometric, electrical, and light absorption/generation properties. For example, bandgap engineering is feasible and polyaromatic linkers provide tunable photon antennae; rigid 1-5 nm pores provide an oriented, intimate host for triplet emitters (to improve light emission in OLEDs) or secondary semiconducting polymers (creating a charge-separation interface in OPV). These atomically engineered, ordered structures will enable critical fundamental questions to be answered concerning charge transport, nanoscale interfaces, and exciton behavior that are inaccessible in disordered systems. Implementing this concept also creates entirely new dimensions for device fabrication that could both improve performance, increase durability, and reduce costs with unprecedented control of over properties. This report summarizes the key results of this project and is divided into sections based on publications that resulted from the work. We begin in Section 2 with an investigation of light harvesting and energy transfer in a MOF infiltrated with donor and acceptor molecules of the type typically used in OPV devices (thiophenes and fullerenes, respectively). The results show that MOFs can provide multiple functions: as a light harvester, as a stabilizer and organizer or the infiltrated molecules, and as a facilitator of energy transfer. Section 3 describes computational design of MOF linker groups to accomplish light harvesting in the visible and facilitate charge separation and transport. The predictions were validated by UV-visible absorption spectroscopy, demonstrating that rational design of MOFs for light-harvesting purposes is feasible. Section 4 extends the infiltration concept discussed in Section to, which we now designate as "Molecule@MOF" to create an electrically conducting framework. The tailorability and high conductivity of this material are unprecedented, meriting publication in the journal Science and spawning several Technical Advances. Section 5 discusses processes we developed for depositing MOFs as thin films on substrates, a critical enabling technology for fabricating MOF-based electronic devices. Finally, in Section 6 we summarize results showing that a MOF thin film can be used as a sensitizer in a DSSC, demonstrating that MOFs can serve as active layers in excitonic devices. Overall, this project provides several crucial proofs-of- concept that the potential of MOFs for use in optoelectronic devices that we predicted several years ago [ 3 ] can be realized in practice.« less

Observation of Exciton-Exciton Interaction Mediated Valley Depolarization in Monolayer MoSe2.

PubMed

Mahmood, Fahad; Alpichshev, Zhanybek; Lee, Yi-Hsien; Kong, Jing; Gedik, Nuh

2018-01-10

The valley pseudospin in monolayer transition metal dichalcogenides (TMDs) has been proposed as a new way to manipulate information in various optoelectronic devices. This relies on a large valley polarization that remains stable over long time scales (hundreds of nanoseconds). However, time-resolved measurements report valley lifetimes of only a few picoseconds. This has been attributed to mechanisms such as phonon-mediated intervalley scattering and a precession of the valley pseudospin through electron-hole exchange. Here we use transient spin grating to directly measure the valley depolarization lifetime in monolayer MoSe 2 . We find a fast valley decay rate that scales linearly with the excitation density at different temperatures. This establishes the presence of strong exciton-exciton Coulomb exchange interactions enhancing the valley depolarization. Our work highlights the microscopic processes inhibiting the efficient use of the exciton valley pseudospin in monolayer TMDs.

Theoretical study on the cooperative exciton dissociation process based on dimensional and hot charge-transfer state effects in an organic photocell

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

Shimazaki, Tomomi; Nakajima, Takahito

2016-06-21

This paper discusses the exciton dissociation process at the donor–acceptor interface in organic photocells. In our previous study, we introduced a local temperature to handle the hot charge-transfer (CT) state and calculated the exciton dissociation probability based on the 1D organic semiconductor model [T. Shimazaki and T. Nakajima, Phys. Chem. Chem. Phys. 17, 12538 (2015)]. Although the hot CT state plays an essential role in exciton dissociations, the probabilities calculated are not high enough to efficiently separate bound electron–hole pairs. This paper focuses on the dimensional (entropy) effect together with the hot CT state effect and shows that cooperative behaviormore » between both effects can improve the exciton dissociation process. In addition, we discuss cooperative effects with site-disorders and external-electric-fields.« less

Direct optical state preparation of the dark exciton in a quantum dot

NASA Astrophysics Data System (ADS)

Lüker, S.; Kuhn, T.; Reiter, D. E.

2015-11-01

Because of their weak coupling to the electromagnetic field, dark excitons in semiconductor quantum dots possess extremely long lifetimes, which makes them attractive candidates for quantum information processing. On the other hand, the preparation and manipulation of dark states is challenging, because commonly used optical excitation mechanisms are not applicable. We propose an efficient mechanism for the deterministic preparation of the dark exciton exploiting the application of a tilted magnetic field and the optical excitation with a chirped, i.e., frequency modulated, laser pulse.

Singlet-triplet splittings and their relevance to the spin-dependent exciton formation in light-emitting polymers: an EOM/CCSD study.

PubMed

Chen, Liping; Zhu, Lingyun; Shuai, Zhigang

2006-12-21

By employing the coupled-cluster equation of motion method (EOM/CCSD) for excited-state structures, we have investigated the structure dependence of the singlet and triplet exciton splittings, through extensive calculations for polythiophene (PT), poly(3,4-ethylenedioxythiophene) (PEDOT), poly(thienylenevinylene) (PTV), polyparaphenylene vinylene (PPV), MEHPPV, polyparaphenylene ethylene (PPE), polyfluorene (PFO), and ladder-type polyparaphenylene (mLPPP). The results for the polymer are extrapolated through computations for the oligomers with increasing length. Recent investigations have been quite controversial about whether the internal quantum efficiency of electroluminescence could be higher than the 25% spin statistics limit or not in polymeric materials. Using a simple relationship between the exciton formation rate and the excitation energy level, we have discussed the material-dependent ratios of singlet and triplet exciton formation, which are in good agreement with the magnetic-field resonance detected transient spectroscopy measurement by Wohlgenannt et al. for a series of electronic polymers. This provides another piece of evidence to support the view that the internal quantum efficiency for conjugated polymers can exceed the 25% limit.

Bulk heterojunction morphology of polymer:fullerene blends revealed by ultrafast spectroscopy

PubMed Central

Serbenta, Almis; Kozlov, Oleg V.; Portale, Giuseppe; van Loosdrecht, Paul H. M.; Pshenichnikov, Maxim S.

2016-01-01

Morphology of organic photovoltaic bulk heterojunctions (BHJs) – a nanoscale texture of the donor and acceptor phases – is one of the key factors influencing efficiency of organic solar cells. Detailed knowledge of the morphology is hampered by the fact that it is notoriously difficult to investigate by microscopic methods. Here we all-optically track the exciton harvesting dynamics in the fullerene acceptor phase from which subdivision of the fullerene domain sizes into the mixed phase (2–15 nm) and large (>50 nm) domains is readily obtained via the Monte-Carlo simulations. These results were independently confirmed by a combination of X-ray scattering, electron and atomic-force microscopies, and time-resolved photoluminescence spectroscopy. In the large domains, the excitons are lost due to the high energy disorder while in the ordered materials the excitons are harvested with high efficiency even from the domains as large as 100 nm due to the absence of low-energy traps. Therefore, optimizing of blend nanomorphology together with increasing the material order are deemed as winning strategies in the exciton harvesting optimization. PMID:27824085

Reconfigurable exciton-plasmon interconversion for nanophotonic circuits

PubMed Central

Lee, Hyun Seok; Luong, Dinh Hoa; Kim, Min Su; Jin, Youngjo; Kim, Hyun; Yun, Seokjoon; Lee, Young Hee

2016-01-01

The recent challenges for improving the operation speed of nanoelectronics have motivated research on manipulating light in on-chip integrated circuits. Hybrid plasmonic waveguides with low-dimensional semiconductors, including quantum dots and quantum wells, are a promising platform for realizing sub-diffraction limited optical components. Meanwhile, two-dimensional transition metal dichalcogenides (TMDs) have received broad interest in optoelectronics owing to tightly bound excitons at room temperature, strong light-matter and exciton-plasmon interactions, available top-down wafer-scale integration, and band-gap tunability. Here, we demonstrate principal functionalities for on-chip optical communications via reconfigurable exciton-plasmon interconversions in ∼200-nm-diameter Ag-nanowires overlapping onto TMD transistors. By varying device configurations for each operation purpose, three active components for optical communications are realized: field-effect exciton transistors with a channel length of ∼32 μm, field-effect exciton multiplexers transmitting multiple signals through a single NW and electrical detectors of propagating plasmons with a high On/Off ratio of∼190. Our results illustrate the unique merits of two-dimensional semiconductors for constructing reconfigurable device architectures in integrated nanophotonic circuits. PMID:27892463

Nanostructured organic/inorganic semicondutor photovoltaics: Investigation on morphology and optoelectronics performance

NASA Astrophysics Data System (ADS)

Wanninayake, Aruna Pushpa Kumara

Organic solar cell is a promising technology because of the versatility of organic materials in terms of tunability of their electrical and optical properties. In addition, their relative insensitivity to film imperfections potentially allows for very low-cost high-throughput roll-to-roll processing. However, the power conversion efficiency of organic solar cell is still limited and needs to be improved in order to be competitive with grid parity. This work is focused on the design and characterization of a new organic/inorganic hybrid device to enhance the efficiency factors of bilayer organic solar cells such as: light absorption, exciton diffusion, exciton dissociation, charge transportation and charge collection at the electrodes. In a hybrid solar cell operation, external quantum efficiency is determined by these five factors. The external quantum efficiency has linear relationship to the power conversation efficiency via short circuit current density. Bulk heterojunction (BHJ) PSCs benefit from a homogeneous donor-acceptor (D-A) contact interface compared to their inorganic counterpart. A homogenous D-A interface offers a longer free path for charge carriers, resulting in a longer diffusional pathway and a larger coulomb interaction between electrons and holes. This is triggered by the low dielectric constant of organic semiconductors. Among various conventional donor-acceptor structures, poly(3-hexylthiophene)/[6,6]-phenyl-C70-butyric acid methyl ester (P3HT/PCBM) mixture is the most promising and ideal donor-acceptor pair due to their unique properties. In order to take benefits from both organic and inorganic materials, inorganic nanoparticles are incorporated in this donor-acceptor polymer structure. Light trapping enhances light absorption and increases efficiencies with thinner device structure. In this study, copper oxide nanoparticles are used in the P3HT/PC70BM active layer to optimize the optical absorption properties in the blend. In addition, zinc oxide nanoparticles are used for tuning the conjugated polymer films due to their high electron accepting ability and optical absorption properties. In the zinc oxide structure, electrons exhibit higher mobility, which enhances the exciton dissociation efficiency. In addition, metal nanoparticles such as gold are added to the hole transport layer to enhance the overall hole transport ability. The optimum morphology of P3HT/PCBM films is described by two main features: 1) the molecular ordering within the donor or acceptor phase, which affects the photon absorption and carrier mobility; and 2) the scale of phase separation between the donor and the acceptor, which can directly influence the exciton dissociation and charge transport and/or collection processes. Hence, the molecular ordering and the phase separation between the donor and acceptor phases are crucial for solar cells with high efficiency. Optimization of the morphology of the organic/inorganic hybrid layers will be achieved via thermal annealing. The main goal of this work is to fabricate inorganic nanoparticles incorporated polymer PV devices with increased power conversion efficiency (PCE). This goal is achieved through four research objectives which are 1) enhancement of exciton generation and morphology by CuO NPs, 2) enhancement of exciton transportation and carrier diffusion by thermal annealing, 3) Improvement of exciton dissociation and electron mobility using ZnO NPs, and 4) improvement of hole collection ability using Au NPs. The key findings in this research can be applied to fabricate solar cells with higher power conversion efficiencies.

First-principles Investigation of the Structure, Mobility and Optical Properties of Self-Trapped Excitons in Alkali Metal, Lanthanum and Barium Halide Scintillators

NASA Astrophysics Data System (ADS)

Bizarri, Gregory; Del Ben, Mauro; Bourret, Edith; Canning, Andrew

The performance of new and improved materials for gamma ray scintillator detectors is dependant on multiple factors such as quantum efficiency, energy transport etc. In halide scintillator materials the energy transport is often impacted by self-trapped exciton (STE) formation and mobility. We present first-principles calculations at the hybrid density functional theory level for the structure, mobility and optical properties of STEs and their associated lattice defects (VK centers) in two important families of scintillator materials, alkali metal and lanthanum halides (AX and LaX). AX and LaX have been extensively characterized by experiments and serve as benchmark systems to assess the accuracy of our theoretical procedure. We show that hydrid functionals accurately predict the different types of self-trapped excitons (on and off-center) found in AX and LX materials in agreement with EPR experiments. We then applied this approach to perform preliminary studies on classes of new scintillator materials including the barium mixed halides and compared with our new experimental results. These studies have the potential to benefit the development of improved scintillator materials tailored for specific applications. This work is supported by the U.S. Department of Energy/NNSA/DNN R&D and is carried out at Lawrence Berkeley National Laboratory under Contract No. AC02-05CH11231.

Simultaneous observation of free and defect-bound excitons in CH3NH3PbI3 using four-wave mixing spectroscopy

NASA Astrophysics Data System (ADS)

March, Samuel A.; Clegg, Charlotte; Riley, Drew B.; Webber, Daniel; Hill, Ian G.; Hall, Kimberley C.

2016-12-01

Solar cells incorporating organic-inorganic perovskite, which may be fabricated using low-cost solution-based processing, have witnessed a dramatic rise in efficiencies yet their fundamental photophysical properties are not well understood. The exciton binding energy, central to the charge collection process, has been the subject of considerable controversy due to subtleties in extracting it from conventional linear spectroscopy techniques due to strong broadening tied to disorder. Here we report the simultaneous observation of free and defect-bound excitons in CH3NH3PbI3 films using four-wave mixing (FWM) spectroscopy. Due to the high sensitivity of FWM to excitons, tied to their longer coherence decay times than unbound electron- hole pairs, we show that the exciton resonance energies can be directly observed from the nonlinear optical spectra. Our results indicate low-temperature binding energies of 13 meV (29 meV) for the free (defect-bound) exciton, with the 16 meV localization energy for excitons attributed to binding to point defects. Our findings shed light on the wide range of binding energies (2-55 meV) reported in recent years.

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

Ahmad, Shahab; Vijaya Prakash, G., E-mail: prakash@physics.iitd.ac.in; Baumberg, Jeremy J.

Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C{sub 12}H{sub 25}NH{sub 3}){sub 2}PbI{sub 4(1−y)}Br{sub 4y} (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed tomore » the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices.« less

Direct Imaging of Frenkel Exciton Transport by Ultrafast Microscopy.

PubMed

Zhu, Tong; Wan, Yan; Huang, Libai

2017-07-18

Long-range transport of Frenkel excitons is crucial for achieving efficient molecular-based solar energy harvesting. Understanding of exciton transport mechanisms is important for designing materials for solar energy applications. One major bottleneck in unraveling of exciton transport mechanisms is the lack of direct measurements to provide information in both spatial and temporal domains, imposed by the combination of fast energy transfer (typically ≤1 ps) and short exciton diffusion lengths (typically ≤100 nm). This challenge requires developing experimental tools to directly characterize excitation energy transport, and thus facilitate the elucidation of mechanisms. To address this challenge, we have employed ultrafast transient absorption microscopy (TAM) as a means to directly image exciton transport with ∼200 fs time resolution and ∼50 nm spatial precision. By mapping population in spatial and temporal domains, such approach has unraveled otherwise obscured information and provided important parameters for testing exciton transport models. In this Account, we discuss the recent progress in imaging Frenkel exciton migration in molecular crystals and aggregates by ultrafast microscopy. First, we establish the validity of the TAM methods by imaging singlet and triplet exciton transport in a series of polyacene single crystals that undergo singlet fission. A new singlet-mediated triplet transport pathway has been revealed by TAM, resulting from the equilibrium between triplet and singlet exciton populations. Such enhancement of triplet exciton transport enables triplet excitons to migrate as singlet excitons and leads to orders of magnitude faster apparent triplet exciton diffusion rate in the picosecond and nanosecond time scales, favorable for solar cell applications. Next we discuss how information obtained by ultrafast microscopy can evaluate coherent effects in exciton transport. We use tubular molecular aggregates that could support large exciton delocalization sizes as a model system. The initial experiments measure exciton diffusion constants of 3-6 cm 2 s -1 , 3-5 times higher than the incoherent limit predicted by theory, suggesting that coherent effects play a role. In summary, combining ultrafast spectroscopic methods with microscopic techniques provides a direct approach for obtaining important parameters to unravel the underlying exciton transport mechanisms in molecular solids. We discuss future directions to bridge the gap in understanding of fundamental energy transfer theories to include coherent and incoherent effects. We are still in the infancy of ultrafast microscopy, and the vast potential is not limited to the systems discussed in this Account.

Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites

NASA Astrophysics Data System (ADS)

Blancon, J.-C.; Tsai, H.; Nie, W.; Stoumpos, C. C.; Pedesseau, L.; Katan, C.; Kepenekian, M.; Soe, C. M. M.; Appavoo, K.; Sfeir, M. Y.; Tretiak, S.; Ajayan, P. M.; Kanatzidis, M. G.; Even, J.; Crochet, J. J.; Mohite, A. D.

2017-03-01

Understanding and controlling charge and energy flow in state-of-the-art semiconductor quantum wells has enabled high-efficiency optoelectronic devices. Two-dimensional (2D) Ruddlesden-Popper perovskites are solution-processed quantum wells wherein the band gap can be tuned by varying the perovskite-layer thickness, which modulates the effective electron-hole confinement. We report that, counterintuitive to classical quantum-confined systems where photogenerated electrons and holes are strongly bound by Coulomb interactions or excitons, the photophysics of thin films made of Ruddlesden-Popper perovskites with a thickness exceeding two perovskite-crystal units (>1.3 nanometers) is dominated by lower-energy states associated with the local intrinsic electronic structure of the edges of the perovskite layers. These states provide a direct pathway for dissociating excitons into longer-lived free carriers that substantially improve the performance of optoelectronic devices.

Diamagnetic excitons and exciton magnetopolaritons in semiconductors

NASA Astrophysics Data System (ADS)

Seisyan, R. P.

2012-05-01

Interband magneto-absorption in semiconductors is reviewed in the light of the diamagnetic exciton (DE) concept. Beginning with a proof of the exciton nature of oscillating-magnetoabsorption (the DE discovery), development of the DE concept is discussed, including definition of observation conditions, quasi-cubic approximation for hexagonal crystals, quantum-well effects in artificial structures, and comprehension of an important role of the DE polariton. The successful use of the concept application to a broad range of substances is reviewed, namely quasi-Landau magnetic spectroscopy of the ‘Rydberg’ exciton states in cubic semiconductors such as InP and GaAs and in hexagonal ones such as CdSe, the proof of exciton participation in the formation of optical spectra in narrow-gap semiconductors such as InSb, InAs, and, especially, PbTe, observation of DE spectra in semiconductor solid solutions like InGaAs. The most fundamental findings of the DE spectroscopy for various quantum systems are brought together, including the ‘Coulomb-well’ effect, fine structure of discrete oscillatory states in the InGaAs/GaAs multiple quantum wells, the magneto-optical observation of above-barrier exciton. Prospects of the DE physics in ultrahigh magnetic field are discussed, including technological creation of controllable low-dimensional objects with extreme oscillator strengths, formation of magneto-quantum exciton polymer, and even modelling of the hydrogen behaviour in the atmosphere of a neutron star.

Time-Resolved Stark Spectroscopy in CdSe Nanoplatelets: Exciton Binding Energy, Polarizability, and Field-Dependent Radiative Rates.

PubMed

Scott, Riccardo; Achtstein, Alexander W; Prudnikau, Anatol V; Antanovich, Artsiom; Siebbeles, Laurens D A; Artemyev, Mikhail; Woggon, Ulrike

2016-10-12

We present a study of the application potential of CdSe nanoplatelets (NPLs), a model system for colloidal 2D materials, as field-controlled emitters. We demonstrate that their emission can be changed by 28% upon application of electrical fields up to 175 kV/cm, a very high modulation depth for field-controlled nanoemitters. From our experimental results we estimate the exciton binding energy in 5.5 monolayer CdSe nanoplatelets to be E B = 170 meV; hence CdSe NPLs exhibit highly robust excitons which are stable even at room temperature. This opens up the possibility to tune the emission and recombination dynamics efficiently by external fields. Our analysis further allows a quantitative discrimination of spectral changes of the emission energy and changes in PL intensity related to broadening of the emission line width as well as changes in the intrinsic radiative rates which are directly connected to the measured changes in the PL decay dynamics. With the developed field-dependent population model treating all occurring field-dependent effects in a global analysis, we are able to quantify, e.g., the ground state exciton transition dipole moment (3.0 × 10 -29 Cm) and its polarizability, which determine the radiative rate, as well as the (static) exciton polarizability (8.6 × 10 -8 eV cm 2 /kV 2 ), all in good agreement with theory. Our results show that an efficient field control over the exciton recombination dynamics, emission line width, and emission energy in these nanoparticles is feasible and opens up application potential as field-controlled emitters.

Stimulated Emission of Terahertz Radiation from Internal ExcitonTransitions in Cu2O

NASA Astrophysics Data System (ADS)

Schmid, B. A.; Huber, R.; Shen, Y. R.; Kaindl, R. A.; Chemla, D. S.

2006-03-01

Excitons are among the most fundamental optical excitation modes in semiconductors. Resonant infrared pulses have been used to sensitively probe absorptive transitions between hydrogen-like bound pair states [1,2]. We report the first observation of the reverse quantum process: stimulated emission of electromagnetic radiation from intra-excitonic transitions [3]. Broadband terahertz pulses monitor the far-infrared electromagnetic response of Cu2O after ultrafast resonant photogeneration of 3p excitons. Stimulated emission from the 3p to the energetically lower 2s bound level occurs at a photon energy of 6.6 meV, with a cross section of ˜10-14 cm^2. Simultaneous excitation of both exciton levels, in turn, drives quantum beats which lead to efficient terahertz emission sharply peaked at the difference frequency. Our results demonstrate a new fundamental process of THz quantum optics and highlight analogies and differences between excitonic and atomic systems. [1] R. A. Kaindl et al., Nature 423, 734 (2003). [2] M. Kubouchi et al., Phys. Rev. Lett. 94, 016403 (2005). [3] R. Huber et al., Phys. Rev. Lett., to appear.

Modeling temperature dependent singlet exciton dynamics in multilayered organic nanofibers

NASA Astrophysics Data System (ADS)

de Sousa, Leonardo Evaristo; de Oliveira Neto, Pedro Henrique; Kjelstrup-Hansen, Jakob; da Silva Filho, Demétrio Antônio

2018-05-01

Organic nanofibers have shown potential for application in optoelectronic devices because of the tunability of their optical properties. These properties are influenced by the electronic structure of the molecules that compose the nanofibers and also by the behavior of the excitons generated in the material. Exciton diffusion by means of Förster resonance energy transfer is responsible, for instance, for the change with temperature of colors in the light emitted by systems composed of different types of nanofibers. To study in detail this mechanism, we model temperature dependent singlet exciton dynamics in multilayered organic nanofibers. By simulating absorption and emission spectra, the possible Förster transitions are identified. Then, a kinetic Monte Carlo model is employed in combination with a genetic algorithm to theoretically reproduce time-resolved photoluminescence measurements for several temperatures. This procedure allows for the obtainment of different information regarding exciton diffusion in such a system, including temperature effects on the Förster transfer efficiency and the activation energy of the Förster mechanism. The method is general and may be employed for different systems where exciton diffusion plays a role.

Exciton-Exciton Annihilation as a Probe of Interchain Interactions in PPV-Oligomer Aggregates.

PubMed

Peteanu, Linda A; Chowdhury, Sanchari; Wildeman, Jurjen; Sfeir, Matthew Y

2017-02-23

One measure of exciton mobility in an aggregate is the efficiency of exciton-exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH-PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed from the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. The wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.

Electrical pumping and tuning of exciton-polaritons in carbon nanotube microcavities

NASA Astrophysics Data System (ADS)

Graf, Arko; Held, Martin; Zakharko, Yuriy; Tropf, Laura; Gather, Malte C.; Zaumseil, Jana

2017-09-01

Exciton-polaritons are hybrid light-matter particles that form upon strong coupling of an excitonic transition to a cavity mode. As bosons, polaritons can form condensates with coherent laser-like emission. For organic materials, optically pumped condensation was achieved at room temperature but electrically pumped condensation remains elusive due to insufficient polariton densities. Here we combine the outstanding optical and electronic properties of purified, solution-processed semiconducting (6,5) single-walled carbon nanotubes (SWCNTs) in a microcavity-integrated light-emitting field-effect transistor to realize efficient electrical pumping of exciton-polaritons at room temperature with high current densities (>10 kA cm-2) and tunability in the near-infrared (1,060 nm to 1,530 nm). We demonstrate thermalization of SWCNT polaritons, exciton-polariton pumping rates ~104 times higher than in current organic polariton devices, direct control over the coupling strength (Rabi splitting) via the applied gate voltage, and a tenfold enhancement of polaritonic over excitonic emission. This powerful material-device combination paves the way to carbon-based polariton emitters and possibly lasers.

Exciton Scattering approach for conjugated macromolecules: from electronic spectra to electron-phonon coupling

NASA Astrophysics Data System (ADS)

Tretiak, Sergei

2014-03-01

The exciton scattering (ES) technique is a multiscale approach developed for efficient calculations of excited-state electronic structure and optical spectra in low-dimensional conjugated macromolecules. Within the ES method, the electronic excitations in the molecular structure are attributed to standing waves representing quantum quasi-particles (excitons), which reside on the graph. The exciton propagation on the linear segments is characterized by the exciton dispersion, whereas the exciton scattering on the branching centers is determined by the energy-dependent scattering matrices. Using these ES energetic parameters, the excitation energies are then found by solving a set of generalized ``particle in a box'' problems on the graph that represents the molecule. All parameters can be extracted from quantum-chemical computations of small molecular fragments and tabulated in the ES library for further applications. Subsequently, spectroscopic modeling for any macrostructure within considered molecular family could be performed with negligible numerical effort. The exciton scattering properties of molecular vertices can be further described by tight-binding or equivalently lattice models. The on-site energies and hopping constants are obtained from the exciton dispersion and scattering matrices. Such tight-binding model approach is particularly useful to describe the exciton-phonon coupling, energetic disorder and incoherent energy transfer in large branched conjugated molecules. Overall the ES applications accurately reproduce the optical spectra compared to the reference quantum chemistry results, and make possible to predict spectra of complex macromolecules, where conventional electronic structure calculations are unfeasible.

High Performing Ternary Solar Cells through Förster Resonance Energy Transfer between Nonfullerene Acceptors.

PubMed

Yang, Lei; Gu, Wenxing; Hong, Ling; Mi, Yang; Liu, Feng; Liu, Ming; Yang, Yufei; Sharma, Bigyan; Liu, Xinfeng; Huang, Hui

2017-08-16

Nonradiative Förster resonance energy transfer (FRET) is an important mechanism of organic solar cells, which can improve the exciton migration over a long distance, resulting in improvement of efficiency of solar cells. However, the current observations of FRET are very limited, and the efficiencies are less than 9%. In this study, FRET effect was first observed between two nonfullerene acceptors in ternary solar cells, which improved both the absorption range and exciton harvesting, leading to the dramatic enhancement in the short circuit current and power conversion efficiency. Moreover, this strategy is proved to be a versatile platform for conjugated polymers with different bandgaps, resulting in a remarkable efficiency of 10.4%. These results demonstrated a novel method to enhance the efficiency of organic soar cells.

Direct Observation of Electron-Phonon Coupling and Slow Vibrational Relaxation in Organic-Inorganic Hybrid Perovskites

NASA Astrophysics Data System (ADS)

Hurtado Parra, Sebastian; Straus, Daniel; Iotov, Natasha; Fichera, Bryan; Gebhardt, Julian; Rappe, Andrew; Subotnik, Joseph; Kikkawa, James; Kagan, Cherie

Quantum and dielectric confinement effects in Ruddlesden-Popper 2D hybrid perovskites create excitons with a binding energy exceeding 150 meV. We exploit the large exciton binding energy to study exciton and carrier dynamics as well as electron-phonon coupling (EPC) in hybrid perovskites using absorption and photoluminescence (PL) spectroscopies. At temperatures <75 K, we resolve splitting of the excitonic absorption and PL into multiple regularly spaced resonances every 40-46 meV, consistent with EPC to phonons located on the organic cation. We also resolve resonances with a 14 meV spacing, in accord with coupling to phonons with mixed organic and inorganic character. These assignments are supported by density-functional theory calculations. Hot exciton PL and time-resolved PL measurements show that vibrational relaxation occurs on a picosecond time scale competitive with that for PL. At temperatures >75 K, excitonic absorption and PL exhibit homogeneous broadening. While absorption remains homogeneous, PL becomes inhomogeneous at temperatures <75K, which we speculate is caused by the formation and subsequent dynamics of a polaronic exciton. This work is supported by the U.S. Department of Energy, Office of Basic Energy Sciences Grant DE-SC0002158 and the National Science Foundation Graduate Research Fellowship Grant DGE-1321851.

Direct Visualization of Exciton Reequilibration in the LH1 and LH2 Complexes of Rhodobacter sphaeroides by Multipulse Spectroscopy

PubMed Central

Cohen Stuart, Thomas A.; Vengris, Mikas; Novoderezhkin, Vladimir I.; Cogdell, Richard J.; Hunter, C. Neil; van Grondelle, Rienk

2011-01-01

The dynamics of the excited states of the light-harvesting complexes LH1 and LH2 of Rhodobacter sphaeroides are governed, mainly, by the excitonic nature of these ring-systems. In a pump-dump-probe experiment, the first pulse promotes LH1 or LH2 to its excited state and the second pulse dumps a portion of the excited state. By selective dumping, we can disentangle the dynamics normally hidden in the excited-state manifold. We find that by using this multiple-excitation technique we can visualize a 400-fs reequilibration reflecting relaxation between the two lowest exciton states that cannot be directly explored by conventional pump-probe. An oscillatory feature is observed within the exciton reequilibration, which is attributed to a coherent motion of a vibrational wavepacket with a period of ∼150 fs. Our disordered exciton model allows a quantitative interpretation of the observed reequilibration processes occurring in these antennas. PMID:21539791

Direct visualization of exciton reequilibration in the LH1 and LH2 complexes of Rhodobacter sphaeroides by multipulse spectroscopy.

PubMed

Cohen Stuart, Thomas A; Vengris, Mikas; Novoderezhkin, Vladimir I; Cogdell, Richard J; Hunter, C Neil; van Grondelle, Rienk

2011-05-04

The dynamics of the excited states of the light-harvesting complexes LH1 and LH2 of Rhodobacter sphaeroides are governed, mainly, by the excitonic nature of these ring-systems. In a pump-dump-probe experiment, the first pulse promotes LH1 or LH2 to its excited state and the second pulse dumps a portion of the excited state. By selective dumping, we can disentangle the dynamics normally hidden in the excited-state manifold. We find that by using this multiple-excitation technique we can visualize a 400-fs reequilibration reflecting relaxation between the two lowest exciton states that cannot be directly explored by conventional pump-probe. An oscillatory feature is observed within the exciton reequilibration, which is attributed to a coherent motion of a vibrational wavepacket with a period of ∼150 fs. Our disordered exciton model allows a quantitative interpretation of the observed reequilibration processes occurring in these antennas. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Strategies for increasing the efficiency of heterojunction organic solar cells: material selection and device architecture.

PubMed

Heremans, Paul; Cheyns, David; Rand, Barry P

2009-11-17

Thin-film blends or bilayers of donor- and acceptor-type organic semiconductors form the core of heterojunction organic photovoltaic cells. Researchers measure the quality of photovoltaic cells based on their power conversion efficiency, the ratio of the electrical power that can be generated versus the power of incident solar radiation. The efficiency of organic solar cells has increased steadily in the last decade, currently reaching up to 6%. Understanding and combating the various loss mechanisms that occur in processes from optical excitation to charge collection should lead to efficiencies on the order of 10% in the near future. In organic heterojunction solar cells, the generation of photocurrent is a cascade of four steps: generation of excitons (electrically neutral bound electron-hole pairs) by photon absorption, diffusion of excitons to the heterojunction, dissociation of the excitons into free charge carriers, and transport of these carriers to the contacts. In this Account, we review our recent contributions to the understanding of the mechanisms that govern these steps. Starting from archetype donor-acceptor systems of planar small-molecule heterojunctions and solution-processed bulk heterojunctions, we outline our search for alternative materials and device architectures. We show that non-planar phthalocynanines have appealing absorption characteristics but also have reduced charge carrier transport. As a result, the donor layer needs to be ultrathin, and all layers of the device have to be tuned to account for optical interference effects. Using these optimization techniques, we illustrate cells with 3.1% efficiency for the non-planar chloroboron subphthalocyanine donor. Molecules offering a better compromise between absorption and carrier mobility should allow for further improvements. We also propose a method for increasing the exciton diffusion length by converting singlet excitons into long-lived triplets. By doping a polymer with a phosphorescent molecule, we demonstrate an increase in the exciton diffusion length of a polymer from 4 to 9 nm. If researchers can identify suitable phosphorescent dopants, this method could be employed with other materials. The carrier transport from the junction to the contacts is markedly different for a bulk heterojunction cell than for planar junction cells. Unlike for bulk heterojunction cells, the open-circuit voltage of planar-junction cells is independent of the contact work functions, as a consequence of the balance of drift and diffusion currents in these systems. This understanding helps to guide the development of new materials (particularly donor materials) that can further boost the efficiency of single-junction cells to 10%. With multijunction architectures, we expect that efficiencies of 12-16% could be attained, at which point organic photovoltaic cells could become an important renewable energy source.

A predictive theory of charge separation in organic photovoltaics interfaces

NASA Astrophysics Data System (ADS)

Troisi, Alessandro; Liu, Tao; Caruso, Domenico; Cheung, David L.; McMahon, David P.

2012-09-01

The key process in organic photovoltaics cells is the separation of an exciton, close to the donor/acceptor interface into a free hole (in the donor) and a free electron (in the acceptor). In an efficient solar cell, the majority of absorbed photons generate such hole-electron pairs but it is not clear why such a charge separation process is so efficient in some blends (for example in the blend formed by poly(3- hexylthiophene) (P3HT) and a C60 derivative (PCBM)) and how can one design better OPV materials. The electronic and geometric structure of the prototypical polymer:fullerene interface (P3HT:PCBM) is investigated theoretically using a combination of classical and quantum simulation methods. It is shown that the electronic structure of P3HT in contact with PCBM is significantly altered compared to bulk P3HT. Due to the additional free volume of the interface, P3HT chains close to PCBM are more disordered and, consequently, they are characterized by an increased band gap. Excitons and holes are therefore repelled by the interface. This provides a possible explanation of the low recombination efficiency and supports the direct formation of "quasi-free" charge separated species at the interface. This idea is further explored here by using a more general system-independent model Hamiltonian. The long range exciton dissociation rate is computed as a function of the exciton distance from the interface and the average dissociation distance is evaluated by comparing this rate with the exciton migration rate with a kinetic model. The phenomenological model shows that also in a generic interface the direct formation if quasi-free charges is extremely likely.

Multistability of cavity exciton polaritons affected by the thermally generated exciton reservoir

NASA Astrophysics Data System (ADS)

Vishnevsky, D. V.; Solnyshkov, D. D.; Gippius, N. A.; Malpuech, G.

2012-04-01

Recently the buildup of an excitonic reservoir in a GaAs cavity polariton system under quasiresonant pumping has been demonstrated experimentally [S. S. Gavrilov , JETP Lett.JTPLA20021-364010.1134/S0021364010150105 92, 171 (2010)]. We show that in microcavities having a small Rabi splitting (typically GaAs cavities with a single quantum well), this reservoir can be efficiently populated by polariton-phonon scattering. We consider the influence of the exciton reservoir on the energy shifts of the resonantly pumped polariton modes. We show that the presence of this reservoir effectively reduces the spin anisotropy of the polariton-polariton interaction, in agreement with recent experimental measurements, where the multistability of cavity polaritons has been analyzed [T. K. Paraiso , Nat. Mater.1476-112210.1038/nmat2787 9, 655 (2010)].

Enhanced energy transport in genetically engineered excitonic networks.

PubMed

Park, Heechul; Heldman, Nimrod; Rebentrost, Patrick; Abbondanza, Luigi; Iagatti, Alessandro; Alessi, Andrea; Patrizi, Barbara; Salvalaggio, Mario; Bussotti, Laura; Mohseni, Masoud; Caruso, Filippo; Johnsen, Hannah C; Fusco, Roberto; Foggi, Paolo; Scudo, Petra F; Lloyd, Seth; Belcher, Angela M

2016-02-01

One of the challenges for achieving efficient exciton transport in solar energy conversion systems is precise structural control of the light-harvesting building blocks. Here, we create a tunable material consisting of a connected chromophore network on an ordered biological virus template. Using genetic engineering, we establish a link between the inter-chromophoric distances and emerging transport properties. The combination of spectroscopy measurements and dynamic modelling enables us to elucidate quantum coherent and classical incoherent energy transport at room temperature. Through genetic modifications, we obtain a significant enhancement of exciton diffusion length of about 68% in an intermediate quantum-classical regime.

Observation of non-Hermitian degeneracies in a chaotic exciton-polariton billiard.

PubMed

Gao, T; Estrecho, E; Bliokh, K Y; Liew, T C H; Fraser, M D; Brodbeck, S; Kamp, M; Schneider, C; Höfling, S; Yamamoto, Y; Nori, F; Kivshar, Y S; Truscott, A G; Dall, R G; Ostrovskaya, E A

2015-10-22

Exciton-polaritons are hybrid light-matter quasiparticles formed by strongly interacting photons and excitons (electron-hole pairs) in semiconductor microcavities. They have emerged as a robust solid-state platform for next-generation optoelectronic applications as well as for fundamental studies of quantum many-body physics. Importantly, exciton-polaritons are a profoundly open (that is, non-Hermitian) quantum system, which requires constant pumping of energy and continuously decays, releasing coherent radiation. Thus, the exciton-polaritons always exist in a balanced potential landscape of gain and loss. However, the inherent non-Hermitian nature of this potential has so far been largely ignored in exciton-polariton physics. Here we demonstrate that non-Hermiticity dramatically modifies the structure of modes and spectral degeneracies in exciton-polariton systems, and, therefore, will affect their quantum transport, localization and dynamical properties. Using a spatially structured optical pump, we create a chaotic exciton-polariton billiard--a two-dimensional area enclosed by a curved potential barrier. Eigenmodes of this billiard exhibit multiple non-Hermitian spectral degeneracies, known as exceptional points. Such points can cause remarkable wave phenomena, such as unidirectional transport, anomalous lasing/absorption and chiral modes. By varying parameters of the billiard, we observe crossing and anti-crossing of energy levels and reveal the non-trivial topological modal structure exclusive to non-Hermitian systems. We also observe mode switching and a topological Berry phase for a parameter loop encircling the exceptional point. Our findings pave the way to studies of non-Hermitian quantum dynamics of exciton-polaritons, which may uncover novel operating principles for polariton-based devices.

Light-trapping for room temperature Bose-Einstein condensation in InGaAs quantum wells.

PubMed

Vasudev, Pranai; Jiang, Jian-Hua; John, Sajeev

2016-06-27

We demonstrate the possibility of room-temperature, thermal equilibrium Bose-Einstein condensation (BEC) of exciton-polaritons in a multiple quantum well (QW) system composed of InGaAs quantum wells surrounded by InP barriers, allowing for the emission of light near telecommunication wavelengths. The QWs are embedded in a cavity consisting of double slanted pore (SP2) photonic crystals composed of InP. We consider exciton-polaritons that result from the strong coupling between the multiple quantum well excitons and photons in the lowest planar guided mode within the photonic band gap (PBG) of the photonic crystal cavity. The collective coupling of three QWs results in a vacuum Rabi splitting of 3% of the bare exciton recombination energy. Due to the full three-dimensional PBG exhibited by the SP2 photonic crystal (16% gap to mid-gap frequency ratio), the radiative decay of polaritons is eliminated in all directions. Due to the short exciton-phonon scattering time in InGaAs quantum wells of 0.5 ps and the exciton non-radiative decay time of 200 ps at room temperature, polaritons can achieve thermal equilibrium with the host lattice to form an equilibrium BEC. Using a SP2 photonic crystal with a lattice constant of a = 516 nm, a unit cell height of 2a=730nm and a pore radius of 0.305a = 157 nm, light in the lowest planar guided mode is strongly localized in the central slab layer. The central slab layer consists of 3 nm InGaAs quantum wells with 7 nm InP barriers, in which excitons have a recombination energy of 0.944 eV, a binding energy of 7 meV and a Bohr radius of aB = 10 nm. We take the exciton recombination energy to be detuned 35 meV above the lowest guided photonic mode so that an exciton-polariton has a photonic fraction of approximately 97% per QW. This increases the energy range of small-effective-mass photonlike states and increases the critical temperature for the onset of a Bose-Einstein condensate. With three quantum wells in the central slab layer, the strong light confinement results in light-matter coupling strength of ℏΩ = 13.7 meV. Assuming an exciton density per QW of (15aB)^-2, well below the saturation density, in a 2-D box-trap with a side length of 10 to 500 µm, we predict thermal equilibrium Bose-Einstein condensation well above room temperature.

Effect of Ag doping on the properties of ZnO thin films for UV stimulated emission

NASA Astrophysics Data System (ADS)

Razeen, Ahmed S.; Gadallah, A.-S.; El-Nahass, M. M.

2018-06-01

Ag doped ZnO thin films have been prepared using sol-gel spin coating method, with different doping concentrations. Structural and morphological properties of the films have been investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. Thin films have been optically pumped and stimulated emission has been observed with strong peaks in the UV region. The UV stimulated emission is found to be due to exciton-exciton scattering, and Ag doping promoted this process by increasing the excitons concentrations in the ZnO lattice. Output-input intensity relation and peak emission, FWHM, and quantum efficiency relations with pump intensity have been reported. The threshold for which stimulated emission started has been evaluated to be about 18 MW/cm2 with quantum efficiency of about 58.7%. Mechanisms explaining the role of Ag in enhancement of stimulated emission from ZnO thin films have been proposed.

Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites

DOE PAGES

Blancon, Jean -Christophe Robert; Tsai, Hsinhan; Nie, Wanyi; ...

2017-03-09

Understanding and controlling charge and energy flow in state-of-the-art semiconductor quantum wells has enabled high-efficiency optoelectronic devices. Two-dimensional (2D) Ruddlesden-Popper perovskites are solution-processed quantum wells wherein the band gap can be tuned by varying the perovskite-layer thickness, which modulates the effective electron-hole confinement. We report that, counterintuitive to classical quantum-confined systems where photogenerated electrons and holes are strongly bound by Coulomb interactions or excitons, the photophysics of thin films made of Ruddlesden-Popper perovskites with a thickness exceeding two perovskite-crystal units (>1.3 nanometers) is dominated by lower-energy states associated with the local intrinsic electronic structure of the edges of the perovskitemore » layers. Furthermore, these states provide a direct pathway for dissociating excitons into longer-lived free carriers that substantially improve the performance of optoelectronic devices.« less

Ultrahigh Responsivity and Detectivity Graphene-Perovskite Hybrid Phototransistors by Sequential Vapor Deposition

NASA Astrophysics Data System (ADS)

Chang, Po-Han; Liu, Shang-Yi; Lan, Yu-Bing; Tsai, Yi-Chen; You, Xue-Qian; Li, Chia-Shuo; Huang, Kuo-You; Chou, Ang-Sheng; Cheng, Tsung-Chin; Wang, Juen-Kai; Wu, Chih-I.

2017-04-01

In this work, graphene-methylammonium lead iodide (MAPbI3) perovskite hybrid phototransistors fabricated by sequential vapor deposition are demonstrated. Ultrahigh responsivity of 1.73 × 107 A W-1 and detectivity of 2 × 1015 Jones are achieved, with extremely high effective quantum efficiencies of about 108% in the visible range (450-700 nm). This excellent performance is attributed to the ultra-flat perovskite films grown by vapor deposition on the graphene sheets. The hybrid structure of graphene covered with uniform perovskite has high exciton separation ability under light exposure, and thus efficiently generates photocurrents. This paper presents photoluminescence (PL) images along with statistical analysis used to study the photo-induced exciton behavior. Both uniform and dramatic PL intensity quenching has been observed over entire measured regions, consistently demonstrating excellent exciton separation in the devices.

Ultrahigh Responsivity and Detectivity Graphene–Perovskite Hybrid Phototransistors by Sequential Vapor Deposition

PubMed Central

Chang, Po-Han; Liu, Shang-Yi; Lan, Yu-Bing; Tsai, Yi-Chen; You, Xue-Qian; Li, Chia-Shuo; Huang, Kuo-You; Chou, Ang-Sheng; Cheng, Tsung-Chin; Wang, Juen-Kai; Wu, Chih-I

2017-01-01

In this work, graphene-methylammonium lead iodide (MAPbI3) perovskite hybrid phototransistors fabricated by sequential vapor deposition are demonstrated. Ultrahigh responsivity of 1.73 × 107 A W−1 and detectivity of 2 × 1015 Jones are achieved, with extremely high effective quantum efficiencies of about 108% in the visible range (450–700 nm). This excellent performance is attributed to the ultra-flat perovskite films grown by vapor deposition on the graphene sheets. The hybrid structure of graphene covered with uniform perovskite has high exciton separation ability under light exposure, and thus efficiently generates photocurrents. This paper presents photoluminescence (PL) images along with statistical analysis used to study the photo-induced exciton behavior. Both uniform and dramatic PL intensity quenching has been observed over entire measured regions, consistently demonstrating excellent exciton separation in the devices. PMID:28422117

Exciton Resonances in Novel Silicon Carbide Polymers

NASA Astrophysics Data System (ADS)

Burggraf, Larry; Duan, Xiaofeng

2015-05-01

A revolutionary technology transformation from electronics to excitionics for faster signal processing and computing will be advantaged by coherent exciton transfer at room temperature. The key feature required of exciton components for this technology is efficient and coherent transfer of long-lived excitons. We report theoretical investigations of optical properties of SiC materials having potential for high-temperature excitonics. Using Car-Parinello simulated annealing and DFT we identified low-energy SiC molecular structures. The closo-Si12C12 isomer, the most stable 12-12 isomer below 1100 C, has potential to make self-assembled chains and 2-D nanostructures to construct exciton components. Using TDDFT, we calculated the optical properties of the isomer as well as oligomers and 2-D crystal formed from the isomer as the monomer unit. This molecule has large optical oscillator strength in the visible. Its high-energy and low-energy transitions (1.15 eV and 2.56 eV) are nearly pure one-electron silicon-to-carbon transitions, while an intermediate energy transition (1.28 eV) is a nearly pure carbon-to-silicon one-electron charge transfer. These results are useful to describe resonant, coherent transfer of dark excitons in the nanostructures. Research supported by the Air Force Office of Scientific Research.

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

Cadiz, Fabian, E-mail: cadiz@insa-toulouse.fr; Tricard, Simon; Gay, Maxime

Developments in optoelectronics and spin-optronics based on transition metal dichalcogenide monolayers (MLs) need materials with efficient optical emission and well-defined transition energies. In as-exfoliated MoS{sub 2} MLs, the photoluminescence (PL) spectra even at low temperature consist typically of broad, overlapping contributions from neutral, charged excitons (trions) and localized states. Here, we show that in superacid treated MoS{sub 2} MLs, the PL intensity increases by up to 60 times at room temperature. The neutral and charged exciton transitions are spectrally well separated in PL and reflectivity at T = 4 K, with linewidth for the neutral exciton of 15 meV, but both transitions have similarmore » intensities compared to the ones in as-exfoliated MLs at the same temperature. Time resolved experiments uncover picoseconds recombination dynamics analyzed separately for charged and neutral exciton emissions. Using the chiral interband selection rules, we demonstrate optically induced valley polarization for both complexes and valley coherence for only the neutral exciton.« less

Excitonic Emission of Monolayer Semiconductors Near-Field Coupled to High-Q Microresonators

NASA Astrophysics Data System (ADS)

Javerzac-Galy, Clément; Kumar, Anshuman; Schilling, Ryan D.; Piro, Nicolas; Khorasani, Sina; Barbone, Matteo; Goykhman, Ilya; Khurgin, Jacob B.; Ferrari, Andrea C.; Kippenberg, Tobias J.

2018-05-01

We present quantum yield measurements of single layer $\\textrm{WSe}_2$ (1L-$\\textrm{WSe}_2$) integrated with high-Q ($Q>10^6$) optical microdisk cavities, using an efficient ($\\eta>$90%) near-field coupling scheme based on a tapered optical fiber. Coupling of the excitonic emission is achieved by placing 1L-WSe$_2$ to the evanescent cavity field. This preserves the microresonator high intrinsic quality factor ($Q>10^6$) below the bandgap of 1L-WSe$_2$. The nonlinear excitation power dependence of the cavity quantum yield is in agreement with an exciton-exciton annihilation model. The cavity quantum yield is $\\textrm{QY}_\\textrm{c}\\sim10^{-3}$, consistent with operation in the \\textit{broad emitter} regime (i.e. the emission lifetime of 1L-WSe$_2$ is significantly shorter than the bare cavity decay time). This scheme can serve as a precise measurement tool for the excitonic emission of layered materials into cavity modes, for both in plane and out of plane excitation.

Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission

NASA Astrophysics Data System (ADS)

Stern, Hannah L.; Cheminal, Alexandre; Yost, Shane R.; Broch, Katharina; Bayliss, Sam L.; Chen, Kai; Tabachnyk, Maxim; Thorley, Karl; Greenham, Neil; Hodgkiss, Justin M.; Anthony, John; Head-Gordon, Martin; Musser, Andrew J.; Rao, Akshay; Friend, Richard H.

2017-12-01

Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S1) into two spin-triplet excitons (T1), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S1 has been shown to occur efficiently and independently of temperature, even when the energy of S1 is as much as 200 meV less than that of 2T1. Here we study films of triisopropylsilyltetracene using transient optical spectroscopy and show that the triplet pair state (TT), which has been proposed to mediate singlet fission, forms on ultrafast timescales (in 300 fs) and that its formation is mediated by the strong coupling of electronic and vibrational degrees of freedom. This is followed by a slower loss of singlet character as the excitation evolves to become only TT. We observe the TT to be thermally dissociated on 10-100 ns timescales to form free triplets. This provides a model for 'temperature-independent' efficient TT formation and thermally activated TT separation.

Nano-scale engineering using lead chalcogenide nanocrystals for opto-electronic applications

NASA Astrophysics Data System (ADS)

Xu, Fan

Colloidal quantum dots (QDs) or nanocrystals of inorganic semiconductors exhibit exceptional optoelectronic properties such as tunable band-gap, high absorption cross-section and narrow emission spectra. This thesis discusses the characterizations and physical properties of lead-chalcogenide nanocrystals, their assembly into more complex nanostructures and applications in solar cells and near-infrared light-emitting devices. In the first part of this work, we demonstrate that the band edge emission of PbS quantum dots can be tuned from the visible to the mid-infrared region through size control, while the self-attachment of PbS nanocrystals can lead to the formation of 1-D nanowires, 2-D quantum dot monolayers and 3-D quantum dot solids. In particular, the assembly of closely-packed quantum dot solids has attracted enormous attention. A series of distinctive optoelectronic properties has been observed, such as superb multiple exciton generation efficiencies, efficient hot-electron transfer and cold-exciton recycling. Since the surfactant determines the quantum dot surface passivation and inter dot electronic coupling, we examine the influence of different cross-linking surfactants on the optoelectronic properties of the quantum dot solids. Then, we discuss the ability to tune the quantum dot band-gap combined with the controllable assembly of lead-chalcogenide quantum dots, which opens new possibilities to engineer the properties of quantum dot solids. The PbS and PbSe quantum dot cascade structures and PbS/PbSe quantum dot heterojunctions are assembled using the layer-by-layer deposition method. We show that exciton funnelling and trap state-bound exciton recycling in the quantum dot cascade structure dramatically enhances the quantum dots photoluminescence. Moreover, we show that both type-I and type-II PbS/PbSe quantum dot heterojunctions can be assembled by carefully choosing the quantum dot sizes. In type-I heterojunctions, the excited electron-hole pairs tend to localize in narrower band-gap quantum dots, leading to significant photoluminescence enhancement. In contrast, the staggered energy bands in type-II heterojunctions lead to rapid exciton separation at the junctions that considerably quenches the photoluminescence. As such, this strategy can be fruitfully employed to enhance performances in nanocrystal-based photovoltaic devices. Using this approach, we achieve efficient PbS nanocrystal-based solar cells using an ITO/ TiO2/ PbS QDs/Au architecture, where a porous TiO2 nanowire network is employed as electron transporting layer. Our best heterojunction solar cells exhibit a decent short circuit current of 2.5 mA/cm2, a large open circuit voltage of 0.6 V and a power converting efficiency of 5.4 % under 8.5 mW/cm2 low-light illumination. On the other hand, nanocrystal-based near infrared LED devices are fabricated using a simple ITO-PbS QDs-Al device structure. There, the active quantum dot layer serves as both the electron- and hole-transporting layer. With appropriate surface chemistry treatment on quantum dots, a high-brightness near-infrared LED device is achieved.

Numerical modeling of exciton-polariton Bose-Einstein condensate in a microcavity

NASA Astrophysics Data System (ADS)

Voronych, Oksana; Buraczewski, Adam; Matuszewski, Michał; Stobińska, Magdalena

2017-06-01

A novel, optimized numerical method of modeling of an exciton-polariton superfluid in a semiconductor microcavity was proposed. Exciton-polaritons are spin-carrying quasiparticles formed from photons strongly coupled to excitons. They possess unique properties, interesting from the point of view of fundamental research as well as numerous potential applications. However, their numerical modeling is challenging due to the structure of nonlinear differential equations describing their evolution. In this paper, we propose to solve the equations with a modified Runge-Kutta method of 4th order, further optimized for efficient computations. The algorithms were implemented in form of C++ programs fitted for parallel environments and utilizing vector instructions. The programs form the EPCGP suite which has been used for theoretical investigation of exciton-polaritons. Catalogue identifier: AFBQ_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AFBQ_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: BSD-3 No. of lines in distributed program, including test data, etc.: 2157 No. of bytes in distributed program, including test data, etc.: 498994 Distribution format: tar.gz Programming language: C++ with OpenMP extensions (main numerical program), Python (helper scripts). Computer: Modern PC (tested on AMD and Intel processors), HP BL2x220. Operating system: Unix/Linux and Windows. Has the code been vectorized or parallelized?: Yes (OpenMP) RAM: 200 MB for single run Classification: 7, 7.7. Nature of problem: An exciton-polariton superfluid is a novel, interesting physical system allowing investigation of high temperature Bose-Einstein condensation of exciton-polaritons-quasiparticles carrying spin. They have brought a lot of attention due to their unique properties and potential applications in polariton-based optoelectronic integrated circuits. This is an out-of-equilibrium quantum system confined within a semiconductor microcavity. It is described by a set of nonlinear differential equations similar in spirit to the Gross-Pitaevskii (GP) equation, but their unique properties do not allow standard GP solving frameworks to be utilized. Finding an accurate and efficient numerical algorithm as well as development of optimized numerical software is necessary for effective theoretical investigation of exciton-polaritons. Solution method: A Runge-Kutta method of 4th order was employed to solve the set of differential equations describing exciton-polariton superfluids. The method was fitted for the exciton-polariton equations and further optimized. The C++ programs utilize OpenMP extensions and vector operations in order to fully utilize the computer hardware. Running time: 6h for 100 ps evolution, depending on the values of parameters

Plasmon-induced carrier polarization in semiconductor nanocrystals.

PubMed

Yin, Penghui; Tan, Yi; Fang, Hanbing; Hegde, Manu; Radovanovic, Pavle V

2018-06-01

Spintronics 1 and valleytronics 2 are emerging quantum electronic technologies that rely on using electron spin and multiple extrema of the band structure (valleys), respectively, as additional degrees of freedom. There are also collective properties of electrons in semiconductor nanostructures that potentially could be exploited in multifunctional quantum devices. Specifically, plasmonic semiconductor nanocrystals 3-10 offer an opportunity for interface-free coupling between a plasmon and an exciton. However, plasmon-exciton coupling in single-phase semiconductor nanocrystals remains challenging because confined plasmon oscillations are generally not resonant with excitonic transitions. Here, we demonstrate a robust electron polarization in degenerately doped In 2 O 3 nanocrystals, enabled by non-resonant coupling of cyclotron magnetoplasmonic modes 11 with the exciton at the Fermi level. Using magnetic circular dichroism spectroscopy, we show that intrinsic plasmon-exciton coupling allows for the indirect excitation of the magnetoplasmonic modes, and subsequent Zeeman splitting of the excitonic states. Splitting of the band states and selective carrier polarization can be manipulated further by spin-orbit coupling. Our results effectively open up the field of plasmontronics, which involves the phenomena that arise from intrinsic plasmon-exciton and plasmon-spin interactions. Furthermore, the dynamic control of carrier polarization is readily achieved at room temperature, which allows us to harness the magnetoplasmonic mode as a new degree of freedom in practical photonic, optoelectronic and quantum-information processing devices.

Plasmon-induced carrier polarization in semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Yin, Penghui; Tan, Yi; Fang, Hanbing; Hegde, Manu; Radovanovic, Pavle V.

2018-06-01

Spintronics1 and valleytronics2 are emerging quantum electronic technologies that rely on using electron spin and multiple extrema of the band structure (valleys), respectively, as additional degrees of freedom. There are also collective properties of electrons in semiconductor nanostructures that potentially could be exploited in multifunctional quantum devices. Specifically, plasmonic semiconductor nanocrystals3-10 offer an opportunity for interface-free coupling between a plasmon and an exciton. However, plasmon-exciton coupling in single-phase semiconductor nanocrystals remains challenging because confined plasmon oscillations are generally not resonant with excitonic transitions. Here, we demonstrate a robust electron polarization in degenerately doped In2O3 nanocrystals, enabled by non-resonant coupling of cyclotron magnetoplasmonic modes11 with the exciton at the Fermi level. Using magnetic circular dichroism spectroscopy, we show that intrinsic plasmon-exciton coupling allows for the indirect excitation of the magnetoplasmonic modes, and subsequent Zeeman splitting of the excitonic states. Splitting of the band states and selective carrier polarization can be manipulated further by spin-orbit coupling. Our results effectively open up the field of plasmontronics, which involves the phenomena that arise from intrinsic plasmon-exciton and plasmon-spin interactions. Furthermore, the dynamic control of carrier polarization is readily achieved at room temperature, which allows us to harness the magnetoplasmonic mode as a new degree of freedom in practical photonic, optoelectronic and quantum-information processing devices.

Giant Gating Tunability of Optical Refractive Index in Transition Metal Dichalcogenide Monolayers.

PubMed

Yu, Yiling; Yu, Yifei; Huang, Lujun; Peng, Haowei; Xiong, Liwei; Cao, Linyou

2017-06-14

We report that the refractive index of transition metal dichacolgenide (TMDC) monolayers, such as MoS 2 , WS 2 , and WSe 2 , can be substantially tuned by >60% in the imaginary part and >20% in the real part around exciton resonances using complementary metal-oxide-semiconductor (CMOS) compatible electrical gating. This giant tunablility is rooted in the dominance of excitonic effects in the refractive index of the monolayers and the strong susceptibility of the excitons to the influence of injected charge carriers. The tunability mainly results from the effects of injected charge carriers to broaden the spectral width of excitonic interband transitions and to facilitate the interconversion of neutral and charged excitons. The other effects of the injected charge carriers, such as renormalizing bandgap and changing exciton binding energy, only play negligible roles. We also demonstrate that the atomically thin monolayers, when combined with photonic structures, can enable the efficiencies of optical absorption (reflection) tuned from 40% (60%) to 80% (20%) due to the giant tunability of the refractive index. This work may pave the way toward the development of field-effect photonics in which the optical functionality can be controlled with CMOS circuits.

The Role of Triplet Exciton Diffusion in Light-Upconverting Polymer Glasses.

PubMed

Raišys, Steponas; Kazlauskas, Karolis; Juršėnas, Saulius; Simon, Yoan C

2016-06-22

Light upconversion (UC) via triplet-triplet annihilation (TTA) by using noncoherent photoexcitation at subsolar irradiance power densities is extremely attractive, particularly for enhanced solar energy harvesting. Unfortunately, practical TTA-UC application is hampered by low UC efficiency of upconverting polymer glasses, which is commonly attributed to poor exciton diffusion of the triplet excitons across emitter molecules. The present study addresses this issue by systematically evaluating triplet exciton diffusion coefficients and diffusion lengths (LD) in a UC model system based on platinum-octaethylporphyrin-sensitized poly(methyl methacrylate)/diphenylanthracene (emitter) films as a function of emitter concentration (15-40 wt %). For this evaluation time-resolved photoluminescence bulk-quenching technique followed by Stern-Volmer-type quenching analysis of experimental data was employed. The key finding is that although increasing emitter concentration in the disordered PMMA/DPA/PtOEP films improves triplet exciton diffusion, and thus LD, this does not result in enhanced UC quantum yield. Conversely, improved LD accompanied by the accelerated decay of UC intensity on millisecond time scale degrades TTA-UC performance at high emitter loadings (>25 wt %) and suggests that diffusion-enhanced nonradiative decay of triplet excitons is the major limiting factor.

Charge carrier localised in zero-dimensional (CH3NH3)3Bi2I9 clusters.

PubMed

Ni, Chengsheng; Hedley, Gordon; Payne, Julia; Svrcek, Vladimir; McDonald, Calum; Jagadamma, Lethy Krishnan; Edwards, Paul; Martin, Robert; Jain, Gunisha; Carolan, Darragh; Mariotti, Davide; Maguire, Paul; Samuel, Ifor; Irvine, John

2017-08-01

A metal-organic hybrid perovskite (CH 3 NH 3 PbI 3 ) with three-dimensional framework of metal-halide octahedra has been reported as a low-cost, solution-processable absorber for a thin-film solar cell with a power-conversion efficiency over 20%. Low-dimensional layered perovskites with metal halide slabs separated by the insulating organic layers are reported to show higher stability, but the efficiencies of the solar cells are limited by the confinement of excitons. In order to explore the confinement and transport of excitons in zero-dimensional metal-organic hybrid materials, a highly orientated film of (CH 3 NH 3 ) 3 Bi 2 I 9 with nanometre-sized core clusters of Bi 2 I 9 3- surrounded by insulating CH 3 NH 3 + was prepared via solution processing. The (CH 3 NH 3 ) 3 Bi 2 I 9 film shows highly anisotropic photoluminescence emission and excitation due to the large proportion of localised excitons coupled with delocalised excitons from intercluster energy transfer. The abrupt increase in photoluminescence quantum yield at excitation energy above twice band gap could indicate a quantum cutting due to the low dimensionality.Understanding the confinement and transport of excitons in low dimensional systems will aid the development of next generation photovoltaics. Via photophysical studies Ni et al. observe 'quantum cutting' in 0D metal-organic hybrid materials based on methylammonium bismuth halide (CH 3 NH 3 )3Bi 2 I 9 .

An easily reversible structural change underlies mechanisms enabling desert crust cyanobacteria to survive desiccation.

PubMed

Bar-Eyal, Leeat; Eisenberg, Ido; Faust, Adam; Raanan, Hagai; Nevo, Reinat; Rappaport, Fabrice; Krieger-Liszkay, Anja; Sétif, Pierre; Thurotte, Adrien; Reich, Ziv; Kaplan, Aaron; Ohad, Itzhak; Paltiel, Yossi; Keren, Nir

2015-10-01

Biological desert sand crusts are the foundation of desert ecosystems, stabilizing the sands and allowing colonization by higher order organisms. The first colonizers of the desert sands are cyanobacteria. Facing the harsh conditions of the desert, these organisms must withstand frequent desiccation-hydration cycles, combined with high light intensities. Here, we characterize structural and functional modifications to the photosynthetic apparatus that enable a cyanobacterium, Leptolyngbya sp., to thrive under these conditions. Using multiple in vivo spectroscopic and imaging techniques, we identified two complementary mechanisms for dissipating absorbed energy in the desiccated state. The first mechanism involves the reorganization of the phycobilisome antenna system, increasing excitonic coupling between antenna components. This provides better energy dissipation in the antenna rather than directed exciton transfer to the reaction center. The second mechanism is driven by constriction of the thylakoid lumen which limits diffusion of plastocyanin to P700. The accumulation of P700(+) not only prevents light-induced charge separation but also efficiently quenches excitation energy. These protection mechanisms employ existing components of the photosynthetic apparatus, forming two distinct functional modes. Small changes in the structure of the thylakoid membranes are sufficient for quenching of all absorbed energy in the desiccated state, protecting the photosynthetic apparatus from photoinhibitory damage. These changes can be easily reversed upon rehydration, returning the system to its high photosynthetic quantum efficiency. Copyright © 2015 Elsevier B.V. All rights reserved.

Formation of plasmon pulses in the cooperative decay of excitons of quantum dots near a metal surface

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

Shesterikov, A. B.; Gubin, M. Yu.; Gladush, M. G.

The formation of pulses of surface electromagnetic waves at a metal–dielectric boundary is considered in the process of cooperative decay of excitons of quantum dots distributed near a metal surface in a dielectric layer. It is shown that the efficiency of exciton energy transfer to excited plasmons can, in principle, be increased by selecting the dielectric material with specified values of the complex permittivity. It is found that in the mean field approximation, the semiclassical model of formation of plasmon pulses in the system under study is reduced to the pendulum equation with the additional term of nonlinear losses.

Excitonic transitions in highly efficient (GaIn)As/Ga(AsSb) type-II quantum-well structures

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

Gies, S.; Kruska, C.; Berger, C.

2015-11-02

The excitonic transitions of the type-II (GaIn)As/Ga(AsSb) gain medium of a “W”-laser structure are characterized experimentally by modulation spectroscopy and analyzed using microscopic quantum theory. On the basis of the very good agreement between the measured and calculated photoreflectivity, the type-I or type-II character of the observable excitonic transitions is identified. Whereas the energetically lowest three transitions exhibit type-II character, the subsequent energetically higher transitions possess type-I character with much stronger dipole moments. Despite the type-II character, the quantum-well structure exhibits a bright luminescence.

Nonlinear absorption in AlGaAs/GaAs multiple quantum well structures grown by metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Lee, H. C.; Hariz, A.; Dapkus, P. D.; Kost, A.; Kawase, M.

1987-01-01

This paper reports the study of growth conditions for achieving the sharp exciton resonances and low-intensity saturation of these resonances in AlGaAs-GaAs multiple quantum well structures grown by metalorganic chemical vapor deposition. Low growth temperature is necessary to observe this sharp resonance feature at room temperature. The optimal growth conditions are a tradeoff between the high temperatures required for high quality AlGaAs and low temperatures required for high-purity GaAs. A strong optical saturation of the excitonic absorption has been observed. A saturation density as low as 250 W/sq cm is reported.

Luminescence of quantum-well exciton polaritons from microstructured AlxGa1-xAs-GaAs multiple quantum wells

NASA Astrophysics Data System (ADS)

Kohl, M.; Heitmann, D.; Grambow, P.; Ploog, K.

1988-06-01

Periodic multiple-quantum-well wires have been prepared by etching five-layer quantum-well structures through a holographically prepared mask. The periodicity was 380 nm, the lateral confinement 180 nm, and the quantum-well width 13, nm. The luminescence from these microstructured systems in the frequency regime of the one-electron-one-heavy-hole transition was strongly polarized with the electric field perpendicular to the periodic structure. This effect was caused by the resonantly enhanced emission of quantum-well-exciton (QWE) polaritons. Excitation of QWE polaritons was also observed in reflection measurements on the microstructured samples.

Impact of undamped and damped intramolecular vibrations on the efficiency of photosynthetic exciton energy transfer

NASA Astrophysics Data System (ADS)

Juhász, Imre Benedek; Csurgay, Árpád I.

2018-04-01

In recent years, the role of molecular vibrations in exciton energy transfer taking place during the first stage of photosynthesis attracted increasing interest. Here, we present a model formulated as a Lindblad-type master equation that enables us to investigate the impact of undamped and especially damped intramolecular vibrational modes on the exciton energy transfer, particularly its efficiency. Our simulations confirm the already reported effects that the presence of an intramolecular vibrational mode can compensate the energy detuning of electronic states, thus promoting the energy transfer; and, moreover, that the damping of such a vibrational mode (in other words, vibrational relaxation) can further enhance the efficiency of the process by generating directionality in the energy flow. As a novel result, we show that this enhancement surpasses the one caused by pure dephasing, and we present its dependence on various system parameters (time constants of the environment-induced relaxation and excitation processes, detuning of the electronic energy levels, frequency of the intramolecular vibrational modes, Huang-Rhys factors, temperature) in dimer model systems. We demonstrate that vibrational-relaxation-enhanced exciton energy transfer (VREEET) is robust against the change of these characteristics of the system and occurs in wide ranges of the investigated parameters. With simulations performed on a heptamer model inspired by the Fenna-Matthews-Olson (FMO) complex, we show that this mechanism can be even more significant in larger systems at T = 300 K. Our results suggests that VREEET might be prevalent in light-harvesting complexes.

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.

A multi-timescale map of radiative and nonradiative decay pathways for excitons in CdSe quantum dots.

PubMed

Knowles, Kathryn E; McArthur, Eric A; Weiss, Emily A

2011-03-22

A combination of transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopies performed on solution-phase samples of colloidal CdSe quantum dots (QDs) allows the construction of a time-resolved, charge carrier-resolved map of decay from the first excitonic state of the QD. Data from TA and TRPL yield the same six exponential components, with time constants ranging from ∼1 ps to 50 ns, for excitonic decay. Comparison of TA signals in the visible and near-infrared (NIR) spectral regions enables determination of the relative contributions of electron and hole dynamics to each decay component, and comparison of TA and TRPL reveals that each component represents a competition between radiative and nonradiative decay pathways. In total, these data suggest that the QD sample comprises at least three distinct populations that differ in both the radiative and nonradiative decay pathways available to the excitonic charge carriers, and provide evidence for multiple emissive excitonic states in which the hole is not in the valence band, but rather a relaxed or trapped state.

Dependence of Exciton Diffusion Length and Diffusion Coefficient on Photophysical Parameters in Bulk Heterojunction Organic Solar Cells

NASA Astrophysics Data System (ADS)

Yeboah, Douglas; Singh, Jai

2017-11-01

Recently, the dependence of exciton diffusion length (LD ) on some photophysical parameters of organic solids has been experimentally demonstrated, however no systematic theoretical analysis of this phenomenon has been carried out. We have conducted a theoretical study by using the Förster resonance energy transfer and Dexter carrier transfer mechanisms together with the Einstein-Smoluchowski diffusion equation to derive analytical models for the diffusion lengths (LD ) and diffusion coefficients (D) of singlet (S) and triplet (T) excitons in organic solids as functions of spectral overlap integral (J) , photoluminescence (PL) quantum yield (φD ) , dipole moment (μT ) and refractive index (n) of the photoactive material. The exciton diffusion lengths and diffusion coefficients in some selected organic solids were calculated, and we found that the singlet exciton diffusion length (LDS ) increases with φD and J, and decreases with n. Also, the triplet exciton diffusion length (LDT ) increases with φD and decreases with μT . These may be achieved through doping the organic solids into broad optical energy gap host materials as observed in previous experiments. The calculated exciton diffusion lengths are compared with experimental values and a reasonably good agreement is found between them. The results presented are expected to provide insight relevant to the synthesis of new organic solids for fabrication of bulk heterojunction organic solar cells characterized by better power conversion efficiency.

Surface plasmon-enhanced light-emitting diodes using silver nanoparticles embedded in p-GaN.

PubMed

Cho, Chu-Young; Kwon, Min-Ki; Lee, Sang-Jun; Han, Sang-Heon; Kang, Jang-Won; Kang, Se-Eun; Lee, Dong-Yul; Park, Seong-Ju

2010-05-21

We demonstrate the surface plasmon-enhanced blue light-emitting diodes (LEDs) using Ag nanoparticles embedded in p-GaN. A large increase in optical output power of 38% is achieved at an injection current of 20 mA due to an improved internal quantum efficiency of the LEDs. The enhancement of optical output power is dependent on the density of the Ag nanoparticles. This improvement can be attributed to an increase in the spontaneous emission rate through resonance coupling between the excitons in multiple quantum wells and localized surface plasmons in Ag nanoparticles embedded in p-GaN.

Controlled defects in semiconducting carbon nanotubes promote efficient generation and luminescence of trions.

PubMed

Brozena, Alexandra H; Leeds, Jarrett D; Zhang, Yin; Fourkas, John T; Wang, YuHuang

2014-05-27

We demonstrate efficient creation of defect-bound trions through chemical doping of controlled sp(3) defect sites in semiconducting, single-walled carbon nanotubes. These tricarrier quasi-particles luminesce almost as brightly as their parent excitons, indicating a remarkably efficient conversion of excitons into trions. Substantial populations of trions can be generated at low excitation intensities, even months after a sample has been prepared. Photoluminescence spectroscopy reveals a trion binding energy as high as 262 meV, which is substantially larger than any previously reported values. This discovery may have important ramifications not only for studying the basic physics of trions but also for the application of these species in fields such as photonics, electronics, and bioimaging.

Exciton generation/dissociation/charge-transfer enhancement in inorganic/organic hybrid solar cells by robust single nanocrystalline LnPxOy (Ln = Eu, Y) doping.

PubMed

Jin, Xiao; Sun, Weifu; Chen, Zihan; Wei, Taihuei; Chen, Chuyang; He, Xingdao; Yuan, Yongbiao; Li, Yue; Li, Qinghua

2014-06-11

Low-temperature solution-processed photovoltaics suffer from low efficiencies because of poor exciton or electron-hole transfer. Inorganic/organic hybrid solar cell, although still in its infancy, has attracted great interest thus far. One of the promising ways to enhance exciton dissociation or electron-hole transport is the doping of lanthanide phosphate ions. However, the underlying photophysical mechanism remains poorly understood. Herein, by applying femtosecond transient absorption spectroscopy, we successfully distinguished hot electron, less energetic electron, hole transport from electron-hole recombination. Concrete evidence has been provided that lanthanide phosphate doping improves the efficiency of both hot electron and "less energetic" electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 12.7 ps, that is, more than 60% faster than pure TiO2 acceptor. Such improvement was ascribed to the facts that the conduction band (CB) edge energy level of TiO2 has been elevated by 0.2 eV, while the valence band level almost remains unchanged, thus not only narrowing the energy offset between CB levels of TiO2 and P3HT, but also meanwhile enlarging the band gap of TiO2 itself that permits one to inhibit electron-hole recombination within TiO2. Consequently, lanthanide phosphate doped TiO2/P3HT bulk-heterojunction solar cell has been demonstrated to be a promising hybrid solar cell, and a notable power conversion efficiency of 2.91% is therefore attained. This work indicates that lanthanide compound ions can efficiently facilitate exciton generation, dissociation, and charge transport, thus enhancing photovoltaic performance.

Enhanced performances for top-emitting white organic light-emitting diodes by utilizing green phosphor as energy transfer medium

NASA Astrophysics Data System (ADS)

Deng, Lingling; Bao, Yiyang; Zhang, Yanan; Peng, Ling; Zhu, Wenjing; Zhao, Yue; Xu, Yewen; Chen, Shufen

2016-06-01

In top-emitting white organic light-emitting diodes (TWOLEDs), the device performances attribute to the several important factors, such as exciton profile, energy transfer, and microcavity effect. In this paper, a TWOLED containing a heterojunction blue emission layer (EML) and a red EML is reported. A host material with high triplet energy level is employed for the adjacent blue and red EML, while the inefficient red emission reduces the emission efficiency of the TWOLED. In order to enhance the red emission efficiency, mixed-host and co-doping technologies are used in the red EML. By mixing the hole transporting and electron transporting host materials, the exciton recombination zone extends to the red EML to increase the red emission intensity and reduce the efficiency roll-off. And by co-doping a green phosphor into the red EML as the energy transfer medium, the energy transfer rate is enhanced, and then the current efficiency increases. Besides, both the mixed-host and co-doping change the carrier transport and the exciton recombination zone, which further affects the microcavity resonance in the devices. Due to the enhancement on the red emission intensity and the shift of resonant wavelength, the chromaticity of the TWOLED is improved.

Crystal-Phase Quantum Wires: One-Dimensional Heterostructures with Atomically Flat Interfaces.

PubMed

Corfdir, Pierre; Li, Hong; Marquardt, Oliver; Gao, Guanhui; Molas, Maciej R; Zettler, Johannes K; van Treeck, David; Flissikowski, Timur; Potemski, Marek; Draxl, Claudia; Trampert, Achim; Fernández-Garrido, Sergio; Grahn, Holger T; Brandt, Oliver

2018-01-10

In semiconductor quantum-wire heterostructures, interface roughness leads to exciton localization and to a radiative decay rate much smaller than that expected for structures with flat interfaces. Here, we uncover the electronic and optical properties of the one-dimensional extended defects that form at the intersection between stacking faults and inversion domain boundaries in GaN nanowires. We show that they act as crystal-phase quantum wires, a novel one-dimensional quantum system with atomically flat interfaces. These quantum wires efficiently capture excitons whose radiative decay gives rise to an optical doublet at 3.36 eV at 4.2 K. The binding energy of excitons confined in crystal-phase quantum wires is measured to be more than twice larger than that of the bulk. As a result of their unprecedented interface quality, these crystal-phase quantum wires constitute a model system for the study of one-dimensional excitons.

Composition-Dependent Energy Splitting between Bright and Dark Excitons in Lead Halide Perovskite Nanocrystals.

PubMed

Chen, Lan; Li, Bin; Zhang, Chunfeng; Huang, Xinyu; Wang, Xiaoyong; Xiao, Min

2018-03-14

Perovskite semiconductor nanocrystals with different compositions have shown promise for applications in light-emitting devices. Dark excitonic states may suppress light emission from such nanocrystals by providing an additional nonradiative recombination channel. Here, we study the composition dependence of dark exciton dynamics in nanocrystals of lead halides by time-resolved photoluminescence spectroscopy at cryogenic temperatures. The presence of a spin-related dark state is revealed by magneto-optical spectroscopy. The energy splitting between bright and dark states is found to be highly sensitive to both halide elements and organic cations, which is explained by considering the effects of size confinement and charge screening, respectively, on the exchange interaction. These findings suggest the possibility of manipulating dark exciton dynamics in perovskite semiconductor nanocrystals by composition engineering, which will be instrumental in the design of highly efficient light-emitting devices.

Exciton versus free carrier photogeneration in organometal trihalide perovskites probed by broadband ultrafast polarization memory dynamics.

PubMed

Sheng, ChuanXiang; Zhang, Chuang; Zhai, Yaxin; Mielczarek, Kamil; Wang, Weiwei; Ma, Wanli; Zakhidov, Anvar; Vardeny, Z Valy

2015-03-20

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH(3)NH(3)PbI(3) and CH(3)NH(3)PbI(1.1)Br(1.9) using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH(3)NH(3)PbI(3) with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH(3)NH(3)PbI(1.1)Br(1.9). Surprisingly, we also discovered in CH(3)NH(3)PbI(3), but not in CH(3)NH(3)PbI(1.1)Br(1.9), transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH(3)NH(3)PbI(3), D≈0.01  cm(2) s(-1).

Exciton versus Free Carrier Photogeneration in Organometal Trihalide Perovskites Probed by Broadband Ultrafast Polarization Memory Dynamics

NASA Astrophysics Data System (ADS)

Sheng, ChuanXiang; Zhang, Chuang; Zhai, Yaxin; Mielczarek, Kamil; Wang, Weiwei; Ma, Wanli; Zakhidov, Anvar; Vardeny, Z. Valy

2015-03-01

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH3NH3PbI3 and CH3NH3PbI1.1Br1.9 using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH3NH3PbI3 with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH3NH3PbI1.1Br1.9 . Surprisingly, we also discovered in CH3NH3PbI3 , but not in CH3NH3PbI1.1Br1.9 , transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH3NH3PbI3 , D ≈0.01 cm2 s-1 .

Toward Computational Design of High-Efficiency Photovoltaics from First-Principles

DTIC Science & Technology

2016-08-15

dependence of exciton diffusion in conjugated small molecules, Applied Physics Letters, (04 2014): 0. doi: 10.1063/1.4871303 Guangfen Wu, Zi Li, Xu...principle approach based on the time- dependent density functional theory (TDDFT) to describe exciton states, including energy levels and many-body wave... depends more sensitively on the dimension and crystallinity of the acceptor parallel to the interface than normal to the interface. Reorganization

Charge recombination in organic photovoltaic devices with high open-circuit voltages.

PubMed

Westenhoff, Sebastian; Howard, Ian A; Hodgkiss, Justin M; Kirov, Kiril R; Bronstein, Hugo A; Williams, Charlotte K; Greenham, Neil C; Friend, Richard H

2008-10-15

A detailed charge recombination mechanism is presented for organic photovoltaic devices with a high open-circuit voltage. In a binary blend comprised of polyfluorene copolymers, the performance-limiting process is found to be the efficient recombination of tightly bound charge pairs into neutral triplet excitons. We arrive at this conclusion using optical transient absorption (TA) spectroscopy with visible and IR probes and over seven decades of time resolution. By resolving the polarization of the TA signal, we track the movement of polaronic states generated at the heterojunction not only in time but also in space. It is found that the photogenerated charge pairs are remarkably immobile at the heterojunction during their lifetime. The charge pairs are shown to be subject to efficient intersystem crossing and terminally recombine into F8BT triplet excitons within approximately 40 ns. Long-range charge separation competes rather unfavorably with intersystem crossing--75% of all charge pairs decay into triplet excitons. Triplet exciton states are thermodynamically accessible in polymer solar cells with high open circuit voltage, and we therefore suggest this loss mechanism to be general. We discuss guidelines for the design of the next generation of organic photovoltaic materials where separating the metastable interfacial charge pairs within approximately 40 ns is paramount.

Effects of Organic Cation Length on Exciton Recombination in Two-Dimensional Layered Lead Iodide Hybrid Perovskite Crystals.

PubMed

Gan, Lu; Li, Jing; Fang, Zhishan; He, Haiping; Ye, Zhizhen

2017-10-19

In recent years, 2D layered organic-inorganic lead halide perovskites have attracted considerable attention due to the distinctive quantum confinement effects as well as prominent excitonic luminescence. Herein, we show that the recombination dynamics and photoluminescence (PL) of the 2D layered perovskites can be tuned by the organic cation length. 2D lead iodide perovskite crystals with increased length of the organic chains reveal blue-shifted PL as well as enhanced relative internal quantum efficiency. Furthermore, we provide experimental evidence that the formation of face-sharing [PbI 6 ] 4- octahedron in perovskites with long alkyls induces additional confinement for the excitons, leading to 1D-like recombination. As a result, the PL spectra show enhanced inhomogeneous broadening at low temperature. Our work provides physical understanding of the role of organic cation in the optical properties of 2D layered perovskites, and would benefit the improvement of luminescence efficiency of such materials.

Invoking Direct Exciton-Plasmon Interactions by Catalytic Ag Deposition on Au Nanoparticles: Photoelectrochemical Bioanalysis with High Efficiency.

PubMed

Ma, Zheng-Yuan; Xu, Fei; Qin, Yu; Zhao, Wei-Wei; Xu, Jing-Juan; Chen, Hong-Yuan

2016-04-19

In this work, direct exciton-plasmon interactions (EPI) between CdS quantum dots (QDs) and Ag nanoparticles (NPs) were invoked ingeniously by catalytic Ag deposition on Au NPs for the stimulation of high efficient damping effect toward the excitonic responses in CdS QDs, on the basis of which a novel photoelectrochemical (PEC) bioanalytical format was achieved for sensitive microRNA detection. Specifically, upon the configurational change from the hairpin probe DNA to the "Y"-shaped ternary conjugate consisting of the original probe DNA, assistant DNA, and the target microRNA, the alkaline phosphatase (ALP) catalytic chemistry would then trigger the transition of the interparticle interplay from the CdS QDs-Au NPs to the CdS QDs-Ag NPs systems for the microRNA detection due to the dependence of the photocurrent quenching on the target concentration. This work not only provided a unique method for EPI generation among the PEC nanosystems but also offered a versatile and general protocol for future PEC bioanalysis development.

Continuous-time quantum walk on an extended star graph: Trapping and superradiance transition

NASA Astrophysics Data System (ADS)

Yalouz, Saad; Pouthier, Vincent

2018-02-01

A tight-binding model is introduced for describing the dynamics of an exciton on an extended star graph whose central node is occupied by a trap. On this graph, the exciton dynamics is governed by two kinds of eigenstates: many eigenstates are associated with degenerate real eigenvalues insensitive to the trap, whereas three decaying eigenstates characterized by complex energies contribute to the trapping process. It is shown that the excitonic population absorbed by the trap depends on the size of the graph, only. By contrast, both the size parameters and the absorption rate control the dynamics of the trapping. When these parameters are judiciously chosen, the efficiency of the transfer is optimized resulting in the minimization of the absorption time. Analysis of the eigenstates reveals that such a feature arises around the superradiance transition. Moreover, depending on the size of the network, two situations are highlighted where the transport efficiency is either superoptimized or suboptimized.

Dual enhancement of electroluminescence efficiency and operational stability by rapid upconversion of triplet excitons in OLEDs

PubMed Central

Furukawa, Taro; Nakanotani, Hajime; Inoue, Munetomo; Adachi, Chihaya

2015-01-01

Recently, triplet harvesting via a thermally activated delayed fluorescence (TADF) process has been established as a realistic route for obtaining ultimate internal electroluminescence (EL) quantum efficiency in organic light-emitting diodes (OLEDs). However, the possibility that the rather long transient lifetime of the triplet excited states would reduce operational stability due to an increased chance for unwarranted chemical reactions has been a concern. Herein, we demonstrate dual enhancement of EL efficiency and operational stability in OLEDs by employing a TADF molecule as an assistant dopant and a fluorescent molecule as an end emitter. The proper combination of assistant dopant and emitter molecules realized a “one-way” rapid Förster energy transfer of singlet excitons from TADF molecules to fluorescent emitters, reducing the number of cycles of intersystem crossing (ISC) and reverse ISC in the TADF molecules and resulting in a significant enhancement of operational stability compared to OLEDs with a TADF molecule as the end emitter. In addition, we found that the presence of this rapid energy transfer significantly suppresses singlet-triplet annihilation. Using this finely-tuned rapid triplet-exciton upconversion scheme, OLED performance and lifetime was greatly improved. PMID:25673259

Hole transfer from CdSe nanoparticles to TQ1 polymer in hybrid solar cell device

NASA Astrophysics Data System (ADS)

Sohail, Muhammad; Shah, Zawar Hussain; Saeed, Shomaila; Bibi, Nasreen; Shahbaz, Sadia; Ahmed, Safeer; Shabbir, Saima; Siddiq, Muhammad; Iqbal, Azhar

2018-05-01

In view of realizing the economic viability, we fabricate a solar cell device containing low band gap and easily processable polymer 5-yl-8-(thiophene-2,5-diyl)-2,3-bis(3-(octyloxy)phenyl) quinoxaline (TQ1) and CdSe nanoparticles (NPs) and investigate its charge transport properties. When the TQ1 is combined with the CdSe NPs a strong photoluminescence quenching and shortening of photoluminescence lifetime of the TQ1 is observed indicating exciton transfer from TQ1 to the CdSe NPs. The time-resolved photoluminescence further reveals that the exciton transfer from the polymer to CdSe NPs is very efficient (68%) and it occurs in <1 ns. The exciton transfer from TQ1 to the NPs and electron-hole pair separation followed by hole transfer from the NPs to the TQ1 at the interface indeed increases the lifetime of the charge carriers. This in turn increases the efficiency of the solar cell as compared to polymer only device. These observations suggest the importance of other II-VI semiconductor NPs to achieve higher efficiency for photovoltaic devices containing TQ1 polymer.

Controlled exciton transfer between quantum dots with acoustic phonons taken into account

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

Golovinski, P. A., E-mail: golovinski@bk.ru

2015-09-15

A system of excitons in two quantum dots coupled by the dipole–dipole interaction is investigated. The excitation transfer process controlled by the optical Stark effect at nonresonant frequencies is considered and the effect of the interaction between excitons and acoustic phonons in a medium on this process is taken into account. The system evolution is described using quantum Heisenberg equations. A truncated set of equations is obtained and the transfer dynamics is numerically simulated. High-efficiency picosecond switching of the excitation transfer by a laser pulse with a rectangular envelope is demonstrated. The dependence of picosecond switching on the quantum-dot parametersmore » and optical-pulse length is presented.« less

Excitonic fine-structure splitting in telecom-wavelength InAs/GaAs quantum dots: Statistical distribution and height-dependence

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

Goldmann, Elias, E-mail: goldmann@itp.uni-bremen.de; Barthel, Stefan; Florian, Matthias

The variation of the excitonic fine-structure splitting is studied for semiconductor quantum dots under the influence of a strain-reducing layer, utilized to shift the emission wavelength of the excitonic transition into the telecom-wavelength regime of 1.3–1.5 μm. By means of a sp{sup 3}s{sup *}-tight-binding model and configuration interaction, we calculate wavelength shifts and fine-structure splittings for various quantum dot geometries. We find the splittings remaining small and even decreasing with strain-reducing layer composition for quantum dots with large height. Combined with an observed increased emission efficiency, the applicability for generation of entanglement photons is persistent.

Light-induced nonadiabatic dynamics in molecular assemblies and nanostructures

NASA Astrophysics Data System (ADS)

Mitric, Roland

The combination of mixed quantum-classical dynamics with efficient electronic structure methods was developed in order to simulate the light-induced processes in complex molecules, multichromophoric aggregates and metallic nanostructures. We will demonstrate how the combination of nonadiabatic dynamics with experimental pump-probe techniques such as time-resolved photoelectron imaging (TRPEI) allows to fully resolve the mechanism of excited state relaxation through conical intersections in several prototype organic- and biomolecules. Specifically, the role of the solvent in the excited state relaxation in microsolvated and fully solvated systems will be addressed. Currently there is growing evidence that nonadiabatic relaxation processes also play a fundamental role in determining the efficiency of excitonic transfer or charge injection in multichromophoric assemblies. Since such systems are currently out of the reach of the state-of-the-art quantum chemistry a development of even more efficient quantum chemical approaches is necessary in order to describe the excited state dynamics in such assemblies. For this purpose we have recently developed long-range corrected time-dependent density functional tight binding (LC-TDDFTB) nonadiabatic dynamics and combined it with the QM/MM approach in order to simulate exciton relaxation in complex systems. The applications of the method to the investigation of the optical properties and dynamics in multichromophoric assemblies including stacked pi-conjugated organic chromophores, model molecular crystals as well as self-organized dye aggregates will be presented. Finally, we will address exciton transport dynamics coupled with the light propagation in hybrid exciton-plasmon nanostructures, which represent promising materials fort the development of novel light-harvesting systems.

Triplet Tellurophene-Based Acceptors for Organic Solar Cells.

PubMed

Yang, Lei; Gu, Wenxing; Lv, Lei; Chen, Yusheng; Yang, Yufei; Ye, Pan; Wu, Jianfei; Hong, Ling; Peng, Aidong; Huang, Hui

2018-01-22

Triplet materials have been employed to achieve high-performing organic solar cells (OSCs) by extending the exciton lifetime and diffusion distances, while the triplet non-fullerene acceptor materials have never been reported for bulk heterojunction OSCs. Herein, for the first time, three triplet molecular acceptors based on tellurophene with different degrees of ring fusing were designed and synthesized for OSCs. Significantly, these molecules have long exciton lifetime and diffusion lengths, leading to efficient power conversion efficiency (7.52 %), which is the highest value for tellurophene-based OSCs. The influence of the extent of ring fusing on molecular geometry and OSCs performance was investigated to show the power conversion efficiencies (PCEs) continuously increased along with increasing the extent of ring fusing. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triplet exciton confinement for enhanced fluorescent organic light-emitting diodes using a co-host system

NASA Astrophysics Data System (ADS)

Yoo, Han Kyu; Lee, Ho Won; Lee, Song Eun; Kim, Young Kwan; Kim, Se Hyun; Yoon, Seung Soo; Park, Jaehoon

2016-05-01

In this work, the co-host system within an emitting layer (EML) consists of the host and triplet managing (TM) host materials. A set of EML structures was fabricated with various concentrations of the TM host (0, 10, 30, 50, and 70%). The TM host triplet energy level is lower than the energy levels of the host and the guest, which leads to a reduction in the triplet exciton density and the singlet-triplet annihilation of the guest. Blue fluorescent organic light-emitting diodes exhibit a maximum luminous efficiency (LE) and an external quantum efficiency (EQE) of 9.74 cd/A and 4.92%, respectively. In addition, the efficiency roll-off ratios of the LE and the EQE are 14.25 and 13.16%, respectively.

Super-Poissonian statistics of photon emission from single CdSe-CdS core-shell nanocrystals coupled to metal nanostructures.

PubMed

Park, Young-Shin; Ghosh, Yagnaseni; Chen, Yongfen; Piryatinski, Andrei; Xu, Ping; Mack, Nathan H; Wang, Hsing-Lin; Klimov, Victor I; Hollingsworth, Jennifer A; Htoon, Han

2013-03-15

We demonstrate that photon antibunching observed for individual nanocrystal quantum dots (NQDs) can be transformed into photon bunching characterized by super-Poissonian statistics when they are coupled to metal nanostructures (MNs). This observation indicates that, while the quantum yield of a biexciton (Q(2X)) is lower than that of a single exciton (Q(1X)) in freestanding NQDs, Q(2X) becomes greater than Q(1X) in NQDs coupled to MNs. This unique phenomenon is attributed to metal-induced quenching with a rate that scales more slowly with exciton multiplicity than the radiative decay rate and dominates over other nonradiative decay channels for both single excitons and biexcitons.

Excitonic recombination dynamics in non-polar GaN/AlGaN quantum wells

NASA Astrophysics Data System (ADS)

Rosales, D.; Gil, B.; Bretagnon, T.; Guizal, B.; Zhang, F.; Okur, S.; Monavarian, M.; Izyumskaya, N.; Avrutin, V.; Özgür, Ü.; Morkoç, H.; Leach, J. H.

2014-02-01

The optical properties of GaN/Al0.15Ga0.85N multiple quantum wells are examined in 8 K-300 K temperature range. Both polarized CW and time resolved temperature-dependent photoluminescence experiment are performed so that we can deduce the relative contributions of the non-radiative and radiative recombination processes. From the calculation of the proportion of the excitonic population having wave vector in the light cone, we can deduce the variation of the radiative decay time with temperature. We find part of the excitonic population to be localized in concert with the report of Corfdir et al. (Jpn. J. Appl. Phys., Part 2 52, 08JC01 (2013)) in case of a-plane quantum wells.

Properties of excited states in organic light emitting diodes and lasers

NASA Astrophysics Data System (ADS)

Giebink, Noel C.

The field of organic semiconductors has grown rapidly over the past decade with the development of light emitting diodes, solar cells, and lasers that promise a new generation of low-cost, flexible optoelectronic devices. In each case, the behavior of molecular excited states, or excitons, is of fundamental importance. The present study explores the nature and interactions of such excited states in the attempt to develop an electrically pumped organic semiconductor laser, and to improve the performance and operational stability of organic light emitting diodes. We begin by investigating intrinsic loss processes in optically pumped organic semiconductor lasers and demonstrate that exciton annihilation implies a fundamental limit that will prevent lasing by electrical injection in currently known materials. Searching for an alternative approach to reach threshold leads us to study metastable geminate charge pairs, where we find that optically generated excitons can be accumulated over time in an external electric field via these intermediate states. Upon field turn-off, the excitons are immediately restored, leading to a sudden burst of excitation density over 30 times higher than that generated by the pump alone. Unfortunately, we identify limitations that have thus far prevented reaching laser threshold with this technique. In a parallel push toward high power density, we investigate the origins of quantum efficiency roll-off in organic light emitting diodes (OLEDs) and find that it is dominated by loss of charge balance in the majority of fluorescent and phosphorescent devices. The second major theme of this work involves understanding the intrinsic modes of OLED operational degradation. Based on extensive modeling and supported directly by experimental evidence, we identify exciton-charge carrier annihilation reactions as a principle degradation pathway. Exploiting the diffusion of triplet excitons, we show that fluorescence and phosphorescence can be combined to increase the operational lifetime of white OLEDs and still retain the potential for unity internal quantum efficiency.

Magnetophotoluminescence de dyades d'azote uniques dans le gallium arsenide

NASA Astrophysics Data System (ADS)

Ouellet-Plamondon, Clauderic

On the goal to achieve an efficient quantum light source, there are many possibilities ranging from lasers to quantum dots. One of those candiate is to use a single nitrogen dyad in GaAs. This nanostructure is composed of two nitrogen atoms in nearest neigbors subsituting for two arsenic atoms. Since both of those atoms have the same valence, the combined effet of the electronegativity and the small size of the nitrogen atoms form a potential well which attracts an electron. A hole is then bound to the electron via coulomb interaction, creating a bound exciton at the dyad from which the luminescence can be studied. In this work, we present an experimental study of the fine structure of the emission from single nitrogen dyads. The photoluminescence measurements are realised using a high resolution confocal microscope and under a magnetic field of up to 7 T. The spatial resolution combined with the sample's surface density of nitrogen dyads allows studying the properties of individual dyads. Since the C2v symmetry of the dyad lifts the degeneracy of the excitonic levels without magnetic field, four or five transitions are observed, depending on the orientation of the dyad with respect to the observation axis. Using a Hamiltonian taking into account the exchange interaction, the local crystal field and the Zeeman effect, the energie of excitonic states as well as their transition probabilites are modelised. This model reproduce the linear polarization of the emmited photons and is used to determine a range of acceptable value for the g-factor of the bound electron as well as the isotropic and anisotropic factors of the interaction of the weakly-bound hole with the magnetic field. Furthermore, from the diamagnetic shift, the radius of the wavefunction of the electron is evalutated at 16.2 °A, confirming that it is strongly localized to the dyad. Of all the dyads studied, a certain number of them had an emission strickingly different from the ones usually observed. In a first case, the environment perturbed the excitonic states making only the two states at higher energy observable. In a second case, an additional depolarised transition is observed at lower energy. We show that this transition is associated to a charged exciton, indicating for the first time that these nanotructures can bind multiple charges like their larger epitaxial and colloidal counterpart. This work gives a better comprehension of excitons bound to a nitrogen dyad and opens the way to many applications.

Room temperature exciton-polariton resonant reflection and suppressed absorption in periodic systems of InGaN quantum wells

NASA Astrophysics Data System (ADS)

Bolshakov, A. S.; Chaldyshev, V. V.; Zavarin, E. E.; Sakharov, A. V.; Lundin, W. V.; Tsatsulnikov, A. F.; Yagovkina, M. A.

2017-04-01

We studied the optical properties of periodic InGaN/GaN multiple quantum well systems with different numbers of periods. A resonant increase in the optical reflection and simultaneous suppression of the optical absorption have been revealed experimentally at room temperature when the Bragg and exciton resonances were tuned to each other. Numerical modeling with a single set of parameters gave a quantitatively accurate fit of the experimental reflection and transmission spectra in a wide wavelength range and various angles of the light incidence. The model included both exciton resonance and non-resonant band-to-band transitions in the InGaN quantum wells, as well as Rayleigh light scattering in the GaN buffer layer. The analysis also involved x-ray diffraction and photoluminescence data. It allowed us to determine the key parameters of the structure. In particular, the radiative broadening of the InGaN QW excitons was evaluated as 0.20 ± 0.02 meV.

Nonlinear absorption properties of AlGaAs/GaAs multiple quantum wells grown by metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Lee, Hsing-Chung; Kost, A.; Kawase, M.; Hariz, A.; Dapkus, P. Daniel

1988-01-01

The nonlinear absorption properties of the excitonic resonances associated with multiple quantum wells (MQWs) in AlGaAs/GaAs grown by metalorganic chemical vapor deposition are reported. The dependence of the saturation properties on growth parameters, especially growth temperature, and the well width are described. The minimum measured saturation intensity for these materials is 250 W/sq cm, the lowest reported value to date. The low saturation intensities are the result of excellent minority carrier properties. A systematic study of minority carrier lifetimes in quantum wells are reported. Lifetimes range from 50-350 ns depending on growth temperature and well width. When corrected for lateral diffusion effects and the measured minority carrier lifetime, the saturation data suggest that saturation intensities as low as 2.3 W/sq cm can be achieved in this system. The first measurements of the dependence of the exciton area and the magnitude of the excitonic absorption on well width are prsented. The growth of MQW structures on transparent GaP substrates is demonstrated and the electroabsorption properties of these structures are reviewed.

Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size.

PubMed

Kim, Young-Hoon; Wolf, Christoph; Kim, Young-Tae; Cho, Himchan; Kwon, Woosung; Do, Sungan; Sadhanala, Aditya; Park, Chan Gyung; Rhee, Shi-Woo; Im, Sang Hyuk; Friend, Richard H; Lee, Tae-Woo

2017-07-25

Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter D B (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nanocrystals (NCs) in a dimension > D B (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than D B show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and perfluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (∼60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs.

A Solution Processed Flexible Nanocomposite Electrode with Efficient Light Extraction for Organic Light Emitting Diodes

NASA Astrophysics Data System (ADS)

Li, Lu; Liang, Jiajie; Chou, Shu-Yu; Zhu, Xiaodan; Niu, Xiaofan; Zhibinyu; Pei, Qibing

2014-03-01

Highly efficient organic light emitting diodes (OLEDs) based on multiple layers of vapor evaporated small molecules, indium tin oxide transparent electrode, and glass substrate have been extensively investigated and are being commercialized. The light extraction from the exciton radiative decay is limited to less than 30% due to plasmonic quenching on the metallic cathode and the waveguide in the multi-layer sandwich structure. Here we report a flexible nanocomposite electrode comprising single-walled carbon nanotubes and silver nanowires stacked and embedded in the surface of a polymer substrate. Nanoparticles of barium strontium titanate are dispersed within the substrate to enhance light extraction efficiency. Green polymer OLED (PLEDs) fabricated on the nanocomposite electrode exhibit a maximum current efficiency of 118 cd/A at 10,000 cd/m2 with the calculated external quantum efficiency being 38.9%. The efficiencies of white PLEDs are 46.7 cd/A and 30.5%, respectively. The devices can be bent to 3 mm radius repeatedly without significant loss of electroluminescent performance. The nanocomposite electrode could pave the way to high-efficiency flexible OLEDs with simplified device structure and low fabrication cost.

A solution processed flexible nanocomposite electrode with efficient light extraction for organic light emitting diodes.

PubMed

Li, Lu; Liang, Jiajie; Chou, Shu-Yu; Zhu, Xiaodan; Niu, Xiaofan; ZhibinYu; Pei, Qibing

2014-03-17

Highly efficient organic light emitting diodes (OLEDs) based on multiple layers of vapor evaporated small molecules, indium tin oxide transparent electrode, and glass substrate have been extensively investigated and are being commercialized. The light extraction from the exciton radiative decay is limited to less than 30% due to plasmonic quenching on the metallic cathode and the waveguide in the multi-layer sandwich structure. Here we report a flexible nanocomposite electrode comprising single-walled carbon nanotubes and silver nanowires stacked and embedded in the surface of a polymer substrate. Nanoparticles of barium strontium titanate are dispersed within the substrate to enhance light extraction efficiency. Green polymer OLED (PLEDs) fabricated on the nanocomposite electrode exhibit a maximum current efficiency of 118 cd/A at 10,000 cd/m(2) with the calculated external quantum efficiency being 38.9%. The efficiencies of white PLEDs are 46.7 cd/A and 30.5%, respectively. The devices can be bent to 3 mm radius repeatedly without significant loss of electroluminescent performance. The nanocomposite electrode could pave the way to high-efficiency flexible OLEDs with simplified device structure and low fabrication cost.

A Solution Processed Flexible Nanocomposite Electrode with Efficient Light Extraction for Organic Light Emitting Diodes

PubMed Central

Li, Lu; Liang, Jiajie; Chou, Shu-Yu; Zhu, Xiaodan; Niu, Xiaofan; ZhibinYu; Pei, Qibing

2014-01-01

Highly efficient organic light emitting diodes (OLEDs) based on multiple layers of vapor evaporated small molecules, indium tin oxide transparent electrode, and glass substrate have been extensively investigated and are being commercialized. The light extraction from the exciton radiative decay is limited to less than 30% due to plasmonic quenching on the metallic cathode and the waveguide in the multi-layer sandwich structure. Here we report a flexible nanocomposite electrode comprising single-walled carbon nanotubes and silver nanowires stacked and embedded in the surface of a polymer substrate. Nanoparticles of barium strontium titanate are dispersed within the substrate to enhance light extraction efficiency. Green polymer OLED (PLEDs) fabricated on the nanocomposite electrode exhibit a maximum current efficiency of 118 cd/A at 10,000 cd/m2 with the calculated external quantum efficiency being 38.9%. The efficiencies of white PLEDs are 46.7 cd/A and 30.5%, respectively. The devices can be bent to 3 mm radius repeatedly without significant loss of electroluminescent performance. The nanocomposite electrode could pave the way to high-efficiency flexible OLEDs with simplified device structure and low fabrication cost. PMID:24632742

Semiconductor quantum dot-sensitized solar cells.

PubMed

Tian, Jianjun; Cao, Guozhong

2013-10-31

Semiconductor quantum dots (QDs) have been drawing great attention recently as a material for solar energy conversion due to their versatile optical and electrical properties. The QD-sensitized solar cell (QDSC) is one of the burgeoning semiconductor QD solar cells that shows promising developments for the next generation of solar cells. This article focuses on recent developments in QDSCs, including 1) the effect of quantum confinement on QDSCs, 2) the multiple exciton generation (MEG) of QDs, 3) fabrication methods of QDs, and 4) nanocrystalline photoelectrodes for solar cells. We also make suggestions for future research on QDSCs. Although the efficiency of QDSCs is still low, we think there will be major breakthroughs in developing QDSCs in the future.

Poly(sodium 4-styrenseulfonate)-modified monolayer graphene for anode applications of organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Zhou, Yongfang; Wang, Min; Wang, Liang; Liu, Shuli; Chen, Shufen; Cao, Kun; Shang, Wenjuan; Mai, Jiangquan; Zhao, Baomin; Feng, Jing; Lu, Xinhui; Huang, Wei

2017-09-01

An insulated poly(sodium 4-styrenseulfonate) (PSS) was used to modify monolayer graphene for anode applications of organic photovoltaics (OPVs). With this PSS interfacial modification layer, the OPVs showed a significant increase of 56.4% in efficiency due to an improved work function and hydrophilic feature of graphene and an enlarged recombination resistance of carriers/excitons. Doping a highly contorted 1,2,5-thiadiazole-fused 12-ring polyaromatic hydrocarbon into the active layer to form ternary blended OPVs further enlarged the recombination resistance of carriers/excitons and improved light absorption of the active layer, with which a high power conversion efficiency of 6.29% was acquired.

Stark shift and electric-field-induced dissociation of excitons in monolayer MoS2 and h BN /MoS2 heterostructures

NASA Astrophysics Data System (ADS)

Haastrup, Sten; Latini, Simone; Bolotin, Kirill; Thygesen, Kristian S.

2016-07-01

Efficient conversion of photons into electrical current in two-dimensional semiconductors requires, as a first step, the dissociation of the strongly bound excitons into free electrons and holes. Here we calculate the dissociation rates and energy shift of excitons in monolayer MoS2 as a function of an applied in-plane electric field. The dissociation rates are obtained as the inverse lifetime of the resonant states of a two-dimensional hydrogenic Hamiltonian which describes the exciton within the Mott-Wannier model. The resonances are computed using complex scaling, and the effective masses and screened electron-hole interaction defining the hydrogenic Hamiltonian are computed from first principles. For field strengths above 0.1 V/nm the dissociation lifetime is shorter than 1 ps, which is below the lifetime associated with competing decay mechanisms. Interestingly, encapsulation of the MoS2 layer in just two layers of hexagonal boron nitride (h BN ), enhances the dissociation rate by around one order of magnitude due to the increased screening. This shows that dielectric engineering is an effective way to control exciton lifetimes in two-dimensional materials.

Long-range energy transport in single supramolecular nanofibres at room temperature

NASA Astrophysics Data System (ADS)

Haedler, Andreas T.; Kreger, Klaus; Issac, Abey; Wittmann, Bernd; Kivala, Milan; Hammer, Natalie; Köhler, Jürgen; Schmidt, Hans-Werner; Hildner, Richard

2015-07-01

Efficient transport of excitation energy over long distances is a key process in light-harvesting systems, as well as in molecular electronics. However, in synthetic disordered organic materials, the exciton diffusion length is typically only around 10 nanometres (refs 4, 5), or about 50 nanometres in exceptional cases, a distance that is largely determined by the probability laws of incoherent exciton hopping. Only for highly ordered organic systems has the transport of excitation energy over macroscopic distances been reported--for example, for triplet excitons in anthracene single crystals at room temperature, as well as along single polydiacetylene chains embedded in their monomer crystalline matrix at cryogenic temperatures (at 10 kelvin, or -263 degrees Celsius). For supramolecular nanostructures, uniaxial long-range transport has not been demonstrated at room temperature. Here we show that individual self-assembled nanofibres with molecular-scale diameter efficiently transport singlet excitons at ambient conditions over more than four micrometres, a distance that is limited only by the fibre length. Our data suggest that this remarkable long-range transport is predominantly coherent. Such coherent long-range transport is achieved by one-dimensional self-assembly of supramolecular building blocks, based on carbonyl-bridged triarylamines, into well defined H-type aggregates (in which individual monomers are aligned cofacially) with substantial electronic interactions. These findings may facilitate the development of organic nanophotonic devices and quantum information technology.

Ultrafast Dynamics of Plasmon-Exciton Interaction of Ag Nanowire- Graphene Hybrids for Surface Catalytic Reactions

PubMed Central

Ding, Qianqian; Shi, Ying; Chen, Maodu; Li, Hui; Yang, Xianzhong; Qu, Yingqi; Liang, Wenjie; Sun, Mengtao

2016-01-01

Using the ultrafast pump-probe transient absorption spectroscopy, the femtosecond-resolved plasmon-exciton interaction of graphene-Ag nanowire hybrids is experimentally investigated, in the VIS-NIR region. The plasmonic lifetime of Ag nanowire is about 150 ± 7 femtosecond (fs). For a single layer of graphene, the fast dynamic process at 275 ± 77 fs is due to the excitation of graphene excitons, and the slow process at 1.4 ± 0.3 picosecond (ps) is due to the plasmonic hot electron interaction with phonons of graphene. For the graphene-Ag nanowire hybrids, the time scale of the plasmon-induced hot electron transferring to graphene is 534 ± 108 fs, and the metal plasmon enhanced graphene plasmon is about 3.2 ± 0.8 ps in the VIS region. The graphene-Ag nanowire hybrids can be used for plasmon-driven chemical reactions. This graphene-mediated surface-enhanced Raman scattering substrate significantly increases the probability and efficiency of surface catalytic reactions co-driven by graphene-Ag nanowire hybridization, in comparison with reactions individually driven by monolayer graphene or single Ag nanowire. This implies that the graphene-Ag nanowire hybrids can not only lead to a significant accumulation of high-density hot electrons, but also significantly increase the plasmon-to-electron conversion efficiency, due to strong plasmon-exciton coupling. PMID:27601199

Ultraviolet Electroluminescence from ZnS@ZnO Core-Shell Nanowires/p-GaN Introduced by Exciton Localization.

PubMed

Fang, Xuan; Wei, Zhipeng; Yang, Yahui; Chen, Rui; Li, Yongfeng; Tang, Jilong; Fang, Dan; Jia, Huimin; Wang, Dengkui; Fan, Jie; Ma, Xiaohui; Yao, Bin; Wang, Xiaohua

2016-01-27

We investigate the electroluminescence (EL) from light emitting diodes (LEDs) of ZnO nanowires/p-GaN structure and ZnS@ZnO core-shell nanowires/p-GaN structure. With the increase of forward bias, the emission peak of ZnO nanowires/p-GaN structure heterojunction shows a blue-shift, while the ZnS@ZnO core-shell nanowires/p-GaN structure demonstrates a changing EL emission; the ultraviolet (UV) emission at 378 nm can be observed. This discrepancy is related to the localized states introduced by ZnS particles, which results in a different carrier recombination process near the interfaces of the heterojunction. The localized states capture the carriers in ZnO nanowires and convert them to localized excitons under high forward bias. A strong UV emission due to localized excitons can be observed. Our results indicated that utilizing localized excitons should be a new route toward ZnO-based ultraviolet LEDs with high efficiency.

Reconstructing Space- and Energy-Dependent Exciton Generation in Solution-Processed Inverted Organic Solar Cells.

PubMed

Wang, Yuheng; Zhang, Yajie; Lu, Guanghao; Feng, Xiaoshan; Xiao, Tong; Xie, Jing; Liu, Xiaoyan; Ji, Jiahui; Wei, Zhixiang; Bu, Laju

2018-04-25

Photon absorption-induced exciton generation plays an important role in determining the photovoltaic properties of donor/acceptor organic solar cells with an inverted architecture. However, the reconstruction of light harvesting and thus exciton generation at different locations within organic inverted device are still not well resolved. Here, we investigate the film depth-dependent light absorption spectra in a small molecule donor/acceptor film. Including depth-dependent spectra into an optical transfer matrix method allows us to reconstruct both film depth- and energy-dependent exciton generation profiles, using which short-circuit current and external quantum efficiency of the inverted device are simulated and compared with the experimental measurements. The film depth-dependent spectroscopy, from which we are able to simultaneously reconstruct light harvesting profile, depth-dependent composition distribution, and vertical energy level variations, provides insights into photovoltaic process. In combination with appropriate material processing methods and device architecture, the method proposed in this work will help optimizing film depth-dependent optical/electronic properties for high-performance solar cells.

Long-range coupling of electron-hole pairs in spatially separated organic donor-acceptor layers

PubMed Central

Nakanotani, Hajime; Furukawa, Taro; Morimoto, Kei; Adachi, Chihaya

2016-01-01

Understanding exciton behavior in organic semiconductor molecules is crucial for the development of organic semiconductor-based excitonic devices such as organic light-emitting diodes and organic solar cells, and the tightly bound electron-hole pair forming an exciton is normally assumed to be localized on an organic semiconducting molecule. We report the observation of long-range coupling of electron-hole pairs in spatially separated electron-donating and electron-accepting molecules across a 10-nanometers-thick spacer layer. We found that the exciton energy can be tuned over 100 megaelectron volts and the fraction of delayed fluorescence can be increased by adjusting the spacer-layer thickness. Furthermore, increasing the spacer-layer thickness produced an organic light-emitting diode with an electroluminescence efficiency nearly eight times higher than that of a device without a spacer layer. Our results demonstrate the first example of a long-range coupled charge-transfer state between electron-donating and electron-accepting molecules in a working device. PMID:26933691

Assessment of strontium oxide functionalized graphene nanoflakes for enhanced photocatalytic activity: A density functional theory approach

NASA Astrophysics Data System (ADS)

Divya, A.; Mathavan, T.; Asath, R. Mohamed; Archana, J.; Hayakawa, Y.; Benial, A. Milton Franklin

2016-05-01

A series of strontium oxide functionalized graphene nanoflakes were designed and their optoelectronic properties were studied for enhanced photocatalytic activity. The efficiency of designed molecules was studied using various parameters such as HOMO-LUMO energy gap, light harvesting efficiency and exciton binding energy. The computed results show that by increasing the degree of functionalization of strontium oxide leads to lowering the band gap of hydrogen terminated graphene nanoflakes. Furthermore, the study explores the role of strontium oxide functionalization in Frontier Molecular Orbitals, ionization potential, electron affinity, exciton binding energy and light harvesting efficiency of designed molecules. The infrared and Raman spectra were simulated for pure and SrO functionalized graphene nanoflakes. The electron rich and electron deficient regions which are favorable for electrophilic and nucleophilic attacks respectively were analyzed using molecular electrostatic potential surface analysis.

Index of refraction of GaAs-Al(x)Ga(1-x)As superlattices and multiple quantum wells

NASA Technical Reports Server (NTRS)

Kahen, K. B.; Leburton, J. P.

1987-01-01

A theoretical study of the index of refraction of superlattices and its variation as a function of frequency and the superlattice parameters, i.e., layer width and AlAs composition, is presented. Gamma-region exciton and valence-band mixing effects are included in the model. It is found that these two effects have an important influence on the value of the index of refraction and that superstructure effects rapidly decrease for energies greater than the superlattice potential barriers. Because of the quasi-two-dimensional character of the Gamma-region excitons, the results indicate that the superlattice index of refraction can vary by about two percent at the quantized, bound-exciton, transition energies. Overall, the theoretical results are in good agreement with the experimental data.

Single-crystal charge transfer interfaces for efficient photonic devices (Conference Presentation)

NASA Astrophysics Data System (ADS)

Alves, Helena; Pinto, Rui M.; Maçôas, Ermelinda M. S.; Baleizão, Carlos; Santos, Isabel C.

2016-09-01

Organic semiconductors have unique optical, mechanical and electronic properties that can be combined with customized chemical functionality. In the crystalline form, determinant features for electronic applications such as molecular purity, the charge mobility or the exciton diffusion length, reveal a superior performance when compared with materials in a more disordered form. Combining crystals of two different conjugated materials as even enable a new 2D electronic system. However, the use of organic single crystals in devices is still limited to a few applications, such as field-effect transistors. In 2013, we presented the first system composed of single-crystal charge transfer interfaces presenting photoconductivity behaviour. The system composed of rubrene and TCNQ has a responsivity reaching 1 A/W, corresponding to an external quantum efficiency of nearly 100%. A similar approach, with a hybrid structure of a PCBM film and rubrene single crystal also presents high responsivity and the possibility to extract excitons generated in acceptor materials. This strategy led to an extended action towards the near IR. By adequate material design and structural organisation of perylediimides, we demonstrate that is possible to improve exciton diffusion efficiency. More recently, we have successfully used the concept of charge transfer interfaces in phototransistors. These results open the possibility of using organic single-crystal interfaces in photonic applications.

Study on optoelectronic properties of Spiro-CN for developing an efficient OLED

NASA Astrophysics Data System (ADS)

Mishra, Ashok Kumar

2018-05-01

There are a class of organic molecules and polymers which exhibit semiconductor behavior because of nearly free conjugate π-electrons. Hopping of these electrons in molecules forms different excited singlet and triplet states named as excitons. Some of these organic molecules can be set to emit photons by triplet-singlet excitonic transition via a process called Thermally Activated Delayed Fluorescence (TADF) which is exploited for designing the Organic Light Emitting diode (OLED.) Spiro-CN (spirobifluorene skeletons) Spiro is one of these reported noble metal-free TADF molecules which offers unique optical and electronic properties arising from the efficient transition and reverse intersystem crossing between the lowest singlet (S) and triplet (T) excited states. Its ability to harvest triplet excitons for fluorescence through facilitated reverse intersystem crossing (T→S) could directly impact their properties and performances, which is attractive for a wide variety of low-cost optoelectronic device. In the present study, the Spiro-CN compounds have been taken up for the investigation of various optoelectronic properties including the thermally activated delayed fluorescence (TADF) by using the Koopmans Method and Density Functional Theory. The present study discusses the utility of the Spiro-CN organic semiconductor as a suitable TADF material essential for developing an efficient Organic Light Emitting Diode (OLED).

Quantum-Dot-Based Solar Cells: Recent Advances, Strategies, and Challenges.

PubMed

Kim, Mee Rahn; Ma, Dongling

2015-01-02

Among next-generation photovoltaic systems requiring low cost and high efficiency, quantum dot (QD)-based solar cells stand out as a very promising candidate because of the unique and versatile characteristics of QDs. The past decade has already seen rapid conceptual and technological advances on various aspects of QD solar cells, and diverse opportunities, which QDs can offer, predict that there is still ample room for further development and breakthroughs. In this Perspective, we first review the attractive advantages of QDs, such as size-tunable band gaps and multiple exciton generation (MEG), beneficial to solar cell applications. We then analyze major strategies, which have been extensively explored and have largely contributed to the most recent and significant achievements in QD solar cells. Finally, their high potential and challenges are discussed. In particular, QD solar cells are considered to hold immense potential to overcome the theoretical efficiency limit of 31% for single-junction cells.

Channeling Excitons to Emissive Defect Sites in Carbon Nanotube Semiconductors beyond the Dilute Regime.

PubMed

Powell, Lyndsey R; Piao, Yanmei; Ng, Allen L; Wang, YuHuang

2018-06-07

The exciton photoluminescence of carbon nanotube semiconductors has been intensively exploited for bioimaging, anticounterfeiting, photodetection, and quantum information science. However, at high concentrations, photoluminescence is lost to self-quenching because of the nearly complete overlap of the absorption and emissive states (∼10 meV Stokes shift). Here we show that by introducing sparse fluorescent quantum defects via covalent chemistry, self-quenching can be efficiently bypassed by means of the new emission route. The defect photoluminescence is significantly red-shifted by 190 meV for p-nitroaryl tailored (6,5)-single-walled carbon nanotubes (SWCNTs) from the native emission of the nanotube. Notably, the defect photoluminescence is more than 34 times brighter than the native photoluminescence of unfunctionalized SWCNTs in the most concentrated nanotube solution tested (2.7 × 10 14 nanotubes/mL). Moreover, we show that defect photoluminescence is more resistant to self-quenching than the native state in a dense film, which is the upper limit of concentration. Our findings open opportunities to harness nanotube excitons in highly concentrated systems for applications where photoluminescence brightness and light-collecting efficiency are mutually important.

Charge Transfer from n-Doped Nanocrystals: Mimicking Intermediate Events in Multielectron Photocatalysis.

PubMed

Wang, Junhui; Ding, Tao; Wu, Kaifeng

2018-06-12

In multielectron photocatalytic reactions, an absorbed photon triggers charge transfer from the light-harvester to the attached catalyst, leaving behind a charge of the opposite sign in the light-harvester. If this charge is not scavenged before the absorption of the following photons, photoexcitation generates not neutral but charged excitons from which the extraction of charges should become more difficult. This is potentially an efficiency-limiting intermediate event in multielectron photocatalysis. To study the charge dynamics in this event, we doped CdS nanocrystal quantum dots (QDs) with an extra electron and measured hole transfer from n-doped QDs to attached acceptors. We find that the Auger decay of charged excitons lowers the charge separation yield to 68.6% from 98.4% for neutral excitons. In addition, the hole transfer rate in the presence of two electrons (1290 ps) is slower than that in the presence one electron (776 ps), and the recombination rate of charge separated states is about 2 times faster in the former case. This model study provides important insights into possible efficiency-limiting intermediate events involved in photocatalysis.

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.

Ultrafast carrier dynamics in GaN/InGaN multiple quantum wells nanorods

NASA Astrophysics Data System (ADS)

Chen, Weijian; Wen, Xiaoming; Latzel, Michael; Yang, Jianfeng; Huang, Shujuan; Shrestha, Santosh; Patterson, Robert; Christiansen, Silke; Conibeer, Gavin

2018-01-01

GaN/InGaN multiple quantum wells (MQW) is a promising material for high-efficiency solid-state lighting. Ultrafast optical pump-probe spectroscopy is an important characterization technique for examining fundamental phenomena in semiconductor nanostructure with sub-picosecond resolution. In this study, ultrafast exciton and charge carrier dynamics in GaN/InGaN MQW planar layer and nanorod are investigated using femtosecond transient absorption (TA) techniques at room temperature. Here nanorods are fabricated by etching the GaN/InGaN MQW planar layers using nanosphere lithography and reactive ion etching. Photoluminescence efficiency of the nanorods have been proved to be much higher than that of the planar layers, but the mechanism of the nanorod structure improvement of PL efficiency is not adequately studied. By comparing the TA profile of the GaN/InGaN MQW planar layers and nanorods, the impact of surface states and nanorods lateral confinement in the ultrafast carrier dynamics of GaN/InGaN MQW is revealed. The nanorod sidewall surface states have a strong influence on the InGaN quantum well carrier dynamics. The ultrafast relaxation processes studied in this GaN/InGaN MQW nanostructure is essential for further optimization of device application.

Strong-coupling of WSe2 in ultra-compact plasmonic nanocavities at room temperature.

PubMed

Kleemann, Marie-Elena; Chikkaraddy, Rohit; Alexeev, Evgeny M; Kos, Dean; Carnegie, Cloudy; Deacon, Will; de Pury, Alex Casalis; Große, Christoph; de Nijs, Bart; Mertens, Jan; Tartakovskii, Alexander I; Baumberg, Jeremy J

2017-11-03

Strong coupling of monolayer metal dichalcogenide semiconductors with light offers encouraging prospects for realistic exciton devices at room temperature. However, the nature of this coupling depends extremely sensitively on the optical confinement and the orientation of electronic dipoles and fields. Here, we show how plasmon strong coupling can be achieved in compact, robust, and easily assembled gold nano-gap resonators at room temperature. We prove that strong-coupling is impossible with monolayers due to the large exciton coherence size, but resolve clear anti-crossings for greater than 7 layer devices with Rabi splittings exceeding 135 meV. We show that such structures improve on prospects for nonlinear exciton functionalities by at least 10 4 , while retaining quantum efficiencies above 50%, and demonstrate evidence for superlinear light emission.

Solid state photon upconversion utilizing thermally activated delayed fluorescence molecules as triplet sensitizer

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

Wu, Tony C.; Congreve, Daniel N.; Baldo, Marc A., E-mail: baldo@mit.edu

2015-07-20

The ability to upconvert light is useful for a range of applications, from biological imaging to solar cells. But modern technologies have struggled to upconvert incoherent incident light at low intensities. Here, we report solid state photon upconversion employing triplet-triplet exciton annihilation in an organic semiconductor, sensitized by a thermally activated-delayed fluorescence (TADF) dye. Compared to conventional phosphorescent sensitizers, the TADF dye maximizes the wavelength shift in upconversion due to its small singlet-triplet splitting. The efficiency of energy transfer from the TADF dye is 9.1%, and the conversion yield of sensitizer exciton pairs to singlet excitons in the annihilator ismore » 1.1%. Our results demonstrate upconversion in solid state geometries and with non-heavy metal-based sensitizer materials.« less

Ultrafast exciton dynamics and light-driven H2 evolution in colloidal semiconductor nanorods and Pt-tipped nanorods.

PubMed

Wu, Kaifeng; Zhu, Haiming; Lian, Tianquan

2015-03-17

Colloidal quantum confined one-dimensional (1D) semiconductor nanorods (NRs) and related semiconductor-metal heterostructures are promising new materials for efficient solar-to-fuel conversion because of their unique physical and chemical properties. NRs can simultaneously exhibit quantum confinement effects in the radial direction and bulk like carrier transport in the axial direction. The former implies that concepts well-established in zero-dimensional quantum dots, such as size-tunable energetics and wave function engineering through band alignment in heterostructures, can also be applied to NRs; while the latter endows NRs with fast carrier transport to achieve long distance charge separation. Selective growth of catalytic metallic nanoparticles, such as Pt, at the tips of NRs provides convenient routes to multicomponent heterostructures with photocatalytic capabilities and controllable charge separation distances. The design and optimization of such materials for efficient solar-to-fuel conversion require the understanding of exciton and charge carrier dynamics. In this Account, we summarize our recent studies of ultrafast charge separation and recombination kinetics and their effects on steady-state photocatalytic efficiencies of colloidal CdS and CdSe/CdS NRs and related NR-Pt heterostructures. After a brief introduction of their electronic structure, we discuss exciton dynamics of CdS NRs. By transient absorption and time-resolved photoluminescence decay, it is shown that although the conduction band electrons are long-lived, photogenerated holes in CdS NRs are trapped on an ultrafast time scale (∼0.7 ps), which forms localized excitons due to strong Coulomb interaction in 1D NRs. In quasi-type II CdSe/CdS dot-in-rod NRs, a large valence band offset drives the ultrafast localization of holes to the CdSe core, and the competition between this process and ultrafast hole trapping on a CdS rod leads to three types of exciton species with distinct spatial distributions. The effect of the exciton dynamics on photoreduction reactions is illustrated using methyl viologen (MV(2+)) as a model electron acceptor. The steady-state MV(2+) photoreduction quantum yield of CdSe/CdS dot-in-rod NRs approaches unity under rod excitation, much larger than CdSe QDs and CdSe/CdS core/shell QDs. Detailed time-resolved studies show that in quasi-type II CdSe/CdS NRs and type II ZnSe/CdS NRs strong quantum confinement in the radial direction facilitates fast electron transfer and hole removal, whereas the fast carrier mobility along the axial direction enables long distance charge separation and slow charge recombination, which is essential for efficient MV(2+) photoreduction. The NR/MV(2+) relay system can be coupled to Pt nanoparticles in solution for light-driven H2 generation. Alternatively, Pt-tipped CdS and CdSe/CdS NRs provide fully integrated all inorganic systems for light-driven H2 generation. In CdS-Pt and CdSe/CdS-Pt hetero-NRs, ultrafast hole trapping on the CdS rod surface or in CdSe core enables efficient electron transfer from NRs to Pt tips by suppressing hole and energy transfer. It is shown that the quantum yields of photodriven H2 generation using these heterostructures correlate well with measured hole transfer rates from NRs to sacrificial donors, revealing that hole removal is the key efficiency-limiting step. These findings provide important insights for designing more efficient quantum confined NR and NR-Pt based systems for solar-to-fuel conversion.

Carrier-density-dependent recombination dynamics of excitons and electron-hole plasma in m -plane InGaN/GaN quantum wells

NASA Astrophysics Data System (ADS)

Liu, W.; Butté, R.; Dussaigne, A.; Grandjean, N.; Deveaud, B.; Jacopin, G.

2016-11-01

We study the carrier-density-dependent recombination dynamics in m -plane InGaN/GaN multiple quantum wells in the presence of n -type background doping by time-resolved photoluminescence. Based on Fermi's golden rule and Saha's equation, we decompose the radiative recombination channel into an excitonic and an electron-hole pair contribution, and extract the injected carrier-density-dependent bimolecular recombination coefficients. Contrary to the standard electron-hole picture, our results confirm the strong influence of excitons even at room temperature. Indeed, at 300 K, excitons represent up to 63 ± 6% of the photoexcited carriers. In addition, following the Shockley-Read-Hall model, we extract the electron and hole capture rates by deep levels and demonstrate that the increase in the effective lifetime with injected carrier density is due to asymmetric capture rates in presence of an n -type background doping. Thanks to the proper determination of the density-dependent recombination coefficients up to high injection densities, our method provides a way to evaluate the importance of Auger recombination.

Highly efficient solution-processed phosphorescent organic light-emitting devices with double-stacked hole injection layers

NASA Astrophysics Data System (ADS)

Chen, Yuehua; Hao, Lin; Zhang, Xinwen; Zhang, Xiaolin; Liu, Mengjiao; Zhang, Mengke; Wang, Jiong; Lai, Wen-Yong; Huang, Wei

2017-08-01

In this paper, solution-processed nickel oxide (NiOx) is used as hole-injection layers (HILs) in solution-processed phosphorescent organic light-emitting diodes (PhOLEDs). Serious exciton quenching is verified at the NiOx/emitting layer (EML) interface, resulting in worse device performance. The device performance is significantly improved by inserting a layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) between the EML and NiOx. The solution-processed blue PhOLED with the double-stacked NiOx/PEDOT:PSS HILs shows a maximum current efficiency of 30.5 cd/A, which is 75% and 30% higher than those of the devices with a single NiOx HIL and a PEDOT:PSS HIL, respectively. Improvement of device efficiency can be attributed to reducing exciton quenching of the PEDOT:PSS layer as well as the electron blocking effect of the NiOx layer.

Vertical phase separation in bulk heterojunction solar cells formed by in situ polymerization of fulleride

PubMed Central

Zhang, Lipei; Xing, Xing; Zheng, Lingling; Chen, Zhijian; Xiao, Lixin; Qu, Bo; Gong, Qihuang

2014-01-01

Vertical phase separation of the donor and the acceptor in organic bulk heterojunction solar cells is crucial to improve the exciton dissociation and charge transport efficiencies. This is because whilst the exciton diffusion length is limited, the organic film must be thick enough to absorb sufficient light. However, it is still a challenge to control the phase separation of a binary blend in a bulk heterojunction device architecture. Here we report the realization of vertical phase separation induced by in situ photo-polymerization of the acrylate-based fulleride. The power conversion efficiency of the devices with vertical phase separation increased by 20%. By optimising the device architecture, the power conversion efficiency of the single junction device reached 8.47%. We believe that in situ photo-polymerization of acrylate-based fulleride is a universal and controllable way to realise vertical phase separation in organic blends. PMID:24861168

Ultrafast dynamics of metal plasmons induced by 2D semiconductor excitons in hybrid nanostructure arrays

DOE PAGES

Boulesbaa, Abdelaziz; Babicheva, Viktoriia E.; Wang, Kai; ...

2016-11-17

With the advanced progress achieved in the field of nanotechnology, localized surface plasmons resonances (LSPRs) are actively considered to improve the efficiency of metal-based photocatalysis, photodetection, and photovoltaics. Here, we report on the exchange of energy and electric charges in a hybrid composed of a two-dimensional tungsten disulfide (2D-WS 2) monolayer and an array of aluminum (Al) nanodisks. Femtosecond pump-probe spectroscopy results indicate that within ~830 fs after photoexcitation of the 2D-WS 2 semiconductor, energy transfer from the 2D-WS 2 excitons excites the plasmons of the Al array. Then, upon the radiative and/or nonradiative damping of these excited plasmons, energymore » and/or electron transfer back to the 2D-WS 2 semiconductor takes place as indicated by an increase in the reflected probe at the 2D exciton transition energies at later time-delays. This simultaneous exchange of energy and charges between the metal and the 2D-WS 2 semiconductor resulted in an extension of the average lifetime of the 2D-excitons from ~15 to ~58 ps in absence and presence of the Al array, respectively. Furthermore, the indirectly excited plasmons were found to live as long as the 2D-WS 2 excitons exist. Furthermore, the demonstrated ability to generate exciton-plasmons coupling in a hybrid nanostructure may open new opportunities for optoelectronic applications such as plasmonic-based photodetection and photocatalysis.« less

Recombination dynamics of excitons with low non-radiative component in semi-polar (10-11)-oriented GaN/AlGaN multiple quantum wells

NASA Astrophysics Data System (ADS)

Rosales, D.; Gil, B.; Bretagnon, T.; Guizal, B.; Izyumskaya, N.; Monavarian, M.; Zhang, F.; Okur, S.; Avrutin, V.; Özgür, Ü.; Morkoç, H.

2014-09-01

Optical properties of GaN/Al0.2Ga0.8N multiple quantum wells grown with semi-polar (10-11) orientation on patterned 7°-off Si (001) substrates have been investigated. Studies performed at 8 K reveal the in-plane anisotropic behavior of the QW photoluminescence (PL) intensity for this semi-polar orientation. The time resolved PL measurements were carried out in the temperature range from 8 to 295 K to deduce the effective recombination decay times, with respective radiative and non-radiative contributions. The non-radiative component remains relatively weak with increasing temperature, indicative of high crystalline quality. The radiative decay time is a consequence of contribution from both localized and free excitons. We report an effective density of interfacial defects of 2.3 × 1012 cm-2 and a radiative recombination time of τloc = 355 ps for the localized excitons. This latter value is significantly larger than those reported for the non-polar structures, which we attribute to the presence of a weak residual electric field in the semi-polar QW layers.

Van Hove singularities and excitonic effects in the optical conductivity of twisted bilayer graphene.

PubMed

Havener, Robin W; Liang, Yufeng; Brown, Lola; Yang, Li; Park, Jiwoong

2014-06-11

We report a systematic study of the optical conductivity of twisted bilayer graphene (tBLG) across a large energy range (1.2-5.6 eV) for various twist angles, combined with first-principles calculations. At previously unexplored high energies, our data show signatures of multiple van Hove singularities (vHSs) in the tBLG bands as well as the nonlinearity of the single layer graphene bands and their electron-hole asymmetry. Our data also suggest that excitonic effects play a vital role in the optical spectra of tBLG. Including electron-hole interactions in first-principles calculations is essential to reproduce the shape of the conductivity spectra, and we find evidence of coherent interactions between the states associated with the multiple vHSs in tBLG.

Light controlled prebreakdown characteristics of a semi-insulating GaAs photoconductive switch

NASA Astrophysics Data System (ADS)

Xiangrong, Ma; Wei, Shi; Weili, Ji; Hong, Xue

2011-12-01

A 4 mm gap semi-insulating (SI) GaAs photoconductive switch (PCSS) was triggered by a pulse laser with a wavelength of 1064 nm and a pulse energy of 0.5 mJ. In the experiment, when the bias field was 4 kV, the switch did not induce self-maintained discharge but worked in nonlinear (lock-on) mode. The phenomenon is analyzed as follows: an exciton effect contributes to photoconduction in the generation and dissociation of excitons. Collision ionization, avalanche multiplication and the exciton effect can supply carrier concentration and energy when an outside light source was removed. Under the combined influence of these factors, the SI-GaAs PCSS develops into self-maintained discharge rather than just in the light-controlled prebreakdown status. The characteristics of the filament affect the degree of damage to the switch.

Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps

DOE PAGES

Zaikowski, Lori; Mauro, Gina; Bird, Matthew; ...

2014-12-22

Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are asmore » large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl 3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length L D =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.« less

Electrical control of charged carriers and excitons in atomically thin materials

NASA Astrophysics Data System (ADS)

Wang, Ke; De Greve, Kristiaan; Jauregui, Luis A.; Sushko, Andrey; High, Alexander; Zhou, You; Scuri, Giovanni; Taniguchi, Takashi; Watanabe, Kenji; Lukin, Mikhail D.; Park, Hongkun; Kim, Philip

2018-02-01

Electrical confinement and manipulation of charge carriers in semiconducting nanostructures are essential for realizing functional quantum electronic devices1-3. The unique band structure4-7 of atomically thin transition metal dichalcogenides (TMDs) offers a new route towards realizing novel 2D quantum electronic devices, such as valleytronic devices and valley-spin qubits8. 2D TMDs also provide a platform for novel quantum optoelectronic devices9-11 due to their large exciton binding energy12,13. However, controlled confinement and manipulation of electronic and excitonic excitations in TMD nanostructures have been technically challenging due to the prevailing disorder in the material, preventing accurate experimental control of local confinement and tunnel couplings14-16. Here we demonstrate a novel method for creating high-quality heterostructures composed of atomically thin materials that allows for efficient electrical control of excitations. Specifically, we demonstrate quantum transport in the gate-defined, quantum-confined region, observing spin-valley locked quantized conductance in quantum point contacts. We also realize gate-controlled Coulomb blockade associated with confinement of electrons and demonstrate electrical control over charged excitons with tunable local confinement potentials and tunnel couplings. Our work provides a basis for novel quantum opto-electronic devices based on manipulation of charged carriers and excitons.

Spectral photosensitivity of an organic semiconductor in a submicron metal grating

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

Blinov, L. M., E-mail: lev39blinov@gmail.com; Lazarev, V. V.; Yudin, S. G.

The photoelectric effect in films of the copper phthalocyanine organic semiconductor (α-CuPc) has been experimentally studied for two fundamentally different geometries. A sample in the first, normal geometry is fabricated in the form of a sandwich with an α-CuPc film between a transparent SnO{sub 2} electrode on a substrate and an upper reflecting Al electrode. In the second case of the planar geometry, the semiconductor is deposited on the substrate with a system of submicron chromium interdigital electrodes. It has been found that the effective photoconductivity in the planar geometry is more than two orders of magnitude higher than thatmore » in the normal geometry. In addition to the classical model (without excitons), a simple exciton model has been proposed within which a relation has been obtained between the probability of the formation of electron–hole pairs and the characteristic recombination and dissociation times of excitons. An increase in the photoconductivity in the planar geometry has been explained within the exciton model by an increase in the rate of dissociation of excitons into electron–hole pairs owing to acceptor oxygen molecules, which diffuse more efficiently into the film in the case of the planar geometry where the upper electrode is absent.« less

Colloquium: Excitons in atomically thin transition metal dichalcogenides

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

Wang, Gang; Chernikov, Alexey; Glazov, Mikhail M.

Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit interactions leads to a unique combination of the spin and valley degrees of freedom. In addition, the 2D character of the monolayers and weakmore » dielectric screening from the environment yield a significant enhancement of the Coulomb interaction. The resulting formation of bound electron-hole pairs, or excitons, dominates the optical and spin properties of the material. In this article, recent progress in understanding of the excitonic properties in monolayer TMDs is reviewed and future challenges are laid out. Discussed are the consequences of the strong direct and exchange Coulomb interaction, exciton light-matter coupling, and influence of finite carrier and electron-hole pair densities on the exciton properties in TMDs. Finally, the impact on valley polarization is described and the tuning of the energies and polarization observed in applied electric and magnetic fields is summarized.« less

Excitonic nature of optical transitions in electroabsorption spectra of perovskite solar cells

NASA Astrophysics Data System (ADS)

Ruf, Fabian; Magin, Alice; Schultes, Moritz; Ahlswede, Erik; Kalt, Heinz; Hetterich, Michael

2018-02-01

We investigate the electronic structure of solution-processed perovskite solar cells using temperature-dependent electroabsorption (EA) spectroscopy. Simultaneous measurements of absorption and electromodulated spectra of semitransparent methylammonium lead iodide solar cells facilitate a direct comparison of the specific features. The EA spectra can be transformed to peak-like line shapes utilizing an approach based on the Kramers-Kronig relations. The resulting peak positions correspond well to the discrete excitonic—rather than the continuum—contribution of the absorption spectra derived from generalized Elliott fits. This indicates the excitonic nature of the observed EA resonance and is found to be consistent over the whole temperature range investigated (from T = 10 K up to room temperature). To further confirm these findings, a line shape analysis of the measured EA spectra was performed. The best agreement was achieved using a first-derivative-like functional form which is expected for excitonic systems and supports the conclusion of an excitonic optical transition. Exciton binding energies EB are estimated for the orthorhombic and tetragonal phases as 26 meV and 19 meV, respectively. Nevertheless, power-conversion efficiencies η up to 13% (11.5% stabilized) demonstrate good charge-carrier separation in the devices due to sufficient thermal dissociation and Sommerfeld-enhanced absorption.

Interfacial disorder drives charge separation in molecular semiconductors

NASA Astrophysics Data System (ADS)

Willard, Adam

One of the fundamental microscopic processes in photocurrent generation is the dissociation of neutral photo-excitations (i.e., Frenkel excitons) into free charge carriers (i.e., electrons and holes). This process requires the physical separation of oppositely charged electrons and holes, which are held to together by an attractive electrostatic binding energy. In traditional inorganic-based photovoltaic (PV) materials, this binding energy is generally small and easily overcome, however, in organic-based PVs (OPVs) the exciton binding energy can significantly exceed thermal energies. The inability of bound charges to overcome this large binding energy has been implicated as a primary source of efficiency loss in OPVs. Here I present results from our recent efforts to explore the role of static molecular disorder in mediating this process. Using a simple lattice model of exciton dynamics we demonstrate that random spatial variations in the energetic landscape can mitigate the attractive Coulomb interaction between electrons and holes. We show that this effect manifests as a reduction in the free energy barrier for exciton dissociation that grows more pronounced with increasing disorder. By considering the competition between this thermodynamic effect and the disorder-induced slowing of dissociation kinetics we demonstrate that exciton dissociation yields are expected to depend non-monotonically on the degree of static disorder.

Colloquium: Excitons in atomically thin transition metal dichalcogenides

DOE PAGES

Wang, Gang; Chernikov, Alexey; Glazov, Mikhail M.; ...

2018-04-04

Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit interactions leads to a unique combination of the spin and valley degrees of freedom. In addition, the 2D character of the monolayers and weakmore » dielectric screening from the environment yield a significant enhancement of the Coulomb interaction. The resulting formation of bound electron-hole pairs, or excitons, dominates the optical and spin properties of the material. In this article, recent progress in understanding of the excitonic properties in monolayer TMDs is reviewed and future challenges are laid out. Discussed are the consequences of the strong direct and exchange Coulomb interaction, exciton light-matter coupling, and influence of finite carrier and electron-hole pair densities on the exciton properties in TMDs. Finally, the impact on valley polarization is described and the tuning of the energies and polarization observed in applied electric and magnetic fields is summarized.« less

Colloquium: Excitons in atomically thin transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Wang, Gang; Chernikov, Alexey; Glazov, Mikhail M.; Heinz, Tony F.; Marie, Xavier; Amand, Thierry; Urbaszek, Bernhard

2018-04-01

Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit interactions leads to a unique combination of the spin and valley degrees of freedom. In addition, the 2D character of the monolayers and weak dielectric screening from the environment yield a significant enhancement of the Coulomb interaction. The resulting formation of bound electron-hole pairs, or excitons, dominates the optical and spin properties of the material. Here recent progress in understanding of the excitonic properties in monolayer TMDs is reviewed and future challenges are laid out. Discussed are the consequences of the strong direct and exchange Coulomb interaction, exciton light-matter coupling, and influence of finite carrier and electron-hole pair densities on the exciton properties in TMDs. Finally, the impact on valley polarization is described and the tuning of the energies and polarization observed in applied electric and magnetic fields is summarized.

Exchange interaction and the tunneling induced transparency in coupled quantum dots

NASA Astrophysics Data System (ADS)

Borges, Halyne; Alcalde, Augusto; Ulloa, Sergio

2014-03-01

Stacked semiconductor quantum dots coupled by tunneling are unique ``quantum molecule'' where it is possible to create a multilevel structure of excitonic states. This structure allows the investigation of quantum interference processes and their control via electric external fields. In this work, we investigate the optical response of a quantum molecule coherently driven by a polarized laser, considering the splitting in excitonic levels caused by isotropic and anisotropic exchange interactions. In our model we consider interdot transitions mediated by the the hole tunneling between states with the same total spin and, between bright and dark exciton states. Using realistic experimental parameters, we demonstrate that the excitonic states coupled by tunneling exhibit an enriched and controllable optical response. Our results show that through the appropriate control of the external electric field and light polarization, the tunneling coupling establishes an efficient destructive quantum interference path that creates a transparency window in the absorption spectra, whenever states of appropriate symmetry are mixed by the hole tunneling. We explore the relevant parameters space that would allows with the experiments. CAPES, INCT-IQ and MWN/CIAM-NSF.

Exciton-dissociation and charge-recombination processes in pentacene/C60 solar cells: theoretical insight into the impact of interface geometry.

PubMed

Yi, Yuanping; Coropceanu, Veaceslav; Brédas, Jean-Luc

2009-11-04

The exciton-dissociation and charge-recombination processes in organic solar cells based on pentacene/C(60) heterojunctions are investigated by means of quantum-mechanical calculations. The electronic couplings and the rates of exciton dissociation and charge recombination have been evaluated for several geometrical configurations of the pentacene/C(60) complex, which are relevant to bilayer and bulk heterojunctions. The results suggest that, irrespective of the actual pentacene-fullerene orientation, both pentacene-based and C(60)-based excitons are able to dissociate efficiently. Also, in the case of parallel configurations of the molecules at the pentacene/C(60) interface, the decay of the lowest charge-transfer state to the ground state is calculated to be very fast; as a result, it can compete with the dissociation process into mobile charge carriers. Since parallel configurations are expected to be found more frequently in bulk heterojunctions than in bilayer heterojunctions, the performance of pentacene/C(60) bulk-heterojunction solar cells is likely to be more affected by charge recombination than that of bilayer devices.

An anomalous interlayer exciton in MoS2

NASA Astrophysics Data System (ADS)

Azhikodan, Dilna; Nautiyal, Tashi; Shallcross, Sam; Sharma, Sangeeta

2016-11-01

The few layer transition metal dichalcogenides are two dimensional materials that have an intrinsic gap of the order of ≈2 eV. The reduced screening in two dimensions implies a rich excitonic physics and, as a consequence, many potential applications in the field of opto-electronics. Here we report that a layer perpendicular electric field, by which the gap size in these materials can be efficiently controlled, generates an anomalous inter-layer exciton whose binding energy is independent of the gap size. We show this originates from the rich gap control and screening physics of TMDCs in a bilayer geometry: gating the bilayer acts on one hand to increase intra-layer screening by reducing the gap and, on the other hand, to decrease the inter-layer screening by field induced charge depletion. This constancy of binding energy is both a striking exception to the universal reduction in binding energy with gap size that all materials are believed to follow, as well as evidence of a degree of control over inter-layer excitons not found in their well studied intra-layer counterparts.

Exciton–exciton annihilation as a probe of interchain interactions in PPV–oligomer aggregates

DOE PAGES

Peteanu, Linda A.; Chowdhury, Sanchari; Wildeman, Jurjen; ...

2017-01-20

One measure of exciton mobility in an aggregate is the efficiency of exciton–exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH–PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed frommore » the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. Furthermore, the wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.« less

Effective-mass model and magneto-optical properties in hybrid perovskites

PubMed Central

Yu, Z. G.

2016-01-01

Hybrid inorganic-organic perovskites have proven to be a revolutionary material for low-cost photovoltaic applications. They also exhibit many other interesting properties, including giant Rashba splitting, large-radius Wannier excitons, and novel magneto-optical effects. Understanding these properties as well as the detailed mechanism of photovoltaics requires a reliable and accessible electronic structure, on which models of transport, excitonic, and magneto-optical properties can be efficiently developed. Here we construct an effective-mass model for the hybrid perovskites based on the group theory, experiment, and first-principles calculations. Using this model, we relate the Rashba splitting with the inversion-asymmetry parameter in the tetragonal perovskites, evaluate anisotropic g-factors for both conduction and valence bands, and elucidate the magnetic-field effect on photoluminescence and its dependence on the intensity of photoexcitation. The diamagnetic effect of exciton is calculated for an arbitrarily strong magnetic field. The pronounced excitonic peak emerged at intermediate magnetic fields in cyclotron resonance is assigned to the 3D±2 states, whose splitting can be used to estimate the difference in the effective masses of electron and hole. PMID:27338834

Effective-mass model and magneto-optical properties in hybrid perovskites.

PubMed

Yu, Z G

2016-06-24

Hybrid inorganic-organic perovskites have proven to be a revolutionary material for low-cost photovoltaic applications. They also exhibit many other interesting properties, including giant Rashba splitting, large-radius Wannier excitons, and novel magneto-optical effects. Understanding these properties as well as the detailed mechanism of photovoltaics requires a reliable and accessible electronic structure, on which models of transport, excitonic, and magneto-optical properties can be efficiently developed. Here we construct an effective-mass model for the hybrid perovskites based on the group theory, experiment, and first-principles calculations. Using this model, we relate the Rashba splitting with the inversion-asymmetry parameter in the tetragonal perovskites, evaluate anisotropic g-factors for both conduction and valence bands, and elucidate the magnetic-field effect on photoluminescence and its dependence on the intensity of photoexcitation. The diamagnetic effect of exciton is calculated for an arbitrarily strong magnetic field. The pronounced excitonic peak emerged at intermediate magnetic fields in cyclotron resonance is assigned to the 3D±2 states, whose splitting can be used to estimate the difference in the effective masses of electron and hole.

Effective-mass model and magneto-optical properties in hybrid perovskites

NASA Astrophysics Data System (ADS)

Yu, Z. G.

2016-06-01

Hybrid inorganic-organic perovskites have proven to be a revolutionary material for low-cost photovoltaic applications. They also exhibit many other interesting properties, including giant Rashba splitting, large-radius Wannier excitons, and novel magneto-optical effects. Understanding these properties as well as the detailed mechanism of photovoltaics requires a reliable and accessible electronic structure, on which models of transport, excitonic, and magneto-optical properties can be efficiently developed. Here we construct an effective-mass model for the hybrid perovskites based on the group theory, experiment, and first-principles calculations. Using this model, we relate the Rashba splitting with the inversion-asymmetry parameter in the tetragonal perovskites, evaluate anisotropic g-factors for both conduction and valence bands, and elucidate the magnetic-field effect on photoluminescence and its dependence on the intensity of photoexcitation. The diamagnetic effect of exciton is calculated for an arbitrarily strong magnetic field. The pronounced excitonic peak emerged at intermediate magnetic fields in cyclotron resonance is assigned to the 3D±2 states, whose splitting can be used to estimate the difference in the effective masses of electron and hole.

Charge generation in organic solar cell materials studied by terahertz spectroscopy

NASA Astrophysics Data System (ADS)

Scarongella, M.; Brauer, J. C.; Douglas, J. D.; Fréchet, J. M. J.; Banerji, N.

2015-09-01

We have investigated the photophysics in neat films of conjugated polymer PBDTTPD and its blend with PCBM using terahertz time-domain spectroscopy. This material has very high efficiency when used in organic solar cells. We were able to identify a THz signature for bound excitons in neat PBDTTPD films, pointing to important delocalization in those excitons. Then, we investigated the nature and local mobility (orders of magnitude higher than bulk mobility) of charges in the PBDTTPPD:PCBM blend as a function of excitation wavelength, fluence and pump-probe time delay. At low pump fluence (no bimolecular recombination phenomena), we were able to observe prompt and delayed charge generation components, the latter originating from excitons created in neat polymer domains which, thanks to delocalization, could reach the PCBM interface and dissociate to charges on a time scale of 1 ps. The nature of the photogenerated charges did not change between 0.5 ps and 800 ps after photo-excitation, which indicated that the excitons split directly into relatively free charges on an ultrafast time scale.

The mechanisms of delayed fluorescence in charge-transfer crystal of tetracyanobenzene-hexamethylbenzene

NASA Astrophysics Data System (ADS)

Kozankiewicz, B.; Prochorow, J.

1989-08-01

Fluorescence, phosphorescence and delayed fluorescence emission characteristics of tetracyanobenzene-hexamethylbenzene (TCNB-HMB) charge-transfer crystal have been studied in the 1.7-340 K temperature range. Delayed fluorescence, originating from heterogeneous triplet-triplet annihilation indicates the presence of mobile charge-transfer triplet excitons at a temperature as low as 1.7 K. However, the behaviour of triplet excitons in TCNB-HMB crystal is strongly controlled by a very efficient trapping process in the whole temperature range investigated. It was found that thermally activated delayed fluorescence, which is a dominating emission of the crystal at elevated temperatures (>60 K), has a different origin (a different initial state) at different temperatures. These observations were analysed and interpreted in terms of a photokinetic model, which is considered to be typical for charge-transfer crystals with high charge-transfer character of triplet excitons.

Employing exciton transfer molecules to increase the lifetime of phosphorescent red organic light emitting diodes

NASA Astrophysics Data System (ADS)

Lindla, Florian; Boesing, Manuel; van Gemmern, Philipp; Bertram, Dietrich; Keiper, Dietmar; Heuken, Michael; Kalisch, Holger; Jansen, Rolf H.

2011-04-01

The lifetime of phosphorescent red organic light emitting diodes (OLEDs) is investigated employing either N,N'-diphenyl-N,N'-bis(1-naphthylphenyl)-1,1'-biphenyl-4,4'-diamine (NPB), TMM117, or 4,4',4″-tris(N-carbazolyl)-triphenylamine (TCTA) as hole-conducting host material (mixed with an electron conductor). All OLED (organic vapor phase deposition-processed) show similar efficiencies around 30 lm/W but strongly different lifetimes. Quickly degrading OLED based on TCTA can be stabilized by doping exciton transfer molecules [tris-(phenyl-pyridyl)-Ir (Ir(ppy)3)] to the emission layer. At a current density of 50 mA/cm2 (12 800 cd/m2), a lifetime of 387 h can be achieved. Employing exciton transfer molecules is suggested to prevent the degradation of the red emission layer in phosphorescent white OLED.

Spectral densities for Frenkel exciton dynamics in molecular crystals: A TD-DFTB approach

NASA Astrophysics Data System (ADS)

Plötz, Per-Arno; Megow, Jörg; Niehaus, Thomas; Kühn, Oliver

2017-02-01

Effects of thermal fluctuations on the electronic excitation energies and intermonomeric Coulomb couplings are investigated for a perylene-tetracarboxylic-diimide crystal. To this end, time dependent density functional theory based tight binding (TD-DFTB) in the linear response formulation is used in combination with electronic ground state classical molecular dynamics. As a result, a parametrized Frenkel exciton Hamiltonian is obtained, with the effect of exciton-vibrational coupling being described by spectral densities. Employing dynamically defined normal modes, these spectral densities are analyzed in great detail, thus providing insight into the effect of specific intramolecular motions on excitation energies and Coulomb couplings. This distinguishes the present method from approaches using fixed transition densities. The efficiency by which intramolecular contributions to the spectral density can be calculated is a clear advantage of this method as compared with standard TD-DFT.

Exciton-phonon bound complex in single-walled carbon nanotubes revealed by high-field magneto-optical spectroscopy

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

Zhou, Weihang; Nakamura, Daisuke; Takeyama, Shojiro, E-mail: takeyama@issp.u-tokyo.ac.jp

2013-12-02

High-field magneto-optical spectroscopy was performed on highly enriched (6,5) single-walled carbon nanotubes. Spectra of phonon sidebands in both 1st and 2nd sub-bands were unchanged by an external magnetic field up to 52 T. The dark K-momentum singlet (D-K-S) exciton, which plays an important role for the external quantum efficiency of the system for both sub-bands in the near-infrared and the visible light region, respectively, was clarified to be the origin of the phonon sidebands.

Significant efficiency enhancement of hybrid solar cells using core-shell nanowire geometry for energy harvesting.

PubMed

Tsai, Shin-Hung; Chang, Hung-Chih; Wang, Hsin-Hua; Chen, Szu-Ying; Lin, Chin-An; Chen, Show-An; Chueh, Yu-Lun; He, Jr-Hau

2011-12-27

A novel strategy employing core-shell nanowire arrays (NWAs) consisting of Si/regioregular poly(3-hexylthiophene) (P3HT) was demonstrated to facilitate efficient light harvesting and exciton dissociation/charge collection for hybrid solar cells (HSCs). We experimentally demonstrate broadband and omnidirectional light-harvesting characteristics of core-shell NWA HSCs due to their subwavelength features, further supported by the simulation based on finite-difference time domain analysis. Meanwhile, core-shell geometry of NWA HSCs guarantees efficient charge separation since the thickness of the P3HT shells is comparable to the exciton diffusion length. Consequently, core-shell HSCs exhibit a 61% improvement of short-circuit current for a conversion efficiency (η) enhancement of 31.1% as compared to the P3HT-infiltrated Si NWA HSCs with layers forming a flat air/polymer cell interface. The improvement of crystal quality of P3HT shells due to the formation of ordering structure at Si interfaces after air mass 1.5 global (AM 1.5G) illumination was confirmed by transmission electron microscopy and Raman spectroscopy. The core-shell geometry with the interfacial improvement by AM 1.5G illumination promotes more efficient exciton dissociation and charge separation, leading to η improvement (∼140.6%) due to the considerable increase in V(oc) from 257 to 346 mV, J(sc) from 11.7 to 18.9 mA/cm(2), and FF from 32.2 to 35.2%, which is not observed in conventional P3HT-infiltrated Si NWA HSCs. The stability of the Si/P3HT core-shell NWA HSCs in air ambient was carefully examined. The core-shell geometry should be applicable to many other material systems of solar cells and thus holds high potential in third-generation solar cells.

Chiral Modes at Exceptional Points in Exciton-Polariton Quantum Fluids

NASA Astrophysics Data System (ADS)

Gao, T.; Li, G.; Estrecho, E.; Liew, T. C. H.; Comber-Todd, D.; Nalitov, A.; Steger, M.; West, K.; Pfeiffer, L.; Snoke, D. W.; Kavokin, A. V.; Truscott, A. G.; Ostrovskaya, E. A.

2018-02-01

We demonstrate the generation of chiral modes-vortex flows with fixed handedness in exciton-polariton quantum fluids. The chiral modes arise in the vicinity of exceptional points (non-Hermitian spectral degeneracies) in an optically induced resonator for exciton polaritons. In particular, a vortex is generated by driving two dipole modes of the non-Hermitian ring resonator into degeneracy. Transition through the exceptional point in the space of the system's parameters is enabled by precise manipulation of real and imaginary parts of the closed-wall potential forming the resonator. As the system is driven to the vicinity of the exceptional point, we observe the formation of a vortex state with a fixed orbital angular momentum (topological charge). This method can be extended to generate higher-order orbital angular momentum states through coalescence of multiple non-Hermitian spectral degeneracies. Our Letter demonstrates the possibility of exploiting nontrivial and counterintuitive properties of waves near exceptional points in macroscopic quantum systems.

Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport.

PubMed

Hartmann, Nicolai F; Pramanik, Rajib; Dowgiallo, Anne-Marie; Ihly, Rachelle; Blackburn, Jeffrey L; Doorn, Stephen K

2016-12-27

Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. Here, we present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. Pump-probe measurements suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. The open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.

Lead Selenide Colloidal Quantum Dot Solar Cells Achieving High Open-Circuit Voltage with One-Step Deposition Strategy.

PubMed

Zhang, Yaohong; Wu, Guohua; Ding, Chao; Liu, Feng; Yao, Yingfang; Zhou, Yong; Wu, Congping; Nakazawa, Naoki; Huang, Qingxun; Toyoda, Taro; Wang, Ruixiang; Hayase, Shuzi; Zou, Zhigang; Shen, Qing

2018-06-18

Lead selenide (PbSe) colloidal quantum dots (CQDs) are considered to be a strong candidate for high-efficiency colloidal quantum dot solar cells (CQDSCs) due to its efficient multiple exciton generation. However, currently, even the best PbSe CQDSCs can only display open-circuit voltage ( V oc ) about 0.530 V. Here, we introduce a solution-phase ligand exchange method to prepare PbI 2 -capped PbSe (PbSe-PbI 2 ) CQD inks, and for the first time, the absorber layer of PbSe CQDSCs was deposited in one step by using this PbSe-PbI 2 CQD inks. One-step-deposited PbSe CQDs absorber layer exhibits fast charge transfer rate, reduced energy funneling, and low trap assisted recombination. The champion large-area (active area is 0.35 cm 2 ) PbSe CQDSCs fabricated with one-step PbSe CQDs achieve a power conversion efficiency (PCE) of 6.0% and a V oc of 0.616 V, which is the highest V oc among PbSe CQDSCs reported to date.

Plasmonic based light manipulation and applications in AIGaN deep-UV devices (Conference Presentation)

NASA Astrophysics Data System (ADS)

Yin, Jun; Li, Jing; Kang, Junyong

2016-09-01

Recently, surface plasmon (SP)-exciton coupling has been wildly applied in nitride semiconductors in order to improve the spontaneous radiative recombination rate [1-3]. However, most works have been focused on the emission enhancement in InGaN-based blue or green light emitting diodes (LEDs). Practically, it is significantly important to improve the emission efficiency in deep-UV AlGaN-base quantum well (QW) structure due to its intrinsically low internal quantum efficiency (IQE) induced by the high defect density in its epitaxy layer [4]. But, the effective SP-exciton coupling with matched energy in deep-UV region is still a challenge issue due to the lack of appropriate metal structures and compatible fabrication techniques. In this work, the Al nanoparticles (NPs) were introduced by the nanosphere lithography (NSL) and deposition techniques into the AlGaN based MQWs with optimized size and structure. Due to the local surface plasmon (LSP) coupling with the excitons in QWs, emission enhancement in deep UV region has been achieved in the Al NPs decorated AlGaN MQWs structure with comparison to the bare MQWs. Theoretical calculations on the energy subbands of AlGaN QWs were further carried out to investigate the corresponding mechanisms, in which the hot carrier transition activated by SP-exciton coupling was believed to be mainly responsible for the enhancement. This work demonstrated a low cost, wafer scale fabrication process, which can be potentially employed to the practical SP-enhanced AlGaN-based deep UV LEDs with high IQEs.

Role of charge separation mechanism and local disorder at hybrid solar cell interfaces

NASA Astrophysics Data System (ADS)

Ehrenreich, Philipp; Pfadler, Thomas; Paquin, Francis; Dion-Bertrand, Laura-Isabelle; Paré-Labrosse, Olivier; Silva, Carlos; Weickert, Jonas; Schmidt-Mende, Lukas

2015-01-01

Dye-sensitized metal oxide polymer hybrid solar cells deliver a promising basis in organic solar cell development due to many conceptual advantages. Since the power conversion efficiency is still in a noncompetitive state, it has to be understood how the photocurrent contribution can be maximized (i.e., which dye-polymer properties are most beneficial for efficient charge generation in hybrid solar cells). By the comparison of three model systems for hybrid solar cells with Ti O2 -dye-polymer interfaces, this paper was aimed at elucidating the role of the exact mechanism of charge generation. In the exciton dissociation (ED) case, an exciton that is generated in the polymer is split at the dye-polymer interface. Alternatively, this exciton can be transferred to the dye via an energy transfer (ET), upon which charge separation occurs between dye and Ti O2 . For comparison, the third case is included in which the high lowest unoccupied molecular orbital of the dye does not allow exciton separation or ET from the dye to the polymer, so that the dye only is responsible for charge generation. To separate effects owing to differences in energy levels of the involved materials from the impact of local order and disorder in the polymer close to the interface, this paper further comprises a detailed analysis of the polymer crystallinity based on the H-aggregate model. While the massive impact of the poly(3-hexylthiophene) crystallinity on device function has been outlined for bare metal oxide-polymer interfaces, it has not been considered for hybrid solar cells with dye-sensitized Ti O2 . The results presented here indicate that all dye molecules in general influence the polymer morphology, which has to be taken into account for future optimization of hybrid solar cells. Apart from that, it can be suggested that ED on the polymer needs an additional driving force to work efficiently; thus, energy transfer seems to be currently the most promising strategy to increase the polymer photocurrent contribution.

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

Lingerfelt, David B.; Lestrange, Patrick J.; Radler, Joseph J.

Materials and molecular systems exhibiting long-lived electronic coherence can facilitate coherent transport, opening the door to efficient charge and energy transport beyond traditional methods. Recently, signatures of a possible coherent, recurrent electronic motion were identified in femtosecond pump-probe spectroscopy experiments on a binuclear platinum complex, where a persistent periodic beating in the transient absorption signal’s anisotropy was observed. In this study, we investigate the excitonic dynamics that underlie the suspected electronic coherence for a series of binuclear platinum complexes exhibiting a range of interplatinum distances. Results suggest that the long-lived coherence can only result when competitive electronic couplings are inmore » balance. At longer Pt-Pt distances, the electronic couplings between the two halves of the binuclear system weaken, and exciton localization and recombination is favored on short time scales. For short Pt-Pt distances, electronic couplings between the states in the coherent superposition are stronger than the coupling with other excitonic states, leading to long-lived coherence.« less

Light Harvesting for Organic Photovoltaics

PubMed Central

2016-01-01

The field of organic photovoltaics has developed rapidly over the last 2 decades, and small solar cells with power conversion efficiencies of 13% have been demonstrated. Light absorbed in the organic layers forms tightly bound excitons that are split into free electrons and holes using heterojunctions of electron donor and acceptor materials, which are then extracted at electrodes to give useful electrical power. This review gives a concise description of the fundamental processes in photovoltaic devices, with the main emphasis on the characterization of energy transfer and its role in dictating device architecture, including multilayer planar heterojunctions, and on the factors that impact free carrier generation from dissociated excitons. We briefly discuss harvesting of triplet excitons, which now attracts substantial interest when used in conjunction with singlet fission. Finally, we introduce the techniques used by researchers for characterization and engineering of bulk heterojunctions to realize large photocurrents, and examine the formed morphology in three prototypical blends. PMID:27951633

Generation of maximally entangled states and coherent control in quantum dot microlenses

NASA Astrophysics Data System (ADS)

Bounouar, Samir; de la Haye, Christoph; Strauß, Max; Schnauber, Peter; Thoma, Alexander; Gschrey, Manuel; Schulze, Jan-Hindrik; Strittmatter, André; Rodt, Sven; Reitzenstein, Stephan

2018-04-01

The integration of entangled photon emitters in nanophotonic structures designed for the broadband enhancement of photon extraction is a major challenge for quantum information technologies. We study the potential of quantum dot (QD) microlenses as efficient emitters of maximally entangled photons. For this purpose, we perform quantum tomography measurements on InGaAs QDs integrated deterministically into microlenses. Even though the studied QDs show non-zero excitonic fine-structure splitting (FSS), polarization entanglement can be prepared with a fidelity close to unity. The quality of the measured entanglement is only dependent on the temporal resolution of the applied single-photon detectors compared to the period of the excitonic phase precession imposed by the FSS. Interestingly, entanglement is kept along the full excitonic wave-packet and is not affected by decoherence. Furthermore, coherent control of the upper biexcitonic state is demonstrated.

Excitonic Gain and Laser Action in Zinc Selenide Based Quantum Confined Structures

NASA Astrophysics Data System (ADS)

Ding, Jian

1992-01-01

Successful doping (both n and p type) and the knowledge obtained through optical pumping studies of ZnSe/ZnCdSe quantum well laser structures have led to the successful realization of ZnCdSe/ZnSe/ZnCdSSe and ZnCdSe/ZnSe injection diode lasers at temperatures above 200K, so far under pulsed excitation, where ZnSe/ZnCdSe quantum wells (single or multiple) are used as the gain media. One of the key design issues in optimizing such diode lasers for eventual room temperature, continuous-wave (cw) operation in technological applications (such as high density optical memories) is the question about the microscopic mechanism responsible for gain and stimulated emission. In other words, are there departures from the standard degenerate electron -hole pair picture which is rooted in population inversion models e.g. for the III-V semiconductor lasers, including quantum wells (QW). That some closer consideration may indeed be appropriate is suggested by the strong excitonic effects which have been recently observed in the optical properties of ZnSe based QW's. In particular, it has been demonstrated that for the type I (Zn,Cd)Se/ZnSe QW system, the quasi-2 dimensional (2D) confinement of electron-hole pairs leads to enhancement of the exciton binding energy E_{rm x}, such that it exceeds the longitudinal optical (LO) phonon energy hbaromega_{sc LO }. In striking contrast to bulk ZnSe, strong, distinct exciton absorption features can be seen well above room temperature. The question hence arises whether exciton effects might also be of fundamental and practical consequence in laser structures. In this thesis, we present experimental evidence to argue that excitons indeed do play a central role in the formation of gain in the (Zn,Cd)Se/ZnSe QW's which have emerged as the prime candidates for diode lasers in the blue-green portion of the spectrum. By employing both steady state and picosecond spectroscopy, we show that the origin of gain and laser action in (Zn,Cd)Se/ZnSe quantum wells in the blue-green is of excitonic nature. Among other observations we find that stimulated emission occurs when excitation takes place resonantly into the n = 1 HH exciton absorption line. Picosecond excite-probe measurements demonstrate directly the existence of gain as well as dynamical process of exciton relaxation. A simple excitonic gain model is also given to explain the phenomena observed in the stimulated emission process in ZnCdSe/ZnSe quantum well structures.

Exciton polariton spectra and limiting factors for the room-temperature photoluminescence efficiency in ZnO

NASA Astrophysics Data System (ADS)

Chichibu, S. F.; Uedono, A.; Tsukazaki, A.; Onuma, T.; Zamfirescu, M.; Ohtomo, A.; Kavokin, A.; Cantwell, G.; Litton, C. W.; Sota, T.; Kawasaki, M.

2005-04-01

Static and dynamic responses of excitons in state-of-the-art bulk and epitaxial ZnO are reviewed to support the possible realization of polariton lasers, which are coherent and monochromatic light sources due to Bose condensation of exciton-polaritons in semiconductor microcavities (MCs). To grasp the current problems and to pave the way for obtaining ZnO epilayers of improved quality, the following four principal subjects are treated: (i) polarized optical reflectance (OR), photoreflectance (PR) and photoluminescence (PL) spectra of the bulk and epitaxial ZnO were recorded at 8 K. Energies of PR resonances corresponded to those of upper and lower exciton-polariton branches, where A-, B- and C-excitons couple simultaneously to an electromagnetic wave. PL peaks due to the corresponding polariton branches were observed. Longitudinal-transverse splittings (ωLT) of the corresponding excitons were 1.5, 11.1 and 13.1 meV, respectively. The latter two values are more than two orders of magnitude greater than that of GaAs being 0.08 meV. (ii) Using these values and material parameters, corresponding vacuum-field Rabi splitting of exciton-polaritons coupled to a model MC mode was calculated to be 191 meV, which is the highest value ever reported for semiconductor MCs and satisfies the requirements to observe the strong exciton-light coupling regime necessary for polariton lasing above room temperature. (iii) Polarized OR and PR spectra of an out-plane nonpolar (1\\,1\\,\\bar{2}\\,0) ZnO epilayer grown by laser-assisted molecular beam epitaxy (L-MBE) were measured, since ZnO quantum wells (QWs) grown in nonpolar orientations are expected to show higher emission efficiencies due to the elimination of spontaneous and piezoelectric polarization fields normal to the QW plane. They exhibited in-plane anisotropic exciton resonances according to the polarization selection rules for anisotropically-strained wurzite material. (iv) Impacts of point defects on the nonradiative processes in L-MBE ZnO were studied using time-resolved PL making a connection with the results of positron annihilation measurement. Free excitonic PL intensity at room temperature naturally increased with the increase in nonradiative lifetime (τnr). The value of τnr increased and density or size of Zn vacancies (VZn) decreased with increasing growth temperature (Tg) in heteroepitaxial films grown on a ScAlMgO4 substrate, and the use of homoepitaxial substrates further reduced VZn density. The value of τnr was shown to increase with the decrease in gross density of positively and negatively charged and neutral point defects including complexes rather than with the decrease in VZn density. The results indicate that the nonradiative recombination process is governed not by single point defects, but by certain defects introduced with the incorporation of VZn, such as VZn-defect complexes. As a result of defect elimination by growing the films at high Tg followed by subsequent post-growth in situ annealing, combined with the use of high-temperature-annealed ZnO self-buffer layer, a record long τnr for spontaneous emission of 3.8 ns was obtained at room temperature. By using progressively improving epitaxial growth methods, the polariton laser effect is expected to be observed at room temperature in the near future.

Exciton Relaxation and Electron Transfer Dynamics of Semiconductor Quantum Dots

NASA Astrophysics Data System (ADS)

Liu, Cunming

Quantum dots (QDs), also referred to as colloidal semiconductor nanocrystals, exhibit unique electronic and optical properties arising from their three-dimensional confinement and strongly enhanced coulomb interactions. Developing a detailed understanding of the exciton relaxation dynamics within QDs is important not only for sake of exploring the fundamental physics of quantum confinement processes, but also for their applications. Ultrafast transient absorption (TA) spectroscopy, as a powerful tool to explore the relaxation dynamics of excitons, was employed to characterize the hot single/multiexciton relaxation dynamics at the first four exciton states of CdSe/CdZnS QDs. We observed for the first time that the hot hole can relax through two possible pathways: Intraband multiple phonon coupling and intrinsic defect trapping, with a lifetime of ˜7 ps. Additionally, an ultra-short component of ˜ 8 ps, directly associated with the Auger recombination of highly energetic exciton states, was discovered. After exploring the exciton relaxation inside QDs, ultrafast TA spectroscopy was further applied to study the electron transferring outside from QDs. By using a brand-new photocatalytic system consisting of CdSe QDs and Ni-dihydrolipoic acid (Ni-DHLA) catalyst, which has represented a robust photocatalysis of H2 from water, the photoinduced electron transfer (ET) dynamics between QD and the catalyst, one of most important steps during H2 generation, was studied. We found smaller bare CdSe QDs exhibit a better ET performance and CdS shelling on the bare QDs leads to worsen the ET. The calculations of effective mass approximation (EMA) and Marcus theory show the ET process is mainly dominated by driving force, electronic coupling strength and reorganization energy between QD and the catalyst.

Broadband Light Collection Efficiency Enhancement of Carbon Nanotube Excitons Coupled to Metallo-Dielectric Antenna Arrays

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

Shayan, Kamran; Rabut, Claire; Kong, Xiaoqing

The realization of on-chip quantum networks ideally requires lossless interfaces between photons and solid-state quantum emitters. We propose and demonstrate on-chip arrays of metallo-dielectric antennas (MDA) that are tailored toward efficient and broadband light collection from individual embedded carbon nanotube quantum emitters by trapping air gaps on chip that form cavity modes. Scalable implementation is realized by employing polymer layer dry-transfer techniques that avoid solvent incompatibility issues, as well as a planar design that avoids solid-immersion lenses. Cryogenic measurements demonstrate 7-fold enhanced exciton intensity when compared to emitters located on bare wafers, corresponding to a light collection efficiency (LCE) upmore » to 92% in the best case (average LCE of 69%) into a narrow output cone of +/-15 degrees that enables a priori fiber-to-chip butt coupling. The demonstrated MDA arrays are directly compatible with other quantum systems, particularly 2D materials, toward enabling efficient on-chip quantum light sources or spin-photon interfaces requiring unity light collection, both at cryogenic or room temperature.« less

Strategies toward High Performance Organic Photovoltaic Cell: Material and Process

NASA Astrophysics Data System (ADS)

Kim, Bong Gi

The power conversion efficiency of organic photovoltaic (OPV) cells has been rapidly improved during the last few years and currently reaches around 10 %. The performance is evenly governed by absorption, exciton diffusion, exciton dissociation, carrier transfer, and collection efficiencies. Establishing a better understanding of OPV device physics combined with the development of new materials for each executive step contributes to this dramatic improvement. This dissertation focuses mainly on material design and development to correlate the intrinsic properties of organic semiconductors and the OPV performance. The introductory Chapter 1 briefly reviews the motivation of OPV research, its working mechanism, and representative organic materials for OPV application. Chapter 2 discusses the modulation of conjugated polymer's (CP's) absorption behavior and an efficient semi-empirical approach to predict CP's energy levels from its constituent monomers' HOMO/LUMO values. A strong acceptor lowered both the HOMO and LUMO levels of the CP, but the LUMO dropped more rapidly which ultimately produced a narrowed band-gap in the electron donating/accepting alternating copolymer system. In addition, the energy level difference between the CP and the constituent monomers converged to a constant value, providing an energy level prediction tool. Chapter 3 illustrates the systematic investigation on the relationship between the molecular structure of an energy harvesting organic dye and the exciton dissociation efficiency. The study showed that the quantum yield decreased as the exciton binding energy increases, and dipole moment direction should be properly oriented in the dye framework in order to improve photo-current generation when used in a dye sensitized photovoltaic device. Chapter 4 demonstrates the ultrasonic-assisted self-assembly of CPs in solution, rapidly and efficiently. Ultrasonication combined with dipolar media accelerated CP's aggregation, and the effect of CP's aggregation on the enhancement of OPV performance by promoting photo-current generation and increasing carrier mobility was systematically investigated. The correlation between the chemical structure of a CP and it aggregation behavior is further described in Chapter 5. To promote CP aggregate, a planar chain conformation was advantageous and CP aggregation improved hole mobility in the OPV device. However, thermally induced CP aggregates caused strong charge recombination, resulting in open circuit voltage drop. In Chapter 6, a novel polymer design principle to enable directed CP alignment is discussed. Regulating chain planarity and preventing massive crystallization of CP achieved by the developed molecular design principle allowed directed CP alignment under small shear flow.

Plasmon-Enhanced Multi-Carrier Photocatalysis.

PubMed

Shaik, Firdoz; Peer, Imanuel; Jain, Prashant K; Amirav, Lilac

2018-06-22

Conversion of solar energy into liquid fuel often relies on multi-electron redox processes that include highly reactive intermediates, with back reaction routes that hinder the overall efficiency of the process. Here we reveal that these undesirable reaction pathways can be minimized, rendering the photocatalytic reactions more efficient, when charge carriers are harvested from a multi-excitonic state of a semiconductor photocatalyst. A plasmonic antenna, comprised of Au nanoprisms, was employed to accomplish feasible levels of multiple carrier excitations in semiconductor nanocrystal-based photocatalytic systems (CdSe@CdS core-shell quantum dots and CdSe@CdS seeded nanorods). The antenna's near-field amplifies the otherwise inherently weak two-photon absorption in the semiconductor. The two-electron photoreduction of Pt and Pd metal precursors served as model reactions. In the presence of the plasmonic antenna, these photocatalyzed two-electron reactions exhibited enhanced yields and kinetics. This work uniquely relies on a non-linear enhancement that has potential for large amplification of photocatalytic activity in the presence of a plasmonic near-field.

Photoinduced Single- and Multiple-Electron Dynamics Processes Enhanced by Quantum Confinement in Lead Halide Perovskite Quantum Dots

DOE PAGES

Vogel, Dayton J.; Kryjevski, Andrei; Inerbaev, Talgat; ...

2017-03-21

Methylammonium lead iodide perovskite (MAPbI 3) is a promising material for photovoltaic devices. A modification of MAPbI 3 into confined nanostructures is expected to further increase efficiency of solar energy conversion. Photoexcited dynamic processes in a MAPbI3 quantum dot (QD) have been modeled by many-body perturbation theory and nonadiabatic dynamics. A photoexcitation is followed by either exciton cooling (EC), its radiative (RR) or nonradiative recombination (NRR), or multiexciton generation (MEG) processes. Computed times of these processes fall in the order of MEG < EC < RR < NRR, where MEG is on the order of a few femtoseconds, EC ismore » in the picosecond range, while RR and NRR are on the order of nanoseconds. Computed time scales indicate which electronic transition pathways can contribute to increase in charge collection efficiency. Simulated mechanisms of relaxation and their rates show that quantum confinement promotes MEG in MAPbI 3 QDs.« less

Fluorescent filtered electrophosphorescence

DOEpatents

Forrest, Stephen; Sun, Yiru; Giebink, Noel; Thompson, Mark E.

2010-08-03

The present invention relates to organic light emitting devices (OLEDs), and more specifically to OLEDS that emit light using a combination of fluorescent emitters and phosphorescent emitters for the efficient utilization of all of the electrically generated excitons.

Fluorescent filtered electrophosphorescence

DOEpatents

Forrest, Stephen R [Princeton, NJ; Sun, Yiru [Princeton, NJ; Giebink, Noel [Princeton, NJ; Thompson, Mark E [Anaheim Hills, CA

2009-01-06

The present invention relates to organic light emitting devices (OLEDs), and more specifically to OLEDS that emit light using a combination of fluorescent emitters and phosphorescent emitters for the efficient utilization of all of the electrically generated excitons.

Low-voltage polariton electroluminescence from an ultrastrongly coupled organic light-emitting diode

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

Gubbin, Christopher R.; Maier, Stefan A.; Kéna-Cohen, Stéphane, E-mail: s.kena-cohen@polymtl.ca

2014-06-09

We demonstrate electroluminescence from Frenkel molecular excitons ultrastrongly coupled to photons of a metal-clad microcavity containing a 2,7-bis[9,9-di(4-methylphenyl)-fluoren-2-yl]-9,9-di(4-methylphenyl)fluorene emissive layer. Thin layers of molybdenum oxide and 4,7-diphenyl-1,10-phenanthroline are used as hole and electron injection layers, respectively. The fabricated devices exhibit an electroluminescence threshold of 3.1 V, a value that is below the bare exciton energy. This result is found to be independent of detuning and consistent with a two-step process for polariton formation. Moreover, we investigate the quantum efficiency of carrier to polariton to photon conversion and obtain an external quantum efficiency of 0.1% for the fabricated structures, an improvement ofmore » 5 orders of magnitude over previous reports.« less

Lineshape theory of pigment-protein complexes: How the finite relaxation time of nuclei influences the exciton relaxation-induced lifetime broadening.

PubMed

Dinh, Thanh-Chung; Renger, Thomas

2016-07-21

In pigment-protein complexes, often the excited states are partially delocalized and the exciton-vibrational coupling in the basis of delocalized states contains large diagonal and small off-diagonal elements. This inequality may be used to introduce potential energy surfaces (PESs) of exciton states and to treat the inter-PES coupling in Markov and secular approximations. The resulting lineshape function consists of a Lorentzian peak that is broadened by the finite lifetime of the exciton states caused by the inter-PES coupling and a vibrational sideband that results from the mutual displacement of the excitonic PESs with respect to that of the ground state. So far analytical expressions have been derived that relate the exciton relaxation-induced lifetime broadening to the Redfield [T. Renger and R. A. Marcus, J. Chem. Phys. 116, 9997 (2002)] or modified Redfield [M. Schröder, U. Kleinekathöfer, and M. Schreiber, J. Chem. Phys. 124, 084903 (2006)] rate constants of exciton relaxation, assuming that intra-PES nuclear relaxation is fast compared to inter-PES transfer. Here, we go beyond this approximation and provide an analytical expression, termed Non-equilibrium Modified Redfield (NeMoR) theory, for the lifetime broadening that takes into account the finite nuclear relaxation time. In an application of the theory to molecular dimers, we find that, for a widely used experimental spectral density of the exciton-vibrational coupling of pigment-protein complexes, the NeMoR spectrum at low-temperatures (T < 150 K) is better approximated by Redfield than by modified Redfield theory. At room temperature, the lifetime broadening obtained with Redfield theory underestimates the NeMoR broadening, whereas modified Redfield theory overestimates it by a similar amount. A fortuitous error compensation in Redfield theory is found to explain the good performance of this theory at low temperatures. Since steady state spectra of PPCs are often measured at low temperatures, Redfield theory still provides a numerically efficient alternative to NeMoR theory. At higher temperatures, we suggest to use NeMoR theory, because it has the same numerical costs as modified Redfield theory, but is more accurate.

Exciton-vibrational coupling in the dynamics and spectroscopy of Frenkel excitons in molecular aggregates

NASA Astrophysics Data System (ADS)

Schröter, M.; Ivanov, S. D.; Schulze, J.; Polyutov, S. P.; Yan, Y.; Pullerits, T.; Kühn, O.

2015-03-01

The influence of exciton-vibrational coupling on the optical and transport properties of molecular aggregates is an old problem that gained renewed interest in recent years. On the experimental side, various nonlinear spectroscopic techniques gave insight into the dynamics of systems as complex as photosynthetic antennae. Striking evidence was gathered that in these protein-pigment complexes quantum coherence is operative even at room temperature conditions. Investigations were triggered to understand the role of vibrational degrees of freedom, beyond that of a heat bath characterized by thermal fluctuations. This development was paralleled by theory, where efficient methods emerged, which could provide the proper frame to perform non-Markovian and non-perturbative simulations of exciton-vibrational dynamics and spectroscopy. This review summarizes the state of affairs of the theory of exciton-vibrational interaction in molecular aggregates and photosynthetic antenna complexes. The focus is put on the discussion of basic effects of exciton-vibrational interaction from the stationary and dynamics points of view. Here, the molecular dimer plays a prominent role as it permits a systematic investigation of absorption and emission spectra by numerical diagonalization of the exciton-vibrational Hamiltonian in a truncated Hilbert space. An extension to larger aggregates, having many coupled nuclear degrees of freedom, becomes possible with the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method for wave packet propagation. In fact it will be shown that this method allows one to approach the limit of almost continuous spectral densities, which is usually the realm of density matrix theory. Real system-bath situations are introduced for two models, which differ in the way strongly coupled nuclear coordinates are treated, as a part of the relevant system or the bath. A rather detailed exposition of the Hierarchy Equations Of Motion (HEOM) method will be given in terms of a stochastic decoupling ansatz. This method has become the standard in exciton-vibrational theory and illustrative examples will be presented as well as a comparison with ML-MCTDH. Applications will be shown for generic model systems as well as for small aggregates mimicking those formed by perylene bisimide dyes. Further, photosynthetic antenna complexes will be discussed, including spectral densities and the role of exciton-vibrational coupling in two-dimensional electronic spectroscopy.

Exploring ultrafast dynamics of excitons and multiexcitons in "giant" nanocrystal quantum dots

NASA Astrophysics Data System (ADS)

Sampat, Siddharth

In this work, we have performed extensive time resolved photoluminescence (PL) studies to further the understanding of charge dynamics in semiconductor nanocrystal quantum dots (QDs). Recent developments in QD synthesis have introduced a new set of QD known as "giant" quantum dots (gQDs) that consist of a CdSe core coated with up to 19 monolayers of a CdS shell. The thick shell layer is grown using a SILAR method resulting in a defect free, alloyed CdSe/CdS interface. This has been attributed to gQDs exhibiting excellent optical properties such as high excitonic quantum yield (QY), prolonged photostability and inhibition of flourescence intermittency ("blinking"), which is regularly observed in conventional QDs. In gQDs, however, owing to unique fabrication methods and material selection, the Auger process is strongly suppressed resulting in efficient radiative recombination of photogenerated excitons as well as high PL QY of charged excitonic and multiexcitonic species. We perform extensive single gQDs studies that establish the role played by gQD shell thickness and core size in governing their optical properties. It is found that both the core and shell dimensions can be tuned in order to achieve the smallest gQDs with the highest vii Auger suppression resulting in photostable dots with high QYs. Next, we perform a study of multiexcitonic species in gQDs that are encapsulated in an insulating SiO2shell. These silica-coated gQDs exhibit strong PL from charged excitons, biexcitons as well as triexcitons. This observation has led to an accurate description of excitonic and multiexcitonic behavior which is modeled using a statistical scaling approach. As a demonstration of the practical applicability of gQDs, energy transfer of excitons as well as multiexcitons to different substrates is studied. Finally, a back gated silicon nanomembrane FET device is discussed that exhibits a large photocurrent increase when sensitized with QDs.

Nearly Perfect Triplet-Triplet Energy Transfer from Wannier Excitons to Naphthalene in Organic-Inorganic Hybrid Quantum-Well Materials

NASA Astrophysics Data System (ADS)

Ema, K.; Inomata, M.; Kato, Y.; Kunugita, H.; Era, M.

2008-06-01

We report the observation of extremely efficient energy transfer (greater than 99%) in an organic-inorganic hybrid quantum-well structure consisting of perovskite-type lead bromide well layers and naphthalene-linked ammonium barrier layers. Time-resolved photoluminescence measurements confirm that the transfer is triplet-triplet Dexter-type energy transfer from Wannier excitons in the inorganic well to the triplet state of naphthalene molecules in the organic barrier. Using measurements in the 10 300 K temperature range, we also investigated the temperature dependence of the energy transfer.

On the possibility of singlet fission in crystalline quaterrylene

NASA Astrophysics Data System (ADS)

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-01

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (ES-2ET) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

On the possibility of singlet fission in crystalline quaterrylene.

PubMed

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-14

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (E S -2E T ) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

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

Highly efficient organic light emitting diodes formed by solution processed red emitters with evaporated blue common layer structure.

PubMed

Cho, Ye Ram; Kim, Hyung Suk; Yu, Young-Jun; Suh, Min Chul

2015-10-30

We prepared highly-efficient solution-processed red phosphorescent organic light emitting diodes (PHOLEDs) with a blue common layer structure that can reasonably confine the triplet excitons inside of the red emission layer (EML) with the assistance of a bipolar exciton blocking layer. The red PHOLEDs containing EML with a 7 : 3 ratio of 11-(4,6-diphenyl-[1,3,5]triazin-2-yl)-12-phenyl-11,12-dihydro-11,12-diaza-indeno[2,1-a]fluorene (n-type host, NH) : 4-(3-(triphenylen-2-yl)phenyl)dibenzo[b,d]thiophene (p-type host, PH) doped with 5% Iridium(III) bis(2-(3,5-dimethylphenyl)quinolinato-N,C2')tetramethylheptadionate (Red Dopant, RD) produced the highest current and power efficiencies at 23.4 cd/A and 13.6 lm/W, with a 19% external quantum efficiency at 1000 cd/m(2). To the best of our knowledge, such efficiency was the best among those that have been obtained from solution-processed small molecular red PHOLEDs. In addition, the host molecules utilized in this study have no flexible spacers, such as an alkyl chain, which normally deteriorate the stability of the device.

Highly efficient organic light emitting diodes formed by solution processed red emitters with evaporated blue common layer structure

NASA Astrophysics Data System (ADS)

Cho, Ye Ram; Kim, Hyung Suk; Yu, Young-Jun; Suh, Min Chul

2015-10-01

We prepared highly-efficient solution-processed red phosphorescent organic light emitting diodes (PHOLEDs) with a blue common layer structure that can reasonably confine the triplet excitons inside of the red emission layer (EML) with the assistance of a bipolar exciton blocking layer. The red PHOLEDs containing EML with a 7 : 3 ratio of 11-(4,6-diphenyl-[1,3,5]triazin-2-yl)-12-phenyl-11,12-dihydro-11,12-diaza-indeno[2,1-a]fluorene (n-type host, NH) : 4-(3-(triphenylen-2-yl)phenyl)dibenzo[b,d]thiophene (p-type host, PH) doped with 5% Iridium(III) bis(2-(3,5-dimethylphenyl)quinolinato-N,C2’)tetramethylheptadionate (Red Dopant, RD) produced the highest current and power efficiencies at 23.4 cd/A and 13.6 lm/W, with a 19% external quantum efficiency at 1000 cd/m2. To the best of our knowledge, such efficiency was the best among those that have been obtained from solution-processed small molecular red PHOLEDs. In addition, the host molecules utilized in this study have no flexible spacers, such as an alkyl chain, which normally deteriorate the stability of the device.

Highly efficient organic light emitting diodes formed by solution processed red emitters with evaporated blue common layer structure

PubMed Central

Cho, Ye Ram; Kim, Hyung Suk; Yu, Young-Jun; Suh, Min Chul

2015-01-01

We prepared highly-efficient solution-processed red phosphorescent organic light emitting diodes (PHOLEDs) with a blue common layer structure that can reasonably confine the triplet excitons inside of the red emission layer (EML) with the assistance of a bipolar exciton blocking layer. The red PHOLEDs containing EML with a 7 : 3 ratio of 11-(4,6-diphenyl-[1,3,5]triazin-2-yl)-12-phenyl-11,12-dihydro-11,12-diaza-indeno[2,1-a]fluorene (n-type host, NH) : 4-(3-(triphenylen-2-yl)phenyl)dibenzo[b,d]thiophene (p-type host, PH) doped with 5% Iridium(III) bis(2-(3,5-dimethylphenyl)quinolinato-N,C2’)tetramethylheptadionate (Red Dopant, RD) produced the highest current and power efficiencies at 23.4 cd/A and 13.6 lm/W, with a 19% external quantum efficiency at 1000 cd/m2. To the best of our knowledge, such efficiency was the best among those that have been obtained from solution-processed small molecular red PHOLEDs. In addition, the host molecules utilized in this study have no flexible spacers, such as an alkyl chain, which normally deteriorate the stability of the device. PMID:26514274

Carrier multiplication in semiconductor nanocrystals: theoretical screening of candidate materials based on band-structure effects.

PubMed

Luo, Jun-Wei; Franceschetti, Alberto; Zunger, Alex

2008-10-01

Direct carrier multiplication (DCM) occurs when a highly excited electron-hole pair decays by transferring its excess energy to the electrons rather than to the lattice, possibly exciting additional electron-hole pairs. Atomistic electronic structure calculations have shown that DCM can be induced by electron-hole Coulomb interactions, in an impact-ionization-like process whose rate is proportional to the density of biexciton states rho XX. Here we introduce a DCM "figure of merit" R2(E) which is proportional to the ratio between the biexciton density of states rhoXX and the single-exciton density of states rhoX, restricted to single-exciton and biexciton states that are coupled by Coulomb interactions. Using R2(E), we consider GaAs, InAs, InP, GaSb, InSb, CdSe, Ge, Si, and PbSe nanocrystals of different sizes. Although DCM can be affected by both quantum-confinement effects (reflecting the underly electronic structure of the confined dot-interior states) and surface effects, here we are interested to isolate the former. To this end the nanocrystal energy levels are obtained from the corresponding bulk band structure via the truncated crystal approximation. We find that PbSe, Si, GaAs, CdSe, and InP nanocrystals have larger DCM figure of merit than the other nanocrystals. Our calculations suggest that high DCM efficiency requires high degeneracy of the corresponding bulk band-edge states. Interestingly, by considering band structure effects we find that as the dot size increases the DCM critical energy E0 (the energy at which R2(E) becomes >or=1) is reduced, suggesting improved DCM. However, whether the normalized E0/epsilong increases or decreases as the dot size increases depends on dot material.

Conformation-related exciton localization and charge-pair formation in polythiophenes: ensemble and single-molecule study.

PubMed

Sugimoto, Toshikazu; Habuchi, Satoshi; Ogino, Kenji; Vacha, Martin

2009-09-10

We study conformation-dependent photophysical properties of polythiophene (PT) by molecular dynamics simulations and by ensemble and single-molecule optical experiments. We use a graft copolymer consisting of a polythiophene backbone and long polystyrene branches and compare its properties with those obtained on the same polythiophene derivative without the side chains. Coarse-grain molecular dynamics simulations show that in a poor solvent, the PT without the side chains (PT-R) forms a globulelike conformation in which distances between any two conjugated segments on the chain are within the Forster radius for efficient energy transfer. In the PT with the polystyrene branches (PT-PS), the polymer main PT chain retains an extended coillike conformation, even in a poor solvent, and the calculated distances between conjugated segments favor energy transfer only between a few neighboring chromophores. The theoretical predictions are confirmed by measurements of fluorescence anisotropy and fluorescence blinking of the polymers' single chains. High anisotropy ratios and two-state blinking in PT-R are due to localization of the exciton on a single conjugated segment. These signatures of exciton localization are absent in single chains of PT-PS. Electric-field-induced quenching measured as a function of concentration of PT dispersed in an inert matrix showed that in well-isolated chains of PT-PS, the exciton dissociation is an intrachain process and that aggregation of the PT-R chains causes an increase in quenching due to the onset of interchain interactions. Measurements of the field-induced quenching on single chains indicate that in PT-R, the exciton dissociation is a slower process that takes place only after the exciton is localized on one conjugated segment.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

DOE PAGES

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.; ...

2017-09-13

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Signatures of correlated excitonic dynamics in two-dimensional spectroscopy of the Fenna-Matthew-Olson photosynthetic complex

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

Caram, Justin R.; Lewis, Nicholas H. C.; Fidler, Andrew F.

2012-03-14

Long-lived excitonic coherence in photosynthetic proteins has become an exciting area of research because it may provide design principles for enhancing the efficiency of energy transfer in a broad range of materials. In this publication, we provide new evidence that long-lived excitonic coherence in the Fenna-Mathew-Olson pigment-protein (FMO) complex is consistent with the assumption of cross correlation in the site basis, indicating that each site shares bath fluctuations. We analyze the structure and character of the beating crosspeak between the two lowest energy excitons in two-dimensional (2D) electronic spectra of the FMO Complex. To isolate this dynamic signature, we usemore » the two-dimensional linear prediction Z-transform as a platform for filtering coherent beating signatures within 2D spectra. By separating signals into components in frequency and decay rate representations, we are able to improve resolution and isolate specific coherences. This strategy permits analysis of the shape, position, character, and phase of these features. Simulations of the crosspeak between excitons 1 and 2 in FMO under different regimes of cross correlation verify that statistically independent site fluctuations do not account for the elongation and persistence of the dynamic crosspeak. To reproduce the experimental results, we invoke near complete correlation in the fluctuations experienced by the sites associated with excitons 1 and 2. This model contradicts ab initio quantum mechanic/molecular mechanics simulations that observe no correlation between the energies of individual sites. This contradiction suggests that a new physical model for long-lived coherence may be necessary. The data presented here details experimental results that must be reproduced for a physical model of quantum coherence in photosynthetic energy transfer.« less

Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport

DOE PAGES

Hartmann, Nicolai F.; Pramanik, Rajib; Dowgiallo, Anne-Marie; ...

2016-12-06

Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. We present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. The pump-probe measurementsmore » suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. Furthermore, the open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.« less

Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport

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

Hartmann, Nicolai F.; Pramanik, Rajib; Dowgiallo, Anne-Marie

Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. We present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. The pump-probe measurementsmore » suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. Furthermore, the open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.« less

Exciton scattering approach for optical spectra calculations in branched conjugated macromolecules

NASA Astrophysics Data System (ADS)

Li, Hao; Wu, Chao; Malinin, Sergey V.; Tretiak, Sergei; Chernyak, Vladimir Y.

2016-12-01

The exciton scattering (ES) technique is a multiscale approach based on the concept of a particle in a box and developed for efficient calculations of excited-state electronic structure and optical spectra in low-dimensional conjugated macromolecules. Within the ES method, electronic excitations in molecular structure are attributed to standing waves representing quantum quasi-particles (excitons), which reside on the graph whose edges and nodes stand for the molecular linear segments and vertices, respectively. Exciton propagation on the linear segments is characterized by the exciton dispersion, whereas exciton scattering at the branching centers is determined by the energy-dependent scattering matrices. Using these ES energetic parameters, the excitation energies are then found by solving a set of generalized "particle in a box" problems on the graph that represents the molecule. Similarly, unique energy-dependent ES dipolar parameters permit calculations of the corresponding oscillator strengths, thus, completing optical spectra modeling. Both the energetic and dipolar parameters can be extracted from quantum-chemical computations in small molecular fragments and tabulated in the ES library for further applications. Subsequently, spectroscopic modeling for any macrostructure within a considered molecular family could be performed with negligible numerical effort. We demonstrate the ES method application to molecular families of branched conjugated phenylacetylenes and ladder poly-para-phenylenes, as well as structures with electron donor and acceptor chemical substituents. Time-dependent density functional theory (TD-DFT) is used as a reference model for electronic structure. The ES calculations accurately reproduce the optical spectra compared to the reference quantum chemistry results, and make possible to predict spectra of complex macromolecules, where conventional electronic structure calculations are unfeasible.

Charge Separation and Triplet Exciton Formation Pathways in Small Molecule Solar Cells as Studied by Time-resolved EPR Spectroscopy.

PubMed

Thomson, Stuart A J; Niklas, Jens; Mardis, Kristy L; Mallares, Christopher; Samuel, Ifor D W; Poluektov, Oleg G

2017-10-19

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2 ) 2 , DTS(F 2 BTTh 2 ) 2 , DTS(PTTh 2 ) 2 , DTG(FBTTh 2 ) 2 and DTG(F 2 BTTh 2 ) 2 ) with the fullerene derivative PC 61 BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2 ) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2 ) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. The higher BET triplet exciton population in the DTS(PTTh 2 ) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

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

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Highly Efficient Defect Emission from ZnO:Zn and ZnO:S Powders

NASA Astrophysics Data System (ADS)

Everitt, Henry

2013-03-01

Bulk Zinc Oxide (ZnO) is a wide band gap semiconductor with an ultraviolet direct band gap energy of 3.4 eV and a broad, defect-related visible wavelength emission band centered near 2 eV. We have shown that the external quantum efficiency can exceed 50% for this nearly white emission band that closely matches the human dark-adapted visual response. To explore the potential of ZnO as a rare earth-free white light phosphor, we investigated the mechanism of efficient defect emission in three types of ZnO powders: unannealed, annealed, and sulfur-doped. Annealing and sulfur-doping of ZnO greatly increase the strength of defect emission while suppressing the UV band edge emission. Continuous wave and ultrafast one- and two-photon excitation spectroscopy are used to examine the defect emission mechanism. Low temperature photoluminescence (PL) and PL excitation (PLE) spectra were measured for all three compounds, and it was found that bound excitons mediate the defect emission. Temperature-dependent PLE spectra for the defect and band edge emission were measured to estimate trapping and activation energies of the bound excitons and clarify the role they play in the defect emission. Time-resolved techniques were used to ascertain the role of exciton diffusion, the effects of reabsorption, and the spatial distributions of radiative and non-radiative traps. In unannealed ZnO we find that defect emission is suppressed and UV band edge emission is inefficient (< 2%) because of reabsorption and non-radiative recombination due to a high density of non-radiative bulk traps. By annealing ZnO, bulk trap densities are reduced, and a high density of defects responsible for the broad visible emission are created near the surface. Interestingly, nearly identical PLE spectra are found for both the band edge and the defect emission, one of many indications that the defect emission is deeply connected to bound excitons. Quantum efficiency, also measured as a function of excitation wavelength, closely mirrors the PLE spectra for both emission bands. Sulfur-doped ZnO exhibits additional PLE and X-ray features indicative of a ZnS-rich surface shell that correlates with even more efficient defect emission. The results presented here offer hope that engineering defects in ZnO materials may significantly improve the quantum efficiency for white light phosphor applications. This work was supported by the Army's in-house laboratory innovative research program.

Enhanced Exciton and Photon Confinement in Ruddlesden-Popper Perovskite Microplatelets for Highly Stable Low-Threshold Polarized Lasing.

PubMed

Li, Mingjie; Wei, Qi; Muduli, Subas Kumar; Yantara, Natalia; Xu, Qiang; Mathews, Nripan; Mhaisalkar, Subodh G; Xing, Guichuan; Sum, Tze Chien

2018-06-01

At the heart of electrically driven semiconductors lasers lies their gain medium that typically comprises epitaxially grown double heterostuctures or multiple quantum wells. The simultaneous spatial confinement of charge carriers and photons afforded by the smaller bandgaps and higher refractive index of the active layers as compared to the cladding layers in these structures is essential for the optical-gain enhancement favorable for device operation. Emulating these inorganic gain media, superb properties of highly stable low-threshold (as low as ≈8 µJ cm -2 ) linearly polarized lasing from solution-processed Ruddlesden-Popper (RP) perovskite microplatelets are realized. Detailed investigations using microarea transient spectroscopies together with finite-difference time-domain simulations validate that the mixed lower-dimensional RP perovskites (functioning as cladding layers) within the microplatelets provide both enhanced exciton and photon confinement for the higher-dimensional RP perovskites (functioning as the active gain media). Furthermore, structure-lasing-threshold relationship (i.e., correlating the content of lower-dimensional RP perovskites in a single microplatelet) vital for design and performance optimization is established. Dual-wavelength lasing from these quasi-2D RP perovskite microplatelets can also be achieved. These unique properties distinguish RP perovskite microplatelets as a new family of self-assembled multilayer planar waveguide gain media favorable for developing efficient lasers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impacts of side chain and excess energy on the charge photogeneration dynamics of low-bandgap copolymer-fullerene blends

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

Huo, Ming-Ming, E-mail: hithuomm@163.com; Zhang, Jian-Ping, E-mail: jpzhang@chem.ruc.edu.cn, E-mail: hjhzlz@iccas.ac.cn; Department of Chemistry, Renmin University of China, Beijing 100872

2014-02-28

Primary charge photogeneration dynamics in neat and fullerene-blended films of a pair of alternating benzo[1,2-b:4,5-b{sup ′}]dithiophene (BDT) and thieno[3,4-b]thiophene (TT) copolymers are comparatively studied by using near-infrared, time-resolved absorption (TA) spectroscopy under low excitation photon fluence. PBDTTT-E and PBDTTT-C, differed merely in the respective TT-substituents of ester (-E) and carbonyl (-C), show distinctly different charge photogeneration dynamics. The pair of neat PBDTTT films show exciton lifetimes of ∼0.1 ns and fluorescence quantum yields below 0.2%, as well as prominent excess-energy enhanced exciton dissociation. In addition, PBDTTT-C gives rise to >50% higher P{sup •+} yield than PBDTTT-E does irrespective to themore » excitation photon energy. Both PBDTTT-E:PC{sub 61}BM and PBDTTT-C:PC{sub 61}BM blends show subpicosecond exciton lifetimes and nearly unitary fluorescence quenching efficiency and, with respect to the former blend, the latter one shows substantially higher branching ratio of charge separated (CS) state over interfacial charge transfer (ICT) state, and hence more efficient exciton-to-CS conversion. For PBDTTT-C:PC{sub 61}BM, the ultrafast charge dynamics clearly show the processes of ICT-CS interconversion and P{sup •+} migration, which are possibly influenced by the ICT excess energy. However, such processes are relatively indistinctive in the case of PBDTTT-E:PC{sub 61}BM. The results strongly prove the importance of ICT dissociation in yielding free charges, and are discussed in terms of the film morphology and the precursory solution-phase macromolecular conformation.« less

Global coherence of quantum evolutions based on decoherent histories: Theory and application to photosynthetic quantum energy transport

NASA Astrophysics Data System (ADS)

Allegra, Michele; Giorda, Paolo; Lloyd, Seth

2016-04-01

Assessing the role of interference in natural and artificial quantum dynamical processes is a crucial task in quantum information theory. To this aim, an appropriate formalism is provided by the decoherent histories framework. While this approach has been deeply explored from different theoretical perspectives, it still lacks of a comprehensive set of tools able to concisely quantify the amount of coherence developed by a given dynamics. In this paper, we introduce and test different measures of the (average) coherence present in dissipative (Markovian) quantum evolutions, at various time scales and for different levels of environmentally induced decoherence. In order to show the effectiveness of the introduced tools, we apply them to a paradigmatic quantum process where the role of coherence is being hotly debated: exciton transport in photosynthetic complexes. To spot out the essential features that may determine the performance of the transport, we focus on a relevant trimeric subunit of the Fenna-Matthews-Olson complex and we use a simplified (Haken-Strobl) model for the system-bath interaction. Our analysis illustrates how the high efficiency of environmentally assisted transport can be traced back to a quantum recoil avoiding effect on the exciton dynamics, that preserves and sustains the benefits of the initial fast quantum delocalization of the exciton over the network. Indeed, for intermediate levels of decoherence, the bath is seen to selectively kill the negative interference between different exciton pathways, while retaining the initial positive one. The concepts and tools here developed show how the decoherent histories approach can be used to quantify the relation between coherence and efficiency in quantum dynamical processes.

Distinct Interfacial Fluorescence in Oil-in-Water Emulsions via Exciton Migration of Conjugated Polymers.

PubMed

Koo, Byungjin; Swager, Timothy M

2017-09-01

Commercial dyes are extensively utilized to stain specific phases for the visualization applications in emulsions and bioimaging. In general, dyes emit only one specific fluorescence signal and thus, in order to stain various phases and/or interfaces, one needs to incorporate multiple dyes and carefully consider their compatibility to avoid undesirable interactions with each other and with the components in the system. Herein, surfactant-type, perylene-endcapped fluorescent conjugated polymers that exhibit two different emissions are reported, which are cyan in water and red at oil-water interfaces. The interfacially distinct red emission results from enhanced exciton migration from the higher-bandgap polymer backbone to the lower-bandgap perylene endgroup. The confocal microscopy images exhibit the localized red emission exclusively from the circumference of oil droplets. This exciton migration and dual fluorescence of the polymers in different physical environments can provide a new concept of visualization methods in many amphiphilic colloidal systems and bioimaging. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrated spectral photocurrent density and reproducibility analyses of excitonic ZnO/NiO heterojunction.

PubMed

Patel, Malkeshkumar; Kim, Joondong

2017-12-01

In this data article, the excitonic ZnO/NiO heterojunction device (Patel et al., 2017) [1] was measured for the integrated photocurrent density and reproducibility. Photograph of the prepared devices of ZnO/NiO on the FTO/glass is presented. Integrated photocurrent density as a function of photon energy from the sunlight is presented. Quantum efficiency measurement system (McScienceK3100, Korea) compliance with International Measurement System was employed to measure ZnO/NIO devices. These data are shown for the 300-440 nm of segment of the sunlight (AM1.5G, http://rredc.nrel.gov/solar/spectra/am1.5/). Reproducibility measure of ZnO/NiO device was presented for nine devices with the estimated device performance parameters including the open circuit voltage, short circuit current density, fill factor and power conversion efficiency.

Enhancing the luminescence efficiency of silicon-nanocrystals by interaction with H+ ions.

PubMed

Cannas, Marco; Camarda, Pietro; Vaccaro, Lavinia; Amato, Francesco; Messina, Fabrizio; Fiore, Tiziana; Li Vigni, Maria

2018-04-18

The emission of silicon nanocrystals (Si-NCs), synthesized by pulsed laser ablation in water, was investigated on varying the pH of the solution. These samples emit μs decaying orange photoluminescence (PL) associated with radiative recombination of quantum-confined excitons. Time-resolved spectra reveal that both the PL intensity and the lifetime increase by a factor of ∼20 when the pH decreases from 10 to 1 thus indicating that the emission quantum efficiency increases by inhibiting nonradiative decay rates. Infrared (IR) absorption and electron paramagnetic resonance (EPR) experiments allow addressing the origin of defects on which the excitons nonradiatively recombine. The linear correlation between the PL and the growth of SiH groups demonstrates that H+ ions passivate the nonradiative defects that are located in the interlayer between the Si-NC core and the amorphous SiO2 shell.

A new efficient method for calculation of Frenkel exciton parameters in molecular aggregates

NASA Astrophysics Data System (ADS)

Plötz, Per-Arno; Niehaus, Thomas; Kühn, Oliver

2014-05-01

The Frenkel exciton Hamiltonian is at the heart of many simulations of excitation energy transfer in molecular aggregates. It separates the aggregate into Coulomb-coupled monomers. Here it is shown that the respective parameters, i.e., monomeric excitation energies and Coulomb couplings between transition densities can be efficiently calculated using time-dependent tight-binding-based density functional theory (TD-DFTB). Specifically, Coulomb couplings are expressed in terms of self-consistently determined Mulliken transition charges. The approach is applied to two dimer systems. First, formaldehyde oxime for which a detailed comparison with standard DFT using the B3LYP and the PBE functionals as well as with SCS-CC2 is provided. Second, the Coulomb coupling is explored in dependence on the intermolecular coordinates for a perylene bisimide dimer. This provides structural evidence for the previously observed biphasic aggregation behavior of this dye.

Comparison of carrier multiplication yields in PbS and PbSe nanocrystals: the role of competing energy-loss processes.

PubMed

Stewart, John T; Padilha, Lazaro A; Qazilbash, M Mumtaz; Pietryga, Jeffrey M; Midgett, Aaron G; Luther, Joseph M; Beard, Matthew C; Nozik, Arthur J; Klimov, Victor I

2012-02-08

Infrared band gap semiconductor nanocrystals are promising materials for exploring generation III photovoltaic concepts that rely on carrier multiplication or multiple exciton generation, the process in which a single high-energy photon generates more than one electron-hole pair. In this work, we present measurements of carrier multiplication yields and biexciton lifetimes for a large selection of PbS nanocrystals and compare these results to the well-studied PbSe nanocrystals. The similar bulk properties of PbS and PbSe make this an important comparison for discerning the pertinent properties that determine efficient carrier multiplication. We observe that PbS and PbSe have very similar biexciton lifetimes as a function of confinement energy. Together with the similar bulk properties, this suggests that the rates of multiexciton generation, which is the inverse of Auger recombination, are also similar. The carrier multiplication yields in PbS nanocrystals, however, are strikingly lower than those observed for PbSe nanocrystals. We suggest that this implies the rate of competing processes, such as phonon emission, is higher in PbS nanocrystals than in PbSe nanocrystals. Indeed, our estimations for phonon emission mediated by the polar Fröhlich-type interaction indicate that the corresponding energy-loss rate is approximately twice as large in PbS than in PbSe. © 2011 American Chemical Society

Synthesis and Characterization of Metal-Organic Frameworks (MOFs) for Photon Collection and Energy Transfer

NASA Astrophysics Data System (ADS)

So, Monica C.

Projected global energy demand is widely believed to reach 30 TW by 2050. Currently, fossil fuels collectively represent over 80% of our total energy supply, while only 10% come from renewable sources. To meet future demands, however, we must maximize our use of renewable resources while minimizing our dependence on fossil fuels. While there are many sources of renewable energy, solar energy is one of the most abundant; in fact, the sun delivers up to 67 TW of power annually, which exceeds the projected energy demand in 2050. While there are multiple ways to convert sunlight to electricity, organic photovoltaics (OPVs) has the shortest energy payback time; this is the time required for the PV module to generate the equivalent amount of energy that originally was used to manufacture the PV module. OPVs show promise for light-to-electrical energy conversion with the best performing cells having power conversion efficiencies of 8%, but the theoretical maximum is at 32%. If efficiencies can be increased to even a fraction of the way to ˜16%, OPVs would be more cost-competitive with their inorganic counterparts. However, there are four major challenges in improving OPV performance. These include (a) poor light harvesting, due to a limited range of absorbance of visible light, (b) inefficient exciton splitting into holes and electrons, due to the limited diffusion length of excitons (typically ca. 10 nm), (c) increased recombination of separated charges at the donor/acceptor interface, and (d) inefficient collection of charges at the active layer/electrode interface (i.e. partial electrical shorting). OPVs constructed from conventional materials and architectures involve conflicting design requirements; this makes it impossible to address all four problems simultaneously. The projects described in this dissertation involve the design, synthesis, and characterization of a new class of OPV materials that have the potential to overcome the problems with conventional cells. To address problem (a), we incorporated antenna molecules (i.e. perylene diimides) to expand light collection and then transfer energy to the primary chromophores. To address problem (b), we observed that excitons can achieve up to 2,025 hops in a porphyrin-based metal-organic framework (MOF) single crystal within its 3 ns lifetime. By precisely aligning the chromophores in the MOF, we showed that long-distance exciton transport (i.e. ultra-fast, sequential hopping) was consistent with the well-established Forster theory. To address problems (c) and (d), we introduced MOF components one step at a time to optimize optical path length and crystal-thickness. This allowed us to incorporate MOFs (normally bulk crystals) into a MOF film. The approach exploited both MOF chemistry and layer-by-layer (LbL) assembly of crystalline MOFs in a highly controlled fashion on functional surfaces. We also incorporated good light-harvesting molecules as struts in MOFs to increase the visible absorption. Designing MOF-based OPVs can provide insight into solar energy conversion. This can potentially lead to much higher efficiencies, based on the simultaneous resolution of the four challenges hindering OPV performance.

Path induced coherent energy transfer in light-harvesting complexes in purple bacteria

NASA Astrophysics Data System (ADS)

Sun, Kewei; Ye, Jun; Zhao, Yang

2014-09-01

Features of path dependent energy transfer in a dual-ring light-harvesting (LH2) complexes (B850) system have been examined in detail systematically. The Frenkel-Dirac time dependent variational method with the Davydov D1 Ansatz is employed with detailed evolution of polaron dynamics in real space readily obtained. It is found that the phase of the transmission amplitude through the LH2 complexes plays an important role in constructing the coherent excitonic energy transfer. It is also found that the symmetry breaking caused by the dimerization of bacteriochlorophylls and coherence or correlation between two rings will be conducive in enhancing the exciton transfer efficiency.

Exciton dynamics and annihilation in WS2 2D semiconductors.

PubMed

Yuan, Long; Huang, Libai

2015-04-28

We systematically investigate the exciton dynamics in monolayered, bilayered, and trilayered WS2 two-dimensional (2D) crystals by time-resolved photoluminescence (TRPL) spectroscopy. The exciton lifetime when free of exciton annihilation was determined to be 806 ± 37 ps, 401 ± 25 ps, and 332 ± 19 ps for WS2 monolayer, bilayer, and trilayer, respectively. By measuring the fluorescence quantum yields, we also establish the radiative and nonradiative lifetimes of the direct and indirect excitons. The exciton decay in monolayered WS2 exhibits a strong excitation density-dependence, which can be described using an exciton-exciton annihilation (two-particle Auger recombination) model. The exciton-exciton annihilation rate for monolayered, bilayered, and trilayered WS2 was determined to be 0.41 ± 0.02, (6.00 ± 1.09) × 10(-3) and (1.88 ± 0.47) × 10(-3) cm(2) s(-1), respectively. Notably, the exciton-exciton annihilation rate is two orders of magnitude faster in the monolayer than in the bilayer and trilayer. We attribute the much slower exciton-exciton annihilation rate in the bilayer and trilayer to reduced many-body interaction and phonon-assisted exciton-exciton annihilation of indirect excitons.

Optoelectronic engineering of colloidal quantum-dot solar cells beyond the efficiency black hole: a modeling approach

NASA Astrophysics Data System (ADS)

Mahpeykar, Seyed Milad; Wang, Xihua

2017-02-01

Colloidal quantum dot (CQD) solar cells have been under the spotlight in recent years mainly due to their potential for low-cost solution-processed fabrication and efficient light harvesting through multiple exciton generation (MEG) and tunable absorption spectrum via the quantum size effect. Despite the impressive advances achieved in charge carrier mobility of quantum dot solids and the cells' light trapping capabilities, the recent progress in CQD solar cell efficiencies has been slow, leaving them behind other competing solar cell technologies. In this work, using comprehensive optoelectronic modeling and simulation, we demonstrate the presence of a strong efficiency loss mechanism, here called the "efficiency black hole", that can significantly hold back the improvements achieved by any efficiency enhancement strategy. We prove that this efficiency black hole is the result of sole focus on enhancement of either light absorption or charge extraction capabilities of CQD solar cells. This means that for a given thickness of CQD layer, improvements accomplished exclusively in optic or electronic aspect of CQD solar cells do not necessarily translate into tangible enhancement in their efficiency. The results suggest that in order for CQD solar cells to come out of the mentioned black hole, incorporation of an effective light trapping strategy and a high quality CQD film at the same time is an essential necessity. Using the developed optoelectronic model, the requirements for this incorporation approach and the expected efficiencies after its implementation are predicted as a roadmap for CQD solar cell research community.

Highly efficient and stable white organic light emitting diode base on double recombination zones of phosphorescent blue/orange emitters.

PubMed

Lee, Seok Jae; Koo, Ja Ryong; Lim, Dong Hwan; Park, Hye Rim; Kim, Young Kwan; Ha, Yunkyoung

2011-08-01

We demonstrated efficient and stable white phosphorescent organic light-emitting diodes (OLEDs) with double-emitting layers (D-EMLs), which were comprised of two emissive layers with a hole transport-type host of N,N'-dicarbazolyl-3,5-benzene (mCP) and a electron transport-type host of 2,2',2"-(1,3,5-benzenetryl)tris(1-phenyl)-1H-benzimidazol (TPBi) with blue/orange emitters, respectively. We fabricated two type white devices with single emitting layer (S-EML) and D-EML of orange emitter, maintaining double recombination zone of blue emitter. In addition, the device architecture was developed to confine excitons inside the D-EMLs and to manage triplet excitons by controlling the charge injection. As a result, light-emitting performances of white OLED with D-EMLs were improved and showed the steady CIE coordinates compared to that with S-EML of orange emitter, which demonstrated the maximum luminous efficiency and external quantum efficiency were 21.38 cd/A and 11.09%. It also showed the stable white emission with CIE(x,y) coordinates from (x = 0.36, y = 0.37) at 6 V to (x = 0.33, y = 0.38) at 12 V.

The entangled triplet pair state in acene and heteroacene materials

PubMed Central

Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L.; Lukman, Steven; Tamura, Hiroyuki; Bubnova, Olga; Hallani, Rawad K.; Meneau, Aurélie; Resel, Roland; Maruyama, Munetaka; Hotta, Shu; Herz, Laura M.; Beljonne, David; Anthony, John E.; Clark, Jenny; Sirringhaus, Henning

2017-01-01

Entanglement of states is one of the most surprising and counter-intuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which mediates the spin-conserving fission of one spin-0 singlet exciton into two spin-1 triplet excitons. Despite long theoretical and experimental exploration, the nature of the triplet-pair state and inter-triplet interactions have proved elusive. Here we use a range of organic semiconductors that undergo singlet exciton fission to reveal the photophysical properties of entangled triplet-pair states. We find that the triplet pair is bound with respect to free triplets with an energy that is largely material independent (∼30 meV). During its lifetime, the component triplets behave cooperatively as a singlet and emit light through a Herzberg–Teller-type mechanism, resulting in vibronically structured photoluminescence. In photovoltaic blends, charge transfer can occur from the bound triplet pairs with >100% photon-to-charge conversion efficiency. PMID:28699637

Polariton-Assisted Singlet Fission in Acene Aggregates.

PubMed

Martínez-Martínez, Luis A; Du, Matthew; F Ribeiro, Raphael; Kéna-Cohen, Stéphane; Yuen-Zhou, Joel

2018-04-19

Singlet fission is an important candidate to increase energy conversion efficiency in organic photovoltaics by providing a pathway to increase the quantum yield of excitons per photon absorbed in select materials. We investigate the dependence of exciton quantum yield for acenes in the strong light-matter interaction (polariton) regime, where the materials are embedded in optical microcavities. Starting from an open-quantum-systems approach, we build a kinetic model for time-evolution of species of interest in the presence of singlet quenchers and show that polaritons can decrease or increase exciton quantum yields compared to the cavity-free case. In particular, we find that hexacene, under the conditions of our model, can feature a higher yield than cavity-free pentacene when assisted by polaritonic effects. Similarly, we show that pentacene yield can be increased when assisted by polariton states. Finally, we address how various relaxation processes between bright and dark states in lossy microcavities affect polariton photochemistry. Our results also provide insights on how to choose microcavities to enhance similarly related chemical processes.

Organic light-emitting diodes for lighting: High color quality by controlling energy transfer processes in host-guest-systems

NASA Astrophysics Data System (ADS)

Weichsel, Caroline; Reineke, Sebastian; Furno, Mauro; Lüssem, Björn; Leo, Karl

2012-02-01

Exciton generation and transfer processes in a multilayer organic light-emitting diode (OLED) are studied in order to realize OLEDs with warm white color coordinates and high color-rendering index (CRI). We investigate a host-guest-system containing four phosphorescent emitters and two matrix materials with different transport properties. We show, by time-resolved spectroscopy, that an energy back-transfer from the blue emitter to the matrix materials occurs, which can be used to transport excitons to the other emitter molecules. Furthermore, we investigate the excitonic and electronic transfer processes by designing suitable emission layer stacks. As a result, we obtain an OLED with Commission Internationale de lÉclairage (CIE) coordinates of (0.444;0.409), a CRI of 82, and a spectrum independent of the applied current. The OLED shows an external quantum efficiency of 10% and a luminous efficacy of 17.4 lm/W at 1000 cd/m2.

Directional Charge Separation in Isolated Organic Semiconductor Crystalline Nanowires

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

Barnes, Michael; Labastide, Joelle; Bond-Thompson, Hilary

2017-03-01

In the conventional view of organic photovoltaics (OPV), localized electronic excitations (excitons) formed in the active layer are transported by random 3D diffusion to an interface where charge separation and extraction take place. Because radiative de-excitation is usually strongly allowed in organic semiconductors, efficient charge separation requires high exciton mobility, with much of the diffusive motion ‘wasted’ in directions that don’t result in an interface encounter. Our research efforts are focused on ways to enforce a preferred directionality in energy and/or charge transport using ordered crystalline nanowires in which the intermolecular interactions that facilitate transport along, for example, the pi-stackingmore » axis, can be made several orders of magnitude stronger than those in a transverse direction. The results presented in our recent work (Nature Communications) is a first step towards realizing the goal of directional control of both energy transport and charge separation, where excitons shared between adjacent molecules dissociate exclusively along the pi-stacking direction.« less

Enhancement of Exciton Emission from Multilayer MoS2 at High Temperatures: Intervalley Transfer versus Interlayer Decoupling.

PubMed

Li, Yuanzheng; Xu, Haiyang; Liu, Weizhen; Yang, Guochun; Shi, Jia; Liu, Zheng; Liu, Xinfeng; Wang, Zhongqiang; Tang, Qingxin; Liu, Yichun

2017-05-01

It is very important to obtain a deeper understand of the carrier dynamics for indirect-bandgap multilayer MoS 2 and to make further improvements to the luminescence efficiency. Herein, an anomalous luminescence behavior of multilayer MoS 2 is reported, and its exciton emission is significantly enhanced at high temperatures. Temperature-dependent Raman studies and electronic structure calculations reveal that this experimental observation cannot be fully explained by a common mechanism of thermal-expansion-induced interlayer decoupling. Instead, a new model involving the intervalley transfer of thermally activated carriers from Λ/Γ point to K point is proposed to understand the high-temperature luminescence enhancement of multilayer MoS 2 . Steady-state and transient-state fluorescence measurements show that both the lifetime and intensity of the exciton emission increase relatively to increasing temperature. These two experimental evidences, as well as a calculation of carrier population, provide strong support for the proposed model. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning open-circuit voltage in organic solar cells by magnesium modified Alq3

PubMed Central

Chou, Chi-Ta; Lin, Chien-Hung; Wu, Meng-Hsiu; Cheng, Tzu-Wei; Lee, Jiun-Haw; Liu, Chin-Hsin J.; Tai, Yian; Chattopadhyay, Surojit; Wang, Juen-Kai; Chen, Kuei-Hsien; Chen, Li-Chyong

2011-01-01

The low molecular weight tris-(8-hydroxyquinoline) aluminum (Alq3) has been incorporated with magnesium (Mg) that altered the nature of its opto-electronic characteristics. The lowering of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in Mg:Alq3, compared to pure Alq3, creates a stronger field (exceeding the exciton binding energy) at the donor-acceptor junction to dissociate the photo-generated exciton and also provides a low barrier for electron transport across the device. In an electron-only device (described in the text), a current enhancement in excess of 103, with respect to pure Alq3, could be observed at 10 V applied bias. Optimized Mg:Alq3 layer, when introduced in the photovoltaic device, improves the power conversion efficiencies significantly to 0.15% compared to the pure Alq3 device. The improvement in the photovoltaic performance has been attributed to the superior exciton dissociation and carrier transport. PMID:22087050

The entangled triplet pair state in acene and heteroacene materials

NASA Astrophysics Data System (ADS)

Yong, Chaw Keong; Musser, Andrew J.; Bayliss, Sam L.; Lukman, Steven; Tamura, Hiroyuki; Bubnova, Olga; Hallani, Rawad K.; Meneau, Aurélie; Resel, Roland; Maruyama, Munetaka; Hotta, Shu; Herz, Laura M.; Beljonne, David; Anthony, John E.; Clark, Jenny; Sirringhaus, Henning

2017-07-01

Entanglement of states is one of the most surprising and counter-intuitive consequences of quantum mechanics, with potent applications in cryptography and computing. In organic materials, one particularly significant manifestation is the spin-entangled triplet-pair state, which mediates the spin-conserving fission of one spin-0 singlet exciton into two spin-1 triplet excitons. Despite long theoretical and experimental exploration, the nature of the triplet-pair state and inter-triplet interactions have proved elusive. Here we use a range of organic semiconductors that undergo singlet exciton fission to reveal the photophysical properties of entangled triplet-pair states. We find that the triplet pair is bound with respect to free triplets with an energy that is largely material independent (~30 meV). During its lifetime, the component triplets behave cooperatively as a singlet and emit light through a Herzberg-Teller-type mechanism, resulting in vibronically structured photoluminescence. In photovoltaic blends, charge transfer can occur from the bound triplet pairs with >100% photon-to-charge conversion efficiency.

Manipulating Nonlinear Emission and Cooperative Effect of CdSe/ZnS Quantum Dots by Coupling to a Silver Nanorod Complex Cavity

PubMed Central

Nan, Fan; Cheng, Zi-Qiang; Wang, Ya-Lan; Zhang, Qing; Zhou, Li; Yang, Zhong-Jian; Zhong, Yu-Ting; Liang, Shan; Xiong, Qihua; Wang, Qu-Quan

2014-01-01

Colloidal semiconductor quantum dots have three-dimensional confined excitons with large optical oscillator strength and gain. The surface plasmons of metallic nanostructures offer an efficient tool to enhance exciton-exciton coupling and excitation energy transfer at appropriate geometric arrangement. Here, we report plasmon-mediated cooperative emissions of approximately one monolayer of ensemble CdSe/ZnS quantum dots coupled with silver nanorod complex cavities at room temperature. Power-dependent spectral shifting, narrowing, modulation, and amplification are demonstrated by adjusting longitudinal surface plasmon resonance of silver nanorods, reflectivity and phase shift of silver nanostructured film, and mode spacing of the complex cavity. The underlying physical mechanism of the nonlinear excitation energy transfer and nonlinear emissions are further investigated and discussed by using time-resolved photoluminescence and finite-difference time-domain numerical simulations. Our results suggest effective strategies to design active plasmonic complex cavities for cooperative emission nanodevices based on semiconductor quantum dots. PMID:24787617

Photon correlation study of background suppressed single InGaN nanocolumns

NASA Astrophysics Data System (ADS)

Yamamoto, Takatoshi; Maekawa, Michiru; Imanishi, Yusuke; Ishizawa, Shunsuke; Nakaoka, Toshihiro; Kishino, Katsumi

2016-04-01

We report on a linearly polarized non-classical light emission from a single InGaN/GaN nanocolumn, which is a site-controlled nanostructure allowing for pixel-like large-scale integration. We have developed a shadow mask technique to reduce background emissions arising from nitride deposits around single nanocolumns and defect states of GaN. The signal to background ratio is improved from 0.5:1 to 10:1, which allows for detailed polarization-dependent measurement and photon-correlation measurements. Polarization-dependent measurements show that linearly polarized emissions arise from excitonic recombination involving a heavy-hole-like electronic state, corresponding to the bulk exciton of an in-plane polarized A exciton. The second-order coherence function at time zero g (2)(0) is 0.52 at 20 K without background correction. This value is explained in terms of a statistical mixture of a single-photon emission with residual weak background emissions, as well as efficient carrier injection from other localized states.

Lineshape theory of pigment-protein complexes: How the finite relaxation time of nuclei influences the exciton relaxation-induced lifetime broadening

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

Dinh, Thanh-Chung; Renger, Thomas, E-mail: thomas.renger@jku.at

2016-07-21

In pigment-protein complexes, often the excited states are partially delocalized and the exciton-vibrational coupling in the basis of delocalized states contains large diagonal and small off-diagonal elements. This inequality may be used to introduce potential energy surfaces (PESs) of exciton states and to treat the inter-PES coupling in Markov and secular approximations. The resulting lineshape function consists of a Lorentzian peak that is broadened by the finite lifetime of the exciton states caused by the inter-PES coupling and a vibrational sideband that results from the mutual displacement of the excitonic PESs with respect to that of the ground state. Somore » far analytical expressions have been derived that relate the exciton relaxation-induced lifetime broadening to the Redfield [T. Renger and R. A. Marcus, J. Chem. Phys. 116, 9997 (2002)] or modified Redfield [M. Schröder, U. Kleinekathöfer, and M. Schreiber, J. Chem. Phys. 124, 084903 (2006)] rate constants of exciton relaxation, assuming that intra-PES nuclear relaxation is fast compared to inter-PES transfer. Here, we go beyond this approximation and provide an analytical expression, termed Non-equilibrium Modified Redfield (NeMoR) theory, for the lifetime broadening that takes into account the finite nuclear relaxation time. In an application of the theory to molecular dimers, we find that, for a widely used experimental spectral density of the exciton-vibrational coupling of pigment-protein complexes, the NeMoR spectrum at low-temperatures (T < 150 K) is better approximated by Redfield than by modified Redfield theory. At room temperature, the lifetime broadening obtained with Redfield theory underestimates the NeMoR broadening, whereas modified Redfield theory overestimates it by a similar amount. A fortuitous error compensation in Redfield theory is found to explain the good performance of this theory at low temperatures. Since steady state spectra of PPCs are often measured at low temperatures, Redfield theory still provides a numerically efficient alternative to NeMoR theory. At higher temperatures, we suggest to use NeMoR theory, because it has the same numerical costs as modified Redfield theory, but is more accurate.« less

Energy Transfer Kinetics in Photosynthesis as an Inspiration for Improving Organic Solar Cells.

PubMed

Nganou, Collins; Lackner, Gerhard; Teschome, Bezu; Deen, M Jamal; Adir, Noam; Pouhe, David; Lupascu, Doru C; Mkandawire, Martin

2017-06-07

Clues to designing highly efficient organic solar cells may lie in understanding the architecture of light-harvesting systems and exciton energy transfer (EET) processes in very efficient photosynthetic organisms. Here, we compare the kinetics of excitation energy tunnelling from the intact phycobilisome (PBS) light-harvesting antenna system to the reaction center in photosystem II in intact cells of the cyanobacterium Acaryochloris marina with the charge transfer after conversion of photons into photocurrent in vertically aligned carbon nanotube (va-CNT) organic solar cells with poly(3-hexyl)thiophene (P3HT) as the pigment. We find that the kinetics in electron hole creation following excitation at 600 nm in both PBS and va-CNT solar cells to be 450 and 500 fs, respectively. The EET process has a 3 and 14 ps pathway in the PBS, while in va-CNT solar cell devices, the charge trapping in the CNT takes 11 and 258 ps. We show that the main hindrance to efficiency of va-CNT organic solar cells is the slow migration of the charges after exciton formation.

Solvents induced ZnO nanoparticles aggregation associated with their interfacial effect on organic solar cells.

PubMed

Li, Pandeng; Jiu, Tonggang; Tang, Gang; Wang, Guojie; Li, Jun; Li, Xiaofang; Fang, Junfeng

2014-10-22

ZnO nanofilm as a cathode buffer layer has surface defects due to the aggregations of ZnO nanoparticles, leading to poor device performance of organic solar cells. In this paper, we report the ZnO nanoparticles aggregations in solution can be controlled by adjusting the solvents ratios (chloroform vs methanol). These aggregations could influence the morphology of ZnO film. Therefore, compact and homogeneous ZnO film can be obtained to help achieve a preferable power conversion efficiency of 8.54% in inverted organic solar cells. This improvement is attributed to the decreased leakage current and the increased electron-collecting efficiency as well as the improved interface contact with the active layer. In addition, we find the enhanced maximum exciton generation rate and exciton dissociation probability lead to the improvement of device performance due to the preferable ZnO dispersion. Compared to other methods of ZnO nanofilm fabrication, it is the more convenient, moderate, and effective to get a preferable ZnO buffer layer for high-efficiency organic solar cells.

Quantum Confined Semiconductors for High Efficiency Photovoltaics

NASA Astrophysics Data System (ADS)

Beard, Matthew

2014-03-01

Semiconductor nanostructures, where at least one dimension is small enough to produce quantum confinement effects, provide new pathways for controlling energy flow and therefore have the potential to increase the efficiency of the primary photon-to-free energy conversion step. In this discussion, I will present the current status of research efforts towards utilizing the unique properties of colloidal quantum dots (NCs confined in three dimensions) in prototype solar cells and demonstrate that these unique systems have the potential to bypass the Shockley-Queisser single-junction limit for solar photon conversion. The solar cells are constructed using a low temperature solution based deposition of PbS or PbSe QDs as the absorber layer. Different chemical treatments of the QD layer are employed in order to obtain good electrical communication while maintaining the quantum-confined properties of the QDs. We have characterized the transport and carrier dynamics using a transient absorption, time-resolved THz, and temperature-dependent photoluminescence. I will discuss the interplay between carrier generation, recombination, and mobility within the QD layers. A unique aspect of our devices is that the QDs exhibit multiple exciton generation with an efficiency that is ~ 2 to 3 times greater than the parental bulk semiconductor.

High-Performance Fluorescent Organic Light-Emitting Diodes Utilizing an Asymmetric Anthracene Derivative as an Electron-Transporting Material.

PubMed

Zhang, Dongdong; Song, Xiaozeng; Li, Haoyuan; Cai, Minghan; Bin, Zhengyang; Huang, Tianyu; Duan, Lian

2018-05-17

Fluorescent organic light-emitting diodes with thermally activated delayed fluorescent sensitizers (TSF-OLEDs) have aroused wide attention, the power efficiencies of which, however, are limited by the mutual exclusion of high electron-transport mobility and large triplet energy of electron-transporting materials (ETMs). Here, an asymmetric anthracene derivative with electronic properties manipulated by different side groups is developed as an ETM to promote TSF-OLED performances. Multiple intermolecular interactions are observed, leading to a kind of "cable-like packing" in the crystal and favoring the simultaneous realization of high electron-transporting mobility and good exciton-confinement ability, albeit the low triplet energy of the ETM. The optimized TSF-OLEDs exhibit a record-high maximum external quantum efficiency/power efficiency of 24.6%/76.0 lm W -1 , which remain 23.8%/69.0 lm W -1 at a high luminance of even 5000 cd m -2 with an extremely low operation voltage of 3.14 V. This work opens a new paradigm for designing ETMs and also paves the way toward practical application of TSF-OLEDs. © 2018 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.

Anomalous temperature dependent magneto-conductance in organic light-emitting diodes with multiple emissive states

NASA Astrophysics Data System (ADS)

Zhao, Chen-xiao; Jia, Wei-yao; Huang, Ke-Xun; Zhang, Qiao-ming; Yang, Xiao-hui; Xiong, Zu-hong

2015-07-01

The temperature dependence of the magneto-conductance (MC) in organic electron donor-acceptor hybrid and layer heterojunction diodes was studied. The MC value increased with temperature in layer heterojunction and in 10 wt. % hybrid devices. An anomalous decrease of the MC with temperature was observed in 25 wt. %-50 wt. % hybrid devices. Further increasing donor concentration to 75 wt. %, the MC again increased with temperature. The endothermic exciplex-exciton energy transfer and the change in electroplex/exciton ratio caused by change in charge transport with temperature may account for these phenomena. Comparative studies of the temperature evolutions of the IV curves and the electroluminescence and photoluminescence spectra back our hypothesis.

Magnetic polarons in a nonequilibrium polariton condensate

NASA Astrophysics Data System (ADS)

Mietki, Paweł; Matuszewski, Michał

2017-09-01

We consider a condensate of exciton polaritons in a diluted magnetic semiconductor microcavity. Such a system may exhibit magnetic self-trapping in the case of sufficiently strong coupling between polaritons and magnetic ions embedded in the semiconductor. We investigate the effect of the nonequilibrium nature of exciton polaritons on the physics of the resulting self-trapped magnetic polarons. We find that multiple polarons can exist at the same time, and we derive a critical condition for self-trapping that is different from the one predicted previously in the equilibrium case. Using the Bogoliubov-de Gennes approximation, we calculate the excitation spectrum and provide a physical explanation in terms of the effective magnetic attraction between polaritons, mediated by the ion subsystem.

Impact of pentacene film thickness on the photoresponse spectra: Determination of the photocarrier generation mechanism

NASA Astrophysics Data System (ADS)

Gorgolis, S.; Giannopoulou, A.; Anastassopoulos, D.; Kounavis, P.

2012-07-01

Photocurrent response, optical absorption, and x-ray diffraction (XRD) measurements in pentacene films grown on glass substrates are performed in order to obtain an insight into the mobile photocarriers generation mechanism. For film thickness of the order of 50 nm and lower, the photocurrent response spectra are found to follow the optical absorption spectra demonstrating the so-called symbatic response. Upon increasing the film thickness, the photoresponse demonstrates a transition to the so-called antibatic response, which is characterized by a maximum and minimum photocurrent for photon energies of minimum and maximum optical absorption, respectively. The experimental results are not in accordance with the model of important surface recombination rate. By taking into account the XRD patterns, the experimental photoresponse spectra can be reproduced by model simulations assuming efficient exciton dissociation at a narrow layer of the order of 20 nm near the pentacene-substrate interface. The simulated spectra are found sensitive to the film thickness, the absolute optical absorption coefficient, and the diffusion exciton length. By comparing the experimental with the simulated spectra, it is deduced that the excitons, which are created by optical excitation in the spectral region of 1.7-2.2 eV, diffuse with a diffusion length of the order of 10-80 nm to the pentacene-substrate interface where efficiently dissociate into mobile charge carriers.

SWCNT Photocatalyst for Hydrogen Production from Water upon Photoexcitation of (8, 3) SWCNT at 680-nm Light

NASA Astrophysics Data System (ADS)

Murakami, Noritake; Tango, Yuto; Miyake, Hideaki; Tajima, Tomoyuki; Nishina, Yuta; Kurashige, Wataru; Negishi, Yuichi; Takaguchi, Yutaka

2017-03-01

Single-walled carbon nanotubes (SWCNTs) are potentially strong optical absorbers with tunable absorption bands depending on their chiral indices (n, m). Their application for solar energy conversion is difficult because of the large binding energy (>100 meV) of electron-hole pairs, known as excitons, produced by optical absorption. Recent development of photovoltaic devices based on SWCNTs as light-absorbing components have shown that the creation of heterojunctions by pairing chirality-controlled SWCNTs with C60 is the key for high power conversion efficiency. In contrast to thin film devices, photocatalytic reactions in a dispersion/solution system triggered by the photoexcitation of SWCNTs have never been reported due to the difficulty of the construction of a well-ordered surface on SWCNTs. Here, we show a clear-cut example of a SWCNT photocatalyst producing H2 from water. Self-organization of a fullerodendron on the SWCNT core affords water-dispersible coaxial nanowires possessing SWCNT/C60 heterojunctions, of which a dendron shell can act as support of a co-catalyst for H2 evolution. Because the band offset between the LUMO levels of (8, 3)SWCNT and C60 satisfactorily exceeds the exciton binding energy to allow efficient exciton dissociation, the (8, 3)SWCNT/fullerodendron coaxial photocatalyst shows H2-evolving activity (QY = 0.015) upon 680-nm illumination, which is E22 absorption of (8, 3) SWCNT.

Analysis of the external and internal quantum efficiency of multi-emitter, white organic light emitting diodes

NASA Astrophysics Data System (ADS)

Furno, Mauro; Rosenow, Thomas C.; Gather, Malte C.; Lüssem, Björn; Leo, Karl

2012-10-01

We report on a theoretical framework for the efficiency analysis of complex, multi-emitter organic light emitting diodes (OLEDs). The calculation approach makes use of electromagnetic modeling to quantify the overall OLED photon outcoupling efficiency and a phenomenological description for electrical and excitonic processes. From the comparison of optical modeling results and measurements of the total external quantum efficiency, we obtain reliable estimates of internal quantum yield. As application of the model, we analyze high-efficiency stacked white OLEDs and comment on the various efficiency loss channels present in the devices.

Hole-Accepting-Ligand-Modified CdSe QDs for Dramatic Enhancement of Photocatalytic and Photoelectrochemical Hydrogen Evolution by Solar Energy.

PubMed

Li, Xu-Bing; Liu, Bin; Wen, Min; Gao, Yu-Ji; Wu, Hao-Lin; Huang, Mao-Yong; Li, Zhi-Jun; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

2016-04-01

Solar H 2 evolution of CdSe QDs can be significantly enhanced simply by introducing a suitable hole-accepting-ligand for achieving efficient hole extraction and transfer at the nanoscale interfaces, which opens an effective pathway for dissociation of excitons to generate long-lived charge separation, thus improving the solar-to-fuel conversion efficiency.

Exciton-phonon coupling in diindenoperylene thin films

NASA Astrophysics Data System (ADS)

Heinemeyer, U.; Scholz, R.; Gisslén, L.; Alonso, M. I.; Ossó, J. O.; Garriga, M.; Hinderhofer, A.; Kytka, M.; Kowarik, S.; Gerlach, A.; Schreiber, F.

2008-08-01

We investigate exciton-phonon coupling and exciton transfer in diindenoperylene (DIP) thin films on oxidized Si substrates by analyzing the dielectric function determined by variable-angle spectroscopic ellipsometry. Since the molecules in the thin-film phase form crystallites that are randomly oriented azimuthally and highly oriented along the surface normal, DIP films exhibit strongly anisotropic optical properties with uniaxial symmetry. This anisotropy can be determined by multiple sample analysis. The thin-film spectrum is compared with a monomer spectrum in solution, which reveals similar vibronic subbands and a Huang-Rhys parameter of S≈0.87 for an effective internal vibration at ℏωeff=0.17eV . However, employing these parameters the observed dielectric function of the DIP films cannot be described by a pure Frenkel exciton model, and the inclusion of charge-transfer (CT) states becomes mandatory. A model Hamiltonian is parametrized with density-functional theory calculations of single DIP molecules and molecule pairs in the stacking geometry of the thin-film phase, revealing the vibronic coupling constants of DIP in its excited and charged states together with electron and hole transfer integrals along the stack. From a fit of the model calculation to the observed dielectric tensor, we find the lowest CT transition E00CT at 0.26±0.05eV above the neutral molecular excitation energy E00F , which is an important parameter for device applications.

Exciton-photon correlations in bosonic condensates of exciton-polaritons

PubMed Central

Kavokin, Alexey V.; Sheremet, Alexandra S.; Shelykh, Ivan A.; Lagoudakis, Pavlos G.; Rubo, Yuri G.

2015-01-01

Exciton-polaritons are mixed light-matter quasiparticles. We have developed a statistical model describing stochastic exciton-photon transitions within a condensate of exciton polaritons. We show that the exciton-photon correlator depends on the rate of incoherent exciton-photon transformations in the condensate. We discuss implications of this effect for the quantum statistics of photons emitted by polariton lasers. PMID:26153979

Exciton-photon correlations in bosonic condensates of exciton-polaritons.

PubMed

Kavokin, Alexey V; Sheremet, Alexandra S; Shelykh, Ivan A; Lagoudakis, Pavlos G; Rubo, Yuri G

2015-07-08

Exciton-polaritons are mixed light-matter quasiparticles. We have developed a statistical model describing stochastic exciton-photon transitions within a condensate of exciton polaritons. We show that the exciton-photon correlator depends on the rate of incoherent exciton-photon transformations in the condensate. We discuss implications of this effect for the quantum statistics of photons emitted by polariton lasers.

Oscillations in two-dimensional photon-echo signals of excitonic and vibronic systems: Stick-spectrum analysis and its computational verification

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

Egorova, Dassia

2014-01-21

Stick-spectrum expressions for electronic two-dimensional (2D) photon-echo (PE) signal of a generic multi-level system are presented and employed to interrelate oscillations in individual peaks of 2D PE signal and the underlying properties (eigenstates and coherent dynamics) of excitonic or vibronic systems. When focusing on the identification of the origin of oscillations in the rephasing part of 2D PE it is found, in particular, that multiple frequencies in the evolution of the individual peaks do not necessarily directly reflect the underlying system dynamics. They may originate from the excited-state absorption contribution to the signal, or arise due to multi-level vibrational structuremore » of the electronic ground state, and represent a superposition of system frequencies, while the latter may evolve independently. The analytical stick-spectrum predictions are verified and illustrated by numerical calculations of 2D PE signals of an excitonic trimer and of a displaced harmonic oscillator with unequal vibrational frequencies in the two electronic states. The excitonic trimer is the smallest excitonic oligomer where excited-state absorption may represent a superposition of excited-state coherences and significantly influence the phase of the observed oscillations. The displaced oscillator is used to distinguish between the frequencies of the ground-state and of the excited-state manifolds, and to demonstrate how the location of a cross peak in 2D pattern of the PE signal “predetermines” its oscillatory behavior. Although the considered models are kept as simple as possible for clarity, the stick-spectrum analysis provides a solid general basis for interpretation of oscillatory signatures in electronic 2D PE signals of much more complex systems with multi-level character of the electronic states.« less

Mechanisms of optical orientation of an individual Mn2+ ion spin in a II-VI quantum dot

NASA Astrophysics Data System (ADS)

Smoleński, T.; Cywiński, Ł.; Kossacki, P.

2018-02-01

We provide a theoretical description of the optical orientation of a single Mn2+ ion spin under quasi-resonant excitation demonstrated experimentally by Goryca et al (2009 Phys. Rev. Lett. 103 087401). We build and analyze a hierarchy of models by starting with the simplest assumptions (transfer of perfectly spin-polarized excitons from Mn-free dot to the other dot containing a single Mn2+ spin, followed by radiative recombination) and subsequently adding more features, such as spin relaxation of electrons and holes. Particular attention is paid to the role of the influx of the dark excitons and the process of biexciton formation, which are shown to contribute significantly to the orientation process in the quasi-resonant excitation case. Analyzed scenarios show how multiple features of the excitonic complexes in magnetically-doped quantum dots, such as the values of exchange integrals, spin relaxation times, etc, lead to a plethora of optical orientation processes, characterized by distinct dependencies on light polarization and laser intensity, and occurring on distinct timescales. Comparison with experimental data shows that the correct description of the optical orientation mechanism requires taking into account Mn2+ spin-flip processes occurring not only when the exciton is already in the orbital ground state of the light-emitting dot, but also those that happen during the exciton transfer from high-energy states to the ground state. Inspired by the experimental results on energy relaxation of electrons and holes in nonmagnetic dots, we focus on the process of biexciton creation allowed by mutual spin-flip of an electron and the Mn2+ spin, and we show that by including it in the model, we obtain good qualitative and quantitative agreement with the experimental data on quasi-resonantly driven Mn2+ spin orientation.

Carbon-dot-decorated TiO2 nanotube arrays used for photo/voltage-induced organic pollutant degradation and the inactivation of bacteria

NASA Astrophysics Data System (ADS)

Feng, Lingyan; Sun, Hanjun; Ren, Jinsong; Qu, Xiaogang

2016-03-01

Photoluminescent carbon dots (c-dots) have recently attracted growing interest as a new member of the carbon-nanomaterial family. Here, we report for the first time that c-dot-decorated TiO2 nanotube arrays (c-dot/TiNTs) exhibit highly enhanced abilities regarding photo/voltage-induced organic pollutant degradation and bacterial inactivation. By applying UV irradiation (365 nm) or an electrochemical potential over 3 V (versus Ag/AgCl), an organic dye and a herbicide were efficiently degraded. Moreover, the inactivation of Gram-positive S. aureus and Gram-negative E. coli bacteria was realized on a c-dot/TiNT film. The c-dots were able to absorb light efficiently resulting in multiple exciton generation and also a reduction in the recombination of the e-/h+ pair produced in c-dot/TiNT film during photo/voltage-induced degradation. It was also possible to readily regenerate the surface using ultraviolet light irradiation, leaving the whole film structure undamaged and with high reproducibility and stability.

Ultrafast Microscopy of Energy and Charge Transport

NASA Astrophysics Data System (ADS)

Huang, Libai

The frontier in solar energy research now lies in learning how to integrate functional entities across multiple length scales to create optimal devices. Advancing the field requires transformative experimental tools that probe energy transfer processes from the nano to the meso lengthscales. To address this challenge, we aim to understand multi-scale energy transport across both multiple length and time scales, coupling simultaneous high spatial, structural, and temporal resolution. In my talk, I will focus on our recent progress on visualization of exciton and charge transport in solar energy harvesting materials from the nano to mesoscale employing ultrafast optical nanoscopy. With approaches that combine spatial and temporal resolutions, we have recently revealed a new singlet-mediated triplet transport mechanism in certain singlet fission materials. This work demonstrates a new triplet exciton transport mechanism leading to favorable long-range triplet exciton diffusion on the picosecond and nanosecond timescales for solar cell applications. We have also performed a direct measurement of carrier transport in space and in time by mapping carrier density with simultaneous ultrafast time resolution and 50 nm spatial precision in perovskite thin films using transient absorption microscopy. These results directly visualize long-range carrier transport of 220nm in 2 ns for solution-processed polycrystalline CH3NH3PbI3 thin films. The spatially and temporally resolved measurements reported here underscore the importance of the local morphology and establish an important first step towards discerning the underlying transport properties of perovskite materials.

Exciton–polaritons in van der Waals heterostructures embedded in tunable microcavities

PubMed Central

Dufferwiel, S.; Schwarz, S.; Withers, F.; Trichet, A. A. P.; Li, F.; Sich, M.; Del Pozo-Zamudio, O.; Clark, C.; Nalitov, A.; Solnyshkov, D. D.; Malpuech, G.; Novoselov, K. S.; Smith, J. M.; Skolnick, M. S.; Krizhanovskii, D. N.; Tartakovskii, A. I.

2015-01-01

Layered materials can be assembled vertically to fabricate a new class of van der Waals heterostructures a few atomic layers thick, compatible with a wide range of substrates and optoelectronic device geometries, enabling new strategies for control of light–matter coupling. Here, we incorporate molybdenum diselenide/hexagonal boron nitride (MoSe2/hBN) quantum wells in a tunable optical microcavity. Part-light–part-matter polariton eigenstates are observed as a result of the strong coupling between MoSe2 excitons and cavity photons, evidenced from a clear anticrossing between the neutral exciton and the cavity modes with a splitting of 20 meV for a single MoSe2 monolayer, enhanced to 29 meV in MoSe2/hBN/MoSe2 double-quantum wells. The splitting at resonance provides an estimate of the exciton radiative lifetime of 0.4 ps. Our results pave the way for room-temperature polaritonic devices based on multiple-quantum-well van der Waals heterostructures, where polariton condensation and electrical polariton injection through the incorporation of graphene contacts may be realized. PMID:26446783

Efficient Flexible Organic/Inorganic Hybrid Perovskite Light-Emitting Diodes Based on Graphene Anode.

PubMed

Seo, Hong-Kyu; Kim, Hobeom; Lee, Jaeho; Park, Min-Ho; Jeong, Su-Hun; Kim, Young-Hoon; Kwon, Sung-Joo; Han, Tae-Hee; Yoo, Seunghyup; Lee, Tae-Woo

2017-03-01

Highly efficient organic/inorganic hybrid perovskite light-emitting diodes (PeLEDs) based on graphene anode are developed for the first time. Chemically inert graphene avoids quenching of excitons by diffused metal atom species from indium tin oxide. The flexible PeLEDs with graphene anode on plastic substrate show good bending stability; they provide an alternative and reliable flexible electrode for highly efficient flexible PeLEDs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of the granule size in porous silicon on the photosensitization efficiency of molecular oxygen on the surface of silicon nanocrystals

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

Demin, V. A.; Konstantinova, E. A., E-mail: liza35@mail.ru; Gongal'skii, M. B.

2009-03-15

Photoluminescence is used to study the effect of the granule size in porous silicon on the generation efficiency of the excited state of molecular oxygen ({sup 1}O{sub 2}) on the surface of silicon nanocrystals. The generation efficiency is found to increase as the granule size becomes smaller than 100 nm, which can be explained by a change in the conditions of exciton diffusion along a network of silicon nanocrystals.

Self-trapping limited exciton diffusion in a monomeric perylene crystal as revealed by femtosecond transient absorption microscopy.

PubMed

Yago, Tomoaki; Tamaki, Yoshiaki; Furube, Akihiro; Katoh, Ryuzi

2008-08-14

Self-trapping and singlet-singlet annihilation of the free excitons in a monomeric (beta) perylene crystal were studied by using femtosecond transient absorption microscopy. The free exciton generated by the photo-excitation of the beta-perylene crystal relaxed to the self-trapped exciton with a rate constant of 7 x 10(10) s(-1). The singlet-singlet annihilation of the free exciton observed under the high excitation density conditions was competed with the self-trapping of the free exciton; we estimated the annihilation rate constant for the free exciton to be 1 x 10(-8) cm(3) s(-1) from the excitation density dependence of the free exciton decay. After self-trapping of the free exciton, no annihilation was observed in the 100 ps time range, suggesting that the diffusion coefficient was reduced drastically by self-trapping. The results show that the major factor limiting the exciton diffusion in the beta-perylene crystal is a relaxation of the free exciton to the self-trapped exciton, and not the lifetime of the exciton. Though the singlet-singlet annihilation rate constants and fluorescence lifetime of the beta-perylene crystal are similar to those of the anthracene crystal, the estimated exciton diffusion length (2 nm) in the beta-perylene crystal is much smaller than that (100 nm) in the anthracene crystal as a result of the exciton self-trapping.

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.

Interfacial Molecular Packing Determines Exciton Dynamics in Molecular Heterostructures: The Case of Pentacene-Perfluoropentacene.

PubMed

Rinn, Andre; Breuer, Tobias; Wiegand, Julia; Beck, Michael; Hübner, Jens; Döring, Robin C; Oestreich, Michael; Heimbrodt, Wolfram; Witte, Gregor; Chatterjee, Sangam

2017-12-06

The great majority of electronic and optoelectronic devices depend on interfaces between p-type and n-type semiconductors. Finding matching donor-acceptor systems in molecular semiconductors remains a challenging endeavor because structurally compatible molecules may not necessarily be suitable with respect to their optical and electronic properties, and the large exciton binding energy in these materials may favor bound electron-hole pairs rather than free carriers or charge transfer at an interface. Regardless, interfacial charge-transfer exciton states are commonly considered as an intermediate step to achieve exciton dissociation. The formation efficiency and decay dynamics of such states will strongly depend on the molecular makeup of the interface, especially the relative alignment of donor and acceptor molecules. Structurally well-defined pentacene-perfluoropentacene heterostructures of different molecular orientations are virtually ideal model systems to study the interrelation between molecular packing motifs at the interface and their electronic properties. Comparing the emission dynamics of the heterosystems and the corresponding unitary films enables accurate assignment of every observable emission signal in the heterosystems. These heterosystems feature two characteristic interface-specific luminescence channels at around 1.4 and 1.5 eV that are not observed in the unitary samples. Their emission strength strongly depends on the molecular alignment of the respective donor and acceptor molecules, emphasizing the importance of structural control for device construction.

Preparation of PCDTBT nanofibers with a diameter of 20 nm and their application to air-processed organic solar cells.

PubMed

Kim, Taehoon; Yang, Seung Jae; Kim, Sung Kyun; Choi, Hong Soo; Park, Chong Rae

2014-03-07

A strategy for fabricating organic photovoltaic (OPV) devices based on PCDTBT nanofibers and PC70BM is described. Electrospinning techniques are used to prepare PCDTBT nanofibers and OPV devices in ambient air. The diameters of the PCDTBT nanofibers are approximately twice the exciton diffusion length, 20 nm. The active layer exhibits 100% photoluminescence quenching due to the small nanofiber diameter, indicating that the excitons are efficiently dissociated. The electrospun PCDTBT nanofibers absorb more photons at longer wavelengths, leading to improved photon harvesting. OPV devices composed of PCDTBT nanofibers show a high short circuit current of 11.54 mA cm(-2) and a high power conversion efficiency of 5.82%. The increase in the short circuit current is attributed to enhanced photon harvesting and charge transport. This method may be applied to the fabrication, in ambient air, of large-area active layers composed of other new conjugated polymers to yield high-performance OPV devices.

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

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

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1,2,3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate thatmore » colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« less

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

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

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.

2015-11-23

Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities1, 2, 3. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. Wemore » demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.« 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.

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Wu, Mengfei; Congreve, Daniel N.; Wilson, Mark W. B.; Jean, Joel; Geva, Nadav; Welborn, Matthew; van Voorhis, Troy; Bulović, Vladimir; Bawendi, Moungi G.; Baldo, Marc A.

2016-01-01

Optical upconversion via sensitized triplet-triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.

Electric dipole moment of magnetoexciton in concentric quantum rings

NASA Astrophysics Data System (ADS)

García, L. F.; Mikhailov, I. D.; Revinova, S. Yu

2017-12-01

We study properties of exciton in a weakly coupled concentric quantum rings, penetrated by an axially directed magnetic flux and subjected to an electric field in the ring’s plane. To this end, we adopt a simple model of quasi-one-dimensional rotator, for which the wave functions and the corresponding energies we found by using the double Fourier series expansion method. Revealed multiple intersections of the energy levels provide conditions for abrupt changes of the radial and the angular quantum numbers, making possible the tunnelling of carriers between rings and allowing the formation of a permanent large dipole moment. We show that the electric and magnetic polarizability of concentric quantum rings with a trapped exciton are very sensible to external electric and magnetic fields.

Temperature-dependent time-resolved photoluminescence measurements of (1-101)-oriented semi-polar AlGaN/GaN MQWs

NASA Astrophysics Data System (ADS)

Rosales, Daniel; Gil, Bernard; Monavarian, Morteza; Zhang, Fan; Okur, Serdal; Izyumskaya, Natalia; Avrutin, Vitaliy; Özgür, Ümit; Morkoç, Hadis

2015-03-01

We studied the temperature dependence and the recombination dynamics of the photoluminescence of (1-101)-oriented semi-polar Al0.2Ga0.8N/GaN multiple quantum wells (MQW). The polarized low-temperature PL measurements reveal that radiative recombination exhibit an anisotropic behavior. The PL intensity at room temperature is reduced by one order of magnitude with respect to low temperature. The radiative decay time exhibits a mixed behavior: it is roughly constant between 8K to ranging near 140-150K and then rapidly increases with a slope of 10 ps.K-1. This behavior is indicative of coexistence of localized excitons and free excitons which relative proportion are statistically computed.

Photoinduced Effects in the ZnO Luminescence Spectra

NASA Astrophysics Data System (ADS)

Akopyan, I. Kh.; Labzovskaya, M. E.; Novikov, B. V.; Lisachenko, A. A.; Serov, A. Yu.; Filosofov, N. G.

2018-02-01

The effect of intense UV irradiation on the photoluminescence (PL) spectra of ZnO powders and nanocrystalline films obtained by atomic layer deposition (ALD) was investigated. At room temperature, the behavior of the spectra under continuous UV irradiation in multiple vacuum-atmosphere cycles was studied. The changes in the intensities of exciton radiation and radiation in the "green" band region, associated with the phenomena of oxygen photodesorption and photoadsorption, are discussed. In the temperature range of 5-300 K, the effect of strong UV irradiation on the near-edge luminescence spectrum of ZnO films was studied. The nature of a new line arising in the photoluminescence spectra of an irradiated film in the region of emission of bound excitons is discussed.

Cathodoluminescence and transmission electron microscopy study of dark line defects in thick In(0.2)Ga(0.8)As/GaAs multiple quantum wells

NASA Technical Reports Server (NTRS)

Rich, D. H.; George, T.; Pike, W. T.; Maserjian, J.; Grunthaner, F. J.; Larsson, A.

1992-01-01

TEM and cathodoluminescence (CL) imaging and spectroscopy have been performed on In(0.2)Ga(0.8)As/GaAs MQW structures. Cross-sectional and plan-view TEM demonstrates that misfit dislocations (MDs) are confined to the MQW-to-GaAs interfacial regions. The observed large variation in the exciton luminescence intensity is interpreted as due to the presence of nonradiative recombination centers spread homogeneously in the MQW region away from interface MDs. These nonradiative recombination centers compete with exciton and midgap radiative centers at wavelengths of 950 nm and 1000-1600 nm, respectively, resulting in spatiallty correlated dark line defects for all CL imaging wavelengths.

Quasiparticle energies, excitonic effects, and dielectric screening in transparent conducting oxides

NASA Astrophysics Data System (ADS)

Schleife, André

Using the power of high-performance super computers, computational materials scientists nowadays employ highly accurate quantum-mechanical approaches to reliably predict materials properties. In particular, many-body perturbation theory is an excellent framework for performing theoretical spectroscopy on novel materials including transparent conducting oxides, since this framework accurately describes quasiparticle and excitonic effects.We recently used hybrid exchange-correlation functionals and an efficient implementation of the Bethe-Salpeter approach to investigate several important transparent conducting oxides. Despite their exceptional potential for applications in photovoltaics and optoelectronics their optical properties oftentimes remain poorly understood: Our calculations explain the optical spectrum of bixbyite indium oxide over a very large photon energy range, which allows us to discuss the importance of quasiparticle and excitonic effects at low photon energies around the absorption onset, but also for excitations up to 40 eV. We show that in this regime the energy dependence of the electronic self energy cannot be neglected. Furthermore, we investigated the influence of excitonic effects on optical absorption for lanthanum-aluminum oxide and hafnium oxide. Their complicated conduction band structures require an accurate description of quasiparticle energies and we find that for these strongly polar materials, a contribution of the lattice polarizability to dielectric screening needs to be taken into account. We discuss how this affects the electron-hole interaction and find a strong influence on excitonic effects.The deep understanding of electronic excitations that can be obtained using these modern first-principles techniques, eventually will allow for computational materials design, e.g. of band gaps, densities of states, and optical properties of transparent conducting oxides and other materials with societally important applications.

Exciton Hybridisation in Organic-Inorganic Semiconductor Microcavities

DTIC Science & Technology

2002-02-01

hybridizing organic and inorganic semiconductors in microcavities to produce a highly efficient light source that could be either a laser or a very efficient...such process may also have an important effect on the spectral distribution of photoluminescence from the microcavity and can be considered as a...Absorption (solid dots) and photoluminescence emission (open circles) of a thin film of J-aggregated cyanine dyes in a PVA matrix. Note, the chemical

Realizing Highly Efficient Solution-Processed Homojunction-Like Sky-Blue OLEDs by Using Thermally Activated Delayed Fluorescent Emitters Featuring an Aggregation-Induced Emission Property.

PubMed

Wu, Kailong; Wang, Zian; Zhan, Lisi; Zhong, Cheng; Gong, Shaolong; Xie, Guohua; Yang, Chuluo

2018-04-05

Two new blue emitters, i.e., bis-[2-(9,9-dimethyl-9,10-dihydroacridine)-phenyl]-sulfone ( o-ACSO2) and bis-[3-(9,9-dimethyl-9,10-dihydroacridine)-phenyl]-sulfone ( m-ACSO2), with reserved fine thermally activated delayed fluorescent (TADF) nature and simply tuned thermal and optoelectronic properties, were synthesized by isomer engineering. The meta-linking compound, i.e., m-ACSO2, obtains the highest photoluminescence quantum yield with a small singlet-triplet energy gap, a moderate delayed fluorescent lifetime, excellent solubility, and neat film homogeneity. Due to its unique aggregation-induced emission (AIE) character, neat film-based heterojunction-like organic light-emitting diodes (OLEDs) are achievable. By inserting an excitonic inert exciton-blocking layer, the PN heterojunction-like emission accompanied by intefacial exciplex was shifted to a homojunction-like channel mainly from the AIE emitter itself, providing a new tactic to generate efficient blue color from neat films. The solution-processed nondoped sky-blue OLED employing m-ACSO2 as emitter with homojunction-like emission achieved a maximum external quantum efficiency of 17.2%. The design strategies presented herein provide practical methods to construct efficient blue TADF dyes and realize high-performance blue TADF devices.

Incorporating an Electrode Modification Layer with a Vertical Phase Separated Photoactive Layer for Efficient and Stable Inverted Nonfullerene Polymer Solar Cells.

PubMed

Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Li, Jinyan; Bai, Yiming; Wang, Fuzhi; Bian, Xingming; Hayat, Tasawar; Alsaedi, Ahmed; Tan, Zhan'ao

2017-12-20

For bulk heterojunction polymer solar cells (PSCs), the donors and acceptors featuring specific phase separation and concentration distribution within the electron donor/acceptor blends crucially affect the exciton dissociation and charge transportation. Herein, efficient and stable nonfullerene inverted PSCs incorporating a phase separated photoactive layer and a titanium chelate electrode modification layer are demonstrated. Water contact angle (WCA), scanning kelvin probe microscopy (SKPM), and atomic force microscopy (AFM) techniques are implemented to characterize the morphology of photoactive layers. Compared with the control conventional device, the short-circuit current density (J sc ) is enhanced from 14.74 to 17.45 mAcm -2 . The power conversion efficiency (PCE) for the inverted PSCs with a titanium (diisopropoxide)-bis-(2,4-pentanedionate) (TIPD) layer increases from 9.67% to 11.69% benefiting from the declined exciton recombination and fairly enhanced charge transportation. Furthermore, the nonencapsulated inverted device with a TIPD layer demonstrates the best long-term stability, 85% of initial PCE remaining and an almost undecayed open-circuit voltage (V oc ) after 1440 h. Our results reveal that the titanium chelate is an excellent electrode modification layer to incorporate with a vertical phase separated photoactive layer for producing high-efficiency and high-stability inverted nonfullerene PSCs.

Unravelling Photocarrier Dynamics beyond the Space Charge Region for Photoelectrochemical Water Splitting

DOE PAGES

Zhang, Wenrui; Yan, Danhua; Appavoo, Kannatassen; ...

2017-04-18

Semiconductor photoelectrodes for photoelectrochemical (PEC) water splitting require efficient carrier generation, separation, and transport at and beyond the space charge region (SCR) formed at the aqueous interface. The trade-off between photon collection and minority carrier delivery governs the photoelectrode design and implies maximum water splitting efficiency at an electrode thickness equivalent to the light absorption depth. Here, using planar ZnO thin films as a model system, we identify the photocarriers beyond the SCR as another significant source to substantially enhance the PEC performance. The high-quality ZnO films synthesized by pulsed laser deposition feature very few deep trap states and supportmore » a long photocarrier lifetime. Combined with photoelectrochemical characterization, ultrafast spectroscopy, and numerical calculations, it is revealed that engineering the exciton concentration gradient by film thickness facilitates the inward diffusion of photocarriers from the neighboring illuminated region to the SCR and, therefore, achieves a record high quantum efficiency over 80% at a thickness far beyond its light absorption depth and the SCR width. Furthermore, these results elucidate the important role of the photocarriers beyond SCR for the PEC process and provide new insight into exploring the full potential for efficient photoelectrode materials with large exciton diffusivity.« less

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

Nelson, Tammie Renee; Fernandez Alberti, Sebastian; Roitberg, Adrian

The efficiency of materials developed for solar energy and technological applications depends on the interplay between molecular architecture and light-induced electronic energy redistribution. The spatial localization of electronic excitations is very sensitive to molecular distortions. Vibrational nuclear motions can couple to electronic dynamics driving changes in localization. The electronic energy transfer among multiple chromophores arises from several distinct mechanisms that can give rise to experimentally measured signals. Atomistic simulations of coupled electron-vibrational dynamics can help uncover the nuclear motions directing energy flow. Through careful analysis of excited state wave function evolution and a useful fragmenting of multichromophore systems, through-bond transportmore » and exciton hopping (through-space) mechanisms can be distinguished. Such insights are crucial in the interpretation of fluorescence anisotropy measurements and can aid materials design. Finally, this Perspective highlights the interconnected vibrational and electronic motions at the foundation of nonadiabatic dynamics where nuclear motions, including torsional rotations and bond vibrations, drive electronic transitions.« less

Frenkel-Charge-Transfer exciton intermixing theory for molecular crystals with two isolated Frenkel exciton states.

NASA Astrophysics Data System (ADS)

Bondarev, Igor; Popescu, Adrian

We develop an analytical theory for the intra-intermolecular exciton intermixing in periodic 1D chains of planar organic molecules with two isolated low-lying Frenkel exciton states, typical of copper phthalocyanine (CuPc) and other transition metal phthalocyanine molecules. We formulate the Hamiltonian and use the exact Bogoliubov diagonalization procedure to derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer (CT) exciton state. By comparing our theoretical spectrum with available experimental CuPc absorption data, we obtain the parameters of the Frenkel-CT exciton intermixing in CuPc thin films. The two Frenkel exciton states here are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the CT exciton, showing the coupling constant 0.17 eV in agreement with earlier electron transport experiments. Our results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines. DOE-DE-SC0007117 (I.B.), UNC-GA ROI Grant (A.P.).

Phosphorescent cyclometalated complexes for efficient blue organic light-emitting diodes

PubMed Central

Suzuri, Yoshiyuki; Oshiyama, Tomohiro; Ito, Hiroto; Hiyama, Kunihisa; Kita, Hiroshi

2014-01-01

Phosphorescent emitters are extremely important for efficient organic light-emitting diodes (OLEDs), which attract significant attention. Phosphorescent emitters, which have a high phosphorescence quantum yield at room temperature, typically contain a heavy metal such as iridium and have been reported to emit blue, green and red light. In particular, the blue cyclometalated complexes with high efficiency and high stability are being developed. In this review, we focus on blue cyclometalated complexes. Recent progress of computational analysis necessary to design a cyclometalated complex is introduced. The prediction of the radiative transition is indispensable to get an emissive cyclometalated complex. We summarize four methods to control phosphorescence peak of the cyclometalated complex: (i) substituent effect on ligands, (ii) effects of ancillary ligands on heteroleptic complexes, (iii) design of the ligand skeleton, and (iv) selection of the central metal. It is considered that novel ligand skeletons would be important to achieve both a high efficiency and long lifetime in the blue OLEDs. Moreover, the combination of an emitter and a host is important as well as the emitter itself. According to the dependences on the combination of an emitter and a host, the control of exciton density of the triplet is necessary to achieve both a high efficiency and a long lifetime, because the annihilations of the triplet state cause exciton quenching and material deterioration. PMID:27877712

Phosphorescent cyclometalated complexes for efficient blue organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Suzuri, Yoshiyuki; Oshiyama, Tomohiro; Ito, Hiroto; Hiyama, Kunihisa; Kita, Hiroshi

2014-10-01

Phosphorescent emitters are extremely important for efficient organic light-emitting diodes (OLEDs), which attract significant attention. Phosphorescent emitters, which have a high phosphorescence quantum yield at room temperature, typically contain a heavy metal such as iridium and have been reported to emit blue, green and red light. In particular, the blue cyclometalated complexes with high efficiency and high stability are being developed. In this review, we focus on blue cyclometalated complexes. Recent progress of computational analysis necessary to design a cyclometalated complex is introduced. The prediction of the radiative transition is indispensable to get an emissive cyclometalated complex. We summarize four methods to control phosphorescence peak of the cyclometalated complex: (i) substituent effect on ligands, (ii) effects of ancillary ligands on heteroleptic complexes, (iii) design of the ligand skeleton, and (iv) selection of the central metal. It is considered that novel ligand skeletons would be important to achieve both a high efficiency and long lifetime in the blue OLEDs. Moreover, the combination of an emitter and a host is important as well as the emitter itself. According to the dependences on the combination of an emitter and a host, the control of exciton density of the triplet is necessary to achieve both a high efficiency and a long lifetime, because the annihilations of the triplet state cause exciton quenching and material deterioration.

Lowest energy Frenkel and charge transfer exciton intermixing in one-dimensional copper phthalocyanine molecular lattice

NASA Astrophysics Data System (ADS)

Bondarev, I. V.; Popescu, A.; Younts, R. A.; Hoffman, B.; McAfee, T.; Dougherty, D. B.; Gundogdu, K.; Ade, H. W.

2016-11-01

We report the results of the combined experimental and theoretical studies of the low-lying exciton states in crystalline copper phthalocyanine. We derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer exciton state and compare it with temperature dependent optical absorption spectra measured experimentally, to obtain the parameters of the Frenkel-charge-transfer exciton intermixing. The two Frenkel exciton states are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the charge transfer exciton, showing the coupling constant 0.17 eV which agrees with earlier experimental measurements. These results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines.

Dynamics of exciton transfer in coupled polymer chains.

PubMed

Zhang, Y L; Liu, X J; Sun, Z; An, Z

2013-05-07

The dynamics of singlet and triplet exciton transfer in coupled polymer chains are investigated within the Su-Schrieffer-Heeger+Pariser-Parr-Pople model including both electron-phonon (e-p) coupling and electron-electron (e-e) interactions, using a multi-configurational time-dependent Hartree-Fock dynamic method. In order to explain the processes involved, the effects of on-site and long-range e-e interactions on the locality of the singlet and triplet excitons are first investigated on an isolated chain. It is found that the locality of the singlet exciton decreases, while the locality of the triplet exciton increases with an increase in the on-site e-e interactions. On the other hand, an increase in the long-range e-e interaction results in a more localized singlet exciton and triplet exciton. In coupled polymer chains, we then quantitatively show the yields of singlet and triplet exciton transfer products under the same interchain coupling. It is found that the yield of singlet interchain excitons is much higher than that of triplet interchain excitons, that is to say, singlet exciton transfer is significantly easier than that for triplet excitons. This results from the fact that the singlet exciton is more delocalized than the triplet exciton. In addition, hopping of electrons with opposite spins between the coupled chains can facilitate the transfer of singlet excitons. The results are of great significance for understanding the photoelectric conversion process and developing high-power organic optoelectronic applications.

Long-lived exciplex formation and delayed exciton emission in bulk heterojunction blends of silole derivative and polyfluorene copolymer: the role of morphology on exciplex formation and charge separation.

PubMed

Benson-Smith, Jessica J; Wilson, Joanne; Dyer-Smith, Clare; Mouri, Kazuhiro; Yamaguchi, Shigehiro; Murata, Hideyuki; Nelson, Jenny

2009-06-04

Long-lived exciplex emission is observed in blend films of poly[9,9-dioctylfluorene-co-N-(4-methoxy-phenyl)diphenylamine] (TFMO) and the soluble silole derivative 2,5-bis-(2,2-bipyridin-6-yl)-1,1-dimethyl-3,4-diphenylsilacyclopentadiene (PyPySPyPy). The exciplex is characterized by a long-lived (approximately 40-90 ns) component in both the photoluminescence and electroluminescence spectra, which is red-shifted relative to the emission of the pristine materials. In addition to exciplex emission, delayed fluorescence from the TFMO singlet state is observed and is attributed to exciton regeneration through the interfacial exciplex state. Comparing blend films made using chlorobenzene and p-xylene solvents, we find that exciplex lifetime and exciton regeneration in the blend film are sensitive to the choice of solvent and the resulting morphology of the blend film. The exciplex emissive lifetime can be correlated to changes in photoluminescence quenching and efficiency of light-emitting diodes.

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

Peteanu, Linda A.; Chowdhury, Sanchari; Wildeman, Jurjen

One measure of exciton mobility in an aggregate is the efficiency of exciton–exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH–PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed frommore » the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. Furthermore, the wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.« less

Exchange interaction and tunneling-induced transparency in coupled quantum dots

NASA Astrophysics Data System (ADS)

Borges, H. S.; Alcalde, A. M.; Ulloa, Sergio E.

2014-11-01

We investigate the optical response of quantum dot molecules coherently driven by polarized laser light. Our description includes the splitting in excitonic levels caused by isotropic and anisotropic exchange interactions. We consider interdot transitions mediated by hole tunneling between states with the same total angular momentum and between bright and dark exciton states as allowed by spin-flip hopping between the dots in the molecule. Using realistic experimental parameters we demonstrate that the excitonic states coupled by tunneling exhibit a rich and controllable optical response. We show that through the appropriate control of an external electric field and light polarization, the tunneling coupling establishes an efficient destructive quantum interference path that creates a transparency window in the absorption spectra whenever states of appropriate symmetry are mixed by the carrier tunneling. We explore the relevant parameter space that allows probing this phenomenon in experiments. Controlled variation in applied field and laser detuning would allow the optical characterization of spin-preserving and spin-flip hopping amplitudes in such systems by measuring the width of the tunneling-induced transparency windows.

Tunneling Injection and Exciton Diffusion of White Organic Light-Emitting Diodes with Composed Buffer Layers

NASA Astrophysics Data System (ADS)

Yang, Su-Hua; Wu, Jian-Ping; Huang, Tao-Liang; Chung, Bin-Fong

2018-02-01

Four configurations of buffer layers were inserted into the structure of a white organic light emitting diode, and their impacts on the hole tunneling-injection and exciton diffusion processes were investigated. The insertion of a single buffer layer of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) resulted in a balanced carrier concentration and excellent color stability with insignificant chromaticity coordinate variations of Δ x < 0.023 and Δ y < 0.023. A device with a 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) buffer layer was beneficial for hole tunneling to the emission layer, resulting in a 1.45-fold increase in current density. The tunneling of holes and the diffusion of excitons were confirmed by the preparation of a dual buffer layer of CBP:tris-(phenylpyridine)-iridine (Ir(ppy)3)/BCP. A maximum current efficiency of 12.61 cd/A with a luminance of 13,850 cd/m2 was obtained at 8 V when a device with a dual-buffer layer of CBP:6 wt.% Ir(ppy)3/BCP was prepared.

[Phosphorescent effect of Ir (ppy)3 on the luminescent characteristic of Rubrene].

PubMed

Xu, Hong-Hua; Xu, Zheng; Zhang, Fu-Jun; Zhao, Su-Ling; Yuan, Guang-Cai; Chen, Yue-Ning

2008-07-01

Many organic matters including heavy metal ions can validly utilize the singlet and triplet for luminescence owiog to the spin-orbit coupling. As a result, the internal quantum efficiency can easily achieve a value higher than traditional organic light emitting diodes in theory. There is a strong luminescence of PVK in PVK : PBD : Rubrene system. PL spectra excited by 345 nm of PVK : PBD : Rubrene thin film has a 410 nm PVK luminescent peak and a 560 nm Rubrene peak. EL still has a PVK luminescent peak, which should be kept from happening. Excitons can not adequately transferred from the matrix solution to Rubrene. The doping with Ir(ppy)3 improves the PVK : PBD : Rubrene system performance. PL spectra excited by 345 nm of PVK : PBD : Ir(ppy)3 : Rubrene with low concentration of Rubrene has a 510 nm Ir(ppy)3 peak and a new 548 nm one. However, the Ir(ppy)3 peak is smaller and the Rubrene one is bigger in EL spectra. Notably a strong and single luminescence of Rubrene is obtained in EL and PL spectra excited by 345 nm of PVK : PBD : Ir(ppy)3 : Rubrene with high concentration of Rubrene. Meanwhile, the Ir(ppy)3 luminescent peak disappears. The mechanism originates from the phosphorescent effect of Ir (ppy)3. The singlet excitons can basically be transferred from PVK : PBD or Ir(ppy)3 to Rubrene. But most excitons from Ir (ppy)3 can directly tunnel to the fluorescent material and come into being singlet states that can return to ground states and cause luminescence. Rubrene can accept proportional excitons with low concentration. While the concentration of Rubrene is higher, excitons can be entirely accepted by Rubrene. The effect also restricts the luminescent intensity of Ir(ppy)3 and boosts up that of Rubrene. Furthermore, the energy transfer in PVK : PBD : Ir(ppy)3 : Rubrene system is primary the Forester energy transfer. Excitation spectra of Rubrene and emission spectra of Ir(ppy)3 have a large overlap revealing that there is a strong energy transfer and further confirmed the phosphorescent effect of Ir(ppy)3. The doping system with phosphorescence material and small molecules can enhance the brightness and internal quantum efficiency.

Exciton Correlations in Intramolecular Singlet Fission

DOE PAGES

Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.; ...

2016-05-16

We have synthesized a series of asymmetric pentacene-tetracene heterodimers with a variable-length conjugated bridge that undergo fast and efficient intramolecular singlet fission (iSF). These compounds have distinct singlet and triplet energies, which allow us to study the spatial dynamics of excitons during the iSF process, including the significant role of exciton correlations in promoting triplet pair generation and recombination. We demonstrate that the primary photoexcitations in conjugated dimers are delocalized singlets that enable fast and efficient iSF. However, in these asymmetric dimers, the singlet becomes more localized on the lower energy unit as the length of the bridge is increased,more » slowing down iSF relative to analogous symmetric dimers. We resolve the recombination kinetics of the inequivalent triplets produced via iSF, and find that they primarily decay via concerted processes. By identifying different decay channels, including delayed fluorescence via triplet-triplet annihilation, we can separate transient species corresponding to both correlated triplet pairs and uncorrelated triplets. Recombination of the triplet pair proceeds rapidly despite our experimental and theoretical demonstration that individual triplets are highly localized and unable to be transported across the conjugated linker. In this class of compounds, the rate of formation and yield of uncorrelated triplets increases with bridge length. Overall, these constrained, asymmetric systems provide a unique platform to isolate and study transient species essential for singlet fission, which are otherwise difficult to observe in symmetric dimers or condensed phases.« less

Spatially indirect excitons in coupled quantum wells

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

Lai, Chih-Wei Eddy

2004-03-01

Microscopic quantum phenomena such as interference or phase coherence between different quantum states are rarely manifest in macroscopic systems due to a lack of significant correlation between different states. An exciton system is one candidate for observation of possible quantum collective effects. In the dilute limit, excitons in semiconductors behave as bosons and are expected to undergo Bose-Einstein condensation (BEC) at a temperature several orders of magnitude higher than for atomic BEC because of their light mass. Furthermore, well-developed modern semiconductor technologies offer flexible manipulations of an exciton system. Realization of BEC in solid-state systems can thus provide new opportunitiesmore » for macroscopic quantum coherence research. In semiconductor coupled quantum wells (CQW) under across-well static electric field, excitons exist as separately confined electron-hole pairs. These spatially indirect excitons exhibit a radiative recombination time much longer than their thermal relaxation time a unique feature in direct band gap semiconductor based structures. Their mutual repulsive dipole interaction further stabilizes the exciton system at low temperature and screens in-plane disorder more effectively. All these features make indirect excitons in CQW a promising system to search for quantum collective effects. Properties of indirect excitons in CQW have been analyzed and investigated extensively. The experimental results based on time-integrated or time-resolved spatially-resolved photoluminescence (PL) spectroscopy and imaging are reported in two categories. (i) Generic indirect exciton systems: general properties of indirect excitons such as the dependence of exciton energy and lifetime on electric fields and densities were examined. (ii) Quasi-two-dimensional confined exciton systems: highly statistically degenerate exciton systems containing more than tens of thousands of excitons within areas as small as (10 micrometer) 2 were observed. The spatial and energy distributions of optically active excitons were used as thermodynamic quantities to construct a phase diagram of the exciton system, demonstrating the existence of distinct phases. Optical and electrical properties of the CQW sample were examined thoroughly to provide deeper understanding of the formation mechanisms of these cold exciton systems. These insights offer new strategies for producing cold exciton systems, which may lead to opportunities for the realization of BEC in solid-state systems.« less

Efficient hybrid white organic light-emitting diodes for application of triplet harvesting with simple structure

NASA Astrophysics Data System (ADS)

Hwang, Kyo Min; Lee, Song Eun; Lee, Sungkyu; Yoo, Han Kyu; Baek, Hyun Jung; Kim, Young Kwan; Kim, Jwajin; Yoon, Seung Soo

2016-08-01

In this study, we fabricated hybrid white organic light-emitting diodes (WOLEDs) based on triplet harvesting with a simple structure. All the hole transporting material and host in the emitting layer (EML) of devices utilized the same material N,N'-di-1-naphthalenyl-N,N'-diphenyl [1,1':4',1″:4″,1‴-quaterphenyl]-4,4‴-diamine (4P-NPD), which is known to be blue fluorescent material. Simple hybrid WOLEDs were fabricated with blue fluorescent, green and red phosphorescent materials. We investigated the effect of triplet harvesting (TH) by an exciton generation zone on simple hybrid WOLEDs. The simple hybrid WOLEDs characteristically had a dominant hole mobility, so an exciton generation zone was expected in the EML. Additionally, the optimal the thickness of the hole transporting layer and electron transporting layer was fabricated a simple hybrid WOLEDs. The simple hybrid WOLED exhibits a maximum luminous efficiency of 29.3 cd/A and a maximum external quantum efficiency of 11.2%. The Commission Internationale de l'Éclairage (International Commission on Illumination) coordinates were (0.45, 0.43) at about 10,000 cd/m2.

Photophysical Study of Polymer-Based Solar Cells with an Organo-Boron Molecule in the Active Layer

PubMed Central

Romero-Servin, Sergio; de Anda Villa, Manuel; Carriles, R.; Ramos-Ortíz, Gabriel; Maldonado, José-Luis; Rodríguez, Mario; Güizado-Rodríguez, M.

2015-01-01

Our group previously reported the synthesis of four polythiophene derivatives (P1–P4) used for solar cells. The cells were prepared under room conditions by spin coating, leading to low efficiencies. However, after the addition of 6-nitro-3-(E)-3-(4-dimethylaminophenyl)allylidene)-2,3-dihydrobenzo[d]-[1,3,2] oxazaborole (M1) to their active layers, the efficiencies of the cells showed approximately a two-fold improvement. In this paper, we study this enhancement mechanism by performing ultrafast transient absorption (TA) experiments on the active layer of the different cells. Our samples consisted of thin films of a mixture of PC61BM with the polythiophenes derivatives P1–P4. We prepared two versions of each sample, one including the molecule M1 and another without it. The TA data suggests that the efficiency improvement after addition of M1 is due not only to an extended absorption spectrum towards the infrared region causing a larger population of excitons but also to the possible creation of additional channels for transport of excitons and/or electrons to the PC61BM interface. PMID:28793438

Exciton characteristics in graphene epoxide.

PubMed

Zhu, Xi; Su, Haibin

2014-02-25

Exciton characteristics in graphene epoxide (GE) are investigated by density functional theory with quasi-particle corrections and many-body interactions. The nature of the exciton is influenced by epoxide content and detailed geometric configurations. Two kinds of excitons are identified in GE: Frenkel-like exciton originated from the sp(2) carbon cluster and charge-transfer exciton formed by localized states involving both oxygen and carbon atoms. The unusual blue shift associated with the Frenkel-like exciton leaking is highlighted. One scaling relationship is proposed to address the power-law dependence of Frenkel-like exciton binding strength on its size. The charge-transfer exciton appears in GE samples with the high oxygen coverage. Particularly, the exciton in GE structures exhibits long lifetime by analyzing both radiative and nonradiative decay processes. This study sheds light on the potential applications of GE-based structures with attractive high quantum yield in light emission and optoelectronic technology.

Manipulation of Thermally Activated Delayed Fluorescence of Blue Exciplex Emission: Fully Utilizing Exciton Energy for Highly Efficient Organic Light Emitting Diodes with Low Roll-Off.

PubMed

Wang, Zixing; Wang, Hedan; Zhu, Jun; Wu, Peng; Shen, Bowen; Dou, Dehai; Wei, Bin

2017-06-28

The application of exciplex energy has become a unique way to achieve organic light-emitting diodes (OLEDs) with high efficiencies, low turn-on voltage, and low roll-off. Novel δ-carboline derivatives with high triplet energy (T 1 ≈ 2.92 eV) and high glass transition temperature (T g ≈ 153 °C) were employed to manipulate exciplex emissions in this paper. Deep blue (peak at 436 nm) and pure blue (peak at 468 nm) thermally activated delayed fluorescence (TADF) of exciplex OLEDs were demonstrated by utilizing them as emitters with the maximum current efficiency (CE) of 4.64 cd A -1 , power efficiency (PE) of 2.91 lm W -1 , and external quantum efficiency (EQE) of 2.36%. Highly efficient blue phosphorescent OLEDs doped with FIrpic showed a maximum CE of 55.6 cd A -1 , PE of 52.9 lm W -1 , and EQE of 24.6% respectively with very low turn on voltage at 2.7 V. The devices still remain high CE of 46.5 cd A -1 at 100 cd m -2 , 45.4 cd A -1 at 1000 cd m -2 and 42.3 cd A -1 at 5000 cd m -2 with EQE close to 20% indicating low roll-off. Manipulating blue exciplex emissions by chemical structure gives an ideal strategy to fully utilize all exciton energies for lighting of OLEDs.

Probing excitons in transition metal dichalcogenides by Drude-like exciton intraband absorption.

PubMed

Zhao, Siqi; He, Dawei; He, Jiaqi; Zhang, Xinwu; Yi, Lixin; Wang, Yongsheng; Zhao, Hui

2018-05-24

Understanding excitonic dynamics in two-dimensional semiconducting transition metal dichalcogenides is important for developing their optoelectronic applications. Recently, transient absorption techniques based on resonant excitonic absorption have been used to study various aspects of excitonic dynamics in these materials. The transient absorption in such measurements originates from phase-space state filling, bandgap renormalization, or screening effects. Here we report a new method to probe excitonic dynamics based on exciton intraband absorption. In this Drude-like process, probe photons are absorbed by excitons in their intraband excitation to higher energy states, causing a transient absorption signal. Although the magnitude of the transient absorption is lower than that of the resonant techniques, the new method is less restrictive on the selection of probe wavelength, has a larger linear range, and can provide complementary information on photocarrier dynamics. Using the WS2 monolayer and bulk samples as examples, we show that the new method can probe exciton-exciton annihilation at high densities and reveal exciton formation processes. We also found that the exciton intraband absorption cross section of the WS2 monolayer is on the order of 10-18 cm2.

Band-edge absorption coefficients from photoluminescence in semiconductor multiple quantum wells

NASA Technical Reports Server (NTRS)

Kost, Alan; Zou, Yao; Dapkus, P. D.; Garmire, Elsa; Lee, H. C.

1989-01-01

A novel approach to determining absorption coefficients in thin films using luminescence is described. The technique avoids many of the difficulties typically encountered in measurements of thin samples, Fabry-Perot effects, for example, and can be applied to a variety of materials. The absorption edge for GaAs/AlGaAs multiple quantum well structures, with quantum well widths ranging from 54 to 193 A is examined. Urbach (1953) parameters and excitonic linewidths are tabulated.

Pressure induced increase of the exciton phonon interaction in ZnO/(ZnMg)O quantum wells

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

Jarosz, D.; Suchocki, A.; Kozanecki, A.

2016-03-15

It is a well-established experimental fact that exciton-phonon coupling is very efficient in ZnO. The intensities of the phonon-replicas in ZnO/(ZnMg)O quantum structures strongly depend on the internal electric field. We performed high-pressure measurements on the single ZnO/(ZnMg)O quantum well. We observed a strong increase of the intensity of the phonon-replicas relative to the zero phonon line. In our opinion this effect is related to pressure induced increase of the strain in quantum structure. As a consequence, an increase of the piezoelectric component of the electric field is observed which leads to an increase of the intensity of the phonon-replicas.

Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer.

PubMed

Chowdhury, Mithun; Sajjad, Muhammad T; Savikhin, Victoria; Hergué, Noémie; Sutija, Karina B; Oosterhout, Stefan D; Toney, Michael F; Dubois, Philippe; Ruseckas, Arvydas; Samuel, Ifor D W

2017-05-17

The influence of various processing conditions on the singlet exciton diffusion is explored in films of a conjugated random copolymer poly-(3-hexylthiophene-co-3-dodecylthiophene) (P3HT-co-P3DDT) and correlated with the degree of crystallinity probed by grazing incidence X-ray scattering and with exciton bandwidth determined from absorption spectra. The exciton diffusion coefficient is deduced from exciton-exciton annihilation measurements and is found to increase by more than a factor of three when thin films are annealed using CS 2 solvent vapour. A doubling of exciton diffusion coefficient is observed upon melt annealing at 200 °C and the corresponding films show about 50% enhancement in the degree of crystallinity. In contrast, films fabricated from polymer solutions containing a small amount of either solvent additive or nucleating agent show a decrease in exciton diffusion coefficient possibly due to formation of traps for excitons. Our results suggest that the enhancement of exciton diffusivity occurs because of increased crystallinity of alkyl-stacking and longer conjugation of aggregated chains which reduces the exciton bandwidth.

Intrachain exciton dynamics in conjugated polymer chains in solution.

PubMed

Tozer, Oliver Robert; Barford, William

2015-08-28

We investigate exciton dynamics on a polymer chain in solution induced by the Brownian rotational motion of the monomers. Poly(para-phenylene) is chosen as the model system and excitons are modeled via the Frenkel exciton Hamiltonian. The Brownian fluctuations of the torsional modes were modeled via the Langevin equation. The rotation of monomers in polymer chains in solution has a number of important consequences for the excited state properties. First, the dihedral angles assume a thermal equilibrium which causes off-diagonal disorder in the Frenkel Hamiltonian. This disorder Anderson localizes the Frenkel exciton center-of-mass wavefunctions into super-localized local exciton ground states (LEGSs) and higher-energy more delocalized quasi-extended exciton states (QEESs). LEGSs correspond to chromophores on polymer chains. The second consequence of rotations-that are low-frequency-is that their coupling to the exciton wavefunction causes local planarization and the formation of an exciton-polaron. This torsional relaxation causes additional self-localization. Finally, and crucially, the torsional dynamics cause the Frenkel Hamiltonian to be time-dependent, leading to exciton dynamics. We identify two distinct types of dynamics. At low temperatures, the torsional fluctuations act as a perturbation on the polaronic nature of the exciton state. Thus, the exciton dynamics at low temperatures is a small-displacement diffusive adiabatic motion of the exciton-polaron as a whole. The temperature dependence of the diffusion constant has a linear dependence, indicating an activationless process. As the temperature increases, however, the diffusion constant increases at a faster than linear rate, indicating a second non-adiabatic dynamics mechanism begins to dominate. Excitons are thermally activated into higher energy more delocalized exciton states (i.e., LEGSs and QEESs). These states are not self-localized by local torsional planarization. During the exciton's temporary occupation of a LEGS-and particularly a quasi-band QEES-its motion is semi-ballistic with a large group velocity. After a short period of rapid transport, the exciton wavefunction collapses again into an exciton-polaron state. We present a simple model for the activated dynamics which is in agreement with the data.

Quantum and Carbon Nanomaterials | Chemistry and Nanoscience Research |

Science.gov Websites

acceptors in composites with thiophene-based conjugated polymers, ultimately determining that the free interface to efficiently dissociate excitons and spatially separate long-lived free carriers, but pointed toward a dependence of the free-carrier yield on the energetic driving force at the interface. By tuning

Permanent Rabi oscillations in coupled exciton-photon systems with PT -symmetry

PubMed Central

Chestnov, Igor Yu.; Demirchyan, Sevak S.; Alodjants, Alexander P.; Rubo, Yuri G.; Kavokin, Alexey V.

2016-01-01

We propose a physical mechanism which enables permanent Rabi oscillations in driven-dissipative condensates of exciton-polaritons in semiconductor microcavities subjected to external magnetic fields. The method is based on stimulated scattering of excitons from the incoherent reservoir. We demonstrate that permanent non-decaying oscillations may appear due to the parity-time symmetry of the coupled exciton-photon system realized in a specific regime of pumping to the exciton state and depletion of the reservoir. At non-zero exciton-photon detuning, robust permanent Rabi oscillations occur with unequal amplitudes of exciton and photon components. Our predictions pave way to realization of integrated circuits based on exciton-polariton Rabi oscillators. PMID:26790534

Permanent Rabi oscillations in coupled exciton-photon systems with PT-symmetry.

PubMed

Chestnov, Igor Yu; Demirchyan, Sevak S; Alodjants, Alexander P; Rubo, Yuri G; Kavokin, Alexey V

2016-01-21

We propose a physical mechanism which enables permanent Rabi oscillations in driven-dissipative condensates of exciton-polaritons in semiconductor microcavities subjected to external magnetic fields. The method is based on stimulated scattering of excitons from the incoherent reservoir. We demonstrate that permanent non-decaying oscillations may appear due to the parity-time symmetry of the coupled exciton-photon system realized in a specific regime of pumping to the exciton state and depletion of the reservoir. At non-zero exciton-photon detuning, robust permanent Rabi oscillations occur with unequal amplitudes of exciton and photon components. Our predictions pave way to realization of integrated circuits based on exciton-polariton Rabi oscillators.

Exciton diffusion in WSe2 monolayers embedded in a van der Waals heterostructure

NASA Astrophysics Data System (ADS)

Cadiz, F.; Robert, C.; Courtade, E.; Manca, M.; Martinelli, L.; Taniguchi, T.; Watanabe, K.; Amand, T.; Rowe, A. C. H.; Paget, D.; Urbaszek, B.; Marie, X.

2018-04-01

We have combined spatially resolved steady-state micro-photoluminescence with time-resolved photoluminescence to investigate the exciton diffusion in a WSe2 monolayer encapsulated with hexagonal boron nitride. At 300 K, we extract an exciton diffusion length of LX = 0.36 ± 0.02 μm and an exciton diffusion coefficient of DX = 14.5 ± 2 cm2/s. This represents a nearly 10-fold increase in the effective mobility of excitons with respect to several previously reported values on nonencapsulated samples. At cryogenic temperatures, the high optical quality of these samples has allowed us to discriminate the diffusion of the different exciton species: bright and dark neutral excitons, as well as charged excitons. The longer lifetime of dark neutral excitons yields a larger diffusion length of LXD=1.5 ±0.02 μ m.

Bound exciton and free exciton states in GaSe thin slab.

PubMed

Wei, Chengrong; Chen, Xi; Li, Dian; Su, Huimin; He, Hongtao; Dai, Jun-Feng

2016-09-22

The photoluminescence (PL) and absorption experiments have been performed in GaSe slab with incident light polarized perpendicular to c-axis of sample at 10 K. An obvious energy difference of about 34 meV between exciton absorption peak and PL peak (the highest energy peak) is observed. By studying the temperature dependence of PL and absorption spectra, we attribute it to energy difference between free exciton and bound exciton states, where main exciton absorption peak comes from free exciton absorption, and PL peak is attributed to recombination of bound exciton at 10 K. This strong bound exciton effect is stable up to 50 K. Moreover, the temperature dependence of integrated PL intensity and PL lifetime reveals that a non-radiative process, with activation energy extracted as 0.5 meV, dominates PL emission.

Cooperative Singlet and Triplet Exciton Transport in Tetracene Crystals Visualized by Ultrafast Microscopys

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

Wan, Yan; Guo, Zhi; Zhu, Tong

2015-09-14

Singlet fission presents an attractive solution to overcome the Shockley–Queisser limit by generating two triplet excitons from one singlet exciton. Although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. We report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. Moreover, these measurements revealmore » a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.« less

Cooperative singlet and triplet exciton transport in tetracene crystals visualized by ultrafast microscopy

NASA Astrophysics Data System (ADS)

Wan, Yan; Guo, Zhi; Zhu, Tong; Yan, Suxia; Johnson, Justin; Huang, Libai

2015-10-01

Singlet fission presents an attractive solution to overcome the Shockley-Queisser limit by generating two triplet excitons from one singlet exciton. However, although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. Here, we report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. These measurements reveal a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.

Highly Efficient Full-Color Thermally Activated Delayed Fluorescent Organic Light-Emitting Diodes: Extremely Low Efficiency Roll-Off Utilizing a Host with Small Singlet-Triplet Splitting.

PubMed

Zhang, Dongdong; Zhao, Chongguang; Zhang, Yunge; Song, Xiaozeng; Wei, Pengcheng; Cai, Minghan; Duan, Lian

2017-02-08

Numerous efforts have been devoted to boost the efficiency of thermally activated delayed fluorescence (TADF) devices; however, strategies to suppress the device efficiency roll-off are still in urgent need. Here, a general and effective approach to suppress the efficiency roll-off of TADF devices is proposed, that is, utilizing TADF materials as the hosts for TADF emitters. Bearing small singlet-triplet splitting (ΔE ST ) with donor and acceptor units, TADF materials as the hosts possess the potential to achieve matched frontier energy levels with the adjacent transporting layers, facilitating balanced charge injection as well as bipolar charge transport mobilities beneficial to the balanced charges transportation. Furthermore, an enhanced Förster energy transfer from the host to the dopant can be anticipated, helpful to reduce the exciton concentration. Based on the principles, a new TADF material based on indeno[2,1-b]carbazole/1,3,5-triazin derivation is synthesized and used as the universal host for the full-color TADF devices. Remarkable low efficiency roll-off was achieved with above 90% of the maximum external quantum efficiencies (EQE max 's) maintained even at a brightness of 2000 cd/m 2 , along with EQE max 's of 23.2, 21.0, and 19.2% for orange, green, and sky-blue TADF devices, respectively. Through computational simulation, we identified the suppressed exciton annihilation rates compared with devices adopting conventional hosts. The state-of-the-art low efficiency roll-off of those TADF devices manifests the great potential of such host design strategy, paving an efficient strategy toward their practical application.

Atomistic model for excitons: Capturing Strongly Bound Excitons in Monolayer Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Tseng, Frank; Simsek, Ergun; Gunlycke, Daniel

2015-03-01

Monolayer transition-metal dichalcogenides form a direct bandgap predicted in the visible regime making them attractive host materials for various electronic and optoelectronic applications. Due to a weak dielectric screening in these materials, strongly bound electron-hole pairs or excitons have binding energies up to at least several hundred meV's. While the conventional wisdom is to think of excitons as hydrogen-like quasi-particles, we show that the hydrogen model breaks down for these experimentally observed strongly bound, room-temperature excitons. To capture these non-hydrogen-like photo-excitations, we introduce an atomistic model for excitons that predicts both bright excitons and dark excitons, and their broken degeneracy in these two-dimensional materials. For strongly bound exciton states, the lattice potential significantly distorts the envelope wave functions, which affects predicted exciton peak energies. The combination of large binding energies and non-degeneracy of exciton states in monolayer transition metal dichalogendies may furthermore be exploited in room temperature applications where prolonged exciton lifetimes are necessary. This work has been funded by the Office of Naval Research (ONR), directly and through the Naval Research Laboratory (NRL). F.T and E.S acknowledge support from NRL through the NRC Research Associateship Program and ONR Summer Faculty Program, respectively.

Matt Beard | NREL

Science.gov Websites

. McNichols, J. Gu, A.J. Nozik, A. Sellinger, G. Galli, M.C. Beard, "Tuning colloidal quantum dot band , 15257, 2017, DOI:10.1038/ncomms15257 Y. Yan, R. W. Crisp, J. Gu, B.D. Chernomodik, G.F. Pach, A.R . Marshall, J. A. Turner, M.C. Beard, "Multiple exciton generation for photoelectrochemical hydrogen

Exceeding Conventional Photovoltaic Efficiency Limits Using Colloidal Quantum Dots

NASA Astrophysics Data System (ADS)

Pach, Gregory F.

Colloidal quantum dots (QDs) are a widely investigated field of research due to their highly tunable nature in which the optical and electronic properties of the nanocrystal can be manipulated by merely changing the nanocrystal's size. Specifically, colloidal quantum dot solar cells (QDSCs) have become a promising candidate for future generation photovoltaic technology. Quantum dots exhibit multiple exciton generation (MEG) in which multiple electron-hole pairs are generated from a single high-energy photon. This process is not observed in bulk-like semiconductors and allows for QDSCs to achieve theoretical efficiency limits above the standard single-junction Shockley-Queisser limit. However, the fast expanding field of QDSC research has lacked standardization of synthetic techniques and device design. Therefore, we sought to detail methodology for synthesizing PbS and PbSe QDs as well as photovoltaic device fabrication techniques as a fast track toward constructing high-performance solar cells. We show that these protocols lead toward consistently achieving efficiencies above 8% for PbS QDSCs. Using the same methodology for building single-junction photovoltaic devices, we incorporated PbS QDs as a bottom cell into a monolithic tandem architecture along with solution-processed CdTe nanocrystals. Modeling shows that near-peak tandem device efficiencies can be achieved across a wide range of bottom cell band gaps, and therefore the highly tunable band gap of lead-chalcogenide QDs lends well towards a bottom cell in a tandem architecture. A fully functioning monolithic tandem device is realized through the development of a ZnTe/ZnO recombination layer that appropriately combines the two subcells in series. Multiple recent reports have shown nanocrystalline heterostructures to undergo the MEG process more efficiency than several other nanostrucutres, namely lead-chalcogenide QDs. The final section of my thesis expands upon a recent publication by Zhang et. al., which details the synthesis of PbS/CdS heterostructures in which the PbS and CdS domains exist on opposite sides of the nanocrystal and are termed "Janus particles". Transient absorption spectroscopy shows MEG quantum yields above unity very the thermodynamic limit of 2Eg for PbS/CdS Janus particles. We further explain a mechanism for enhanced MEG using photoluminescence studies.

Visualization of exciton transport in ordered and disordered molecular solids.

PubMed

Akselrod, Gleb M; Deotare, Parag B; Thompson, Nicholas J; Lee, Jiye; Tisdale, William A; Baldo, Marc A; Menon, Vinod M; Bulović, Vladimir

2014-04-16

Transport of nanoscale energy in the form of excitons is at the core of photosynthesis and the operation of a wide range of nanostructured optoelectronic devices such as solar cells, light-emitting diodes and excitonic transistors. Of particular importance is the relationship between exciton transport and nanoscale disorder, the defining characteristic of molecular and nanostructured materials. Here we report a spatial, temporal and spectral visualization of exciton transport in molecular crystals and disordered thin films. Using tetracene as an archetype molecular crystal, the imaging reveals that exciton transport occurs by random walk diffusion, with a transition to subdiffusion as excitons become trapped. By controlling the morphology of the thin film, we show that this transition to subdiffusive transport occurs at earlier times as disorder is increased. Our findings demonstrate that the mechanism of exciton transport depends strongly on the nanoscale morphology, which has wide implications for the design of excitonic materials and devices.

Identification of effective exciton-exciton annihilation in squaraine-squaraine copolymers.

PubMed

Hader, Kilian; May, Volkhard; Lambert, Christoph; Engel, Volker

2016-05-11

Ultrafast time-resolved transient absorption spectroscopy is able to monitor the fate of the excited state population in molecular aggregates or polymers. Due to many competing decay processes, the identification of exciton-exciton annihilation (EEA) is difficult. Here, we use a microscopic model to describe exciton annihilation processes in squaraine-squaraine copolymers. Transient absorption time traces measured at different laser powers exhibit an unusual time-dependence. The analysis points towards dynamics taking place on three time-scales. Immediately after laser-excitation a localization of excitons takes place within the femtosecond time-regime. This is followed by exciton-exciton annihilation which is responsible for a fast decay of the exciton population. At later times, excitations being localized on units which are not directly connected remain so that diffusion dominates the dynamics and leads to a slower decay. We thus provide evidence for EEA tracked by time-resolved spectroscopy which has not been reported that clearly before.

Cross-circularly polarized two-exciton states in one to three dimensions

NASA Astrophysics Data System (ADS)

Ajiki, Hiroshi

2015-03-01

Biexciton and two-exciton dissociated states of Frenkel-type excitons are studied theoretically using an exciton tight-binding (TB) model including a polarization degree of freedom. Because the biexciton consists of two cross-circularly polarized excitons, an on-site interaction (V) between the two excitons should be considered in addition to a nearest-neighbor two-exciton attractive interaction (δ). Although there are an infinitely large number of combinations of V and δ providing the observed binding energy of a biexciton, the wave function of the biexciton and two-exciton dissociated states is nearly independent of these parameter sets. This means that all the two-exciton states are uniquely determined from the exciton TB model. There are a spatially symmetric and an antisymmetric biexciton state for a one-dimensional (1D) lattice and two symmetric and one antisymmetric biexciton states at most for two- (2D) and three-dimensional (3D) lattices. In contrast, when the polarization degree of freedom is ignored, there is one biexciton state for 1D, 2D, and 3D lattices. For this study, a rapid and memory-saving calculation method for two-exciton states is extended to include the polarization degree of freedom.

Cross-circularly polarized two-exciton states in one to three dimensions.

PubMed

Ajiki, Hiroshi

2015-03-14

Biexciton and two-exciton dissociated states of Frenkel-type excitons are studied theoretically using an exciton tight-binding (TB) model including a polarization degree of freedom. Because the biexciton consists of two cross-circularly polarized excitons, an on-site interaction (V) between the two excitons should be considered in addition to a nearest-neighbor two-exciton attractive interaction (δ). Although there are an infinitely large number of combinations of V and δ providing the observed binding energy of a biexciton, the wave function of the biexciton and two-exciton dissociated states is nearly independent of these parameter sets. This means that all the two-exciton states are uniquely determined from the exciton TB model. There are a spatially symmetric and an antisymmetric biexciton state for a one-dimensional (1D) lattice and two symmetric and one antisymmetric biexciton states at most for two- (2D) and three-dimensional (3D) lattices. In contrast, when the polarization degree of freedom is ignored, there is one biexciton state for 1D, 2D, and 3D lattices. For this study, a rapid and memory-saving calculation method for two-exciton states is extended to include the polarization degree of freedom.

Effective Mass Theory of 2D Excitons Revisited

NASA Astrophysics Data System (ADS)

Gonzalez, Joseph; Oleynik, Ivan

Two-dimensional (2D) semiconducting materials possess an exceptionally unique set of electronic and excitonic properties due to the combined effects of quantum and dielectric confinement. Reliable determination of exciton binding energies from both first-principles many-body perturbation theory (GW/BSE) and experiment is very challenging due to the enormous computational expense as well as the tremendous technical difficulties in experiment.. Very recently, effective mass theories of 2D excitons have been developed as an attractive alternative for inexpensive and accurate evaluation of the exciton binding energies. In this presentation, we evaluate two effective mass theory approaches by Velizhanin et al and Olsen et al in predicting exciton binding energies across a wide range of 2D materials. We specifically analyze the trends related to the varying screening lengths and exciton effective masses. We also extended the effective mass theory of 2D excitons to include effects of electron and hole mass anisotropies (mx ≠ my) , the latter showing a substantial influence on exciton binding energies. The recent predictions of exciton binding energies being independent of the exciton effective mass and a linear correlation with the band gap of a specific material are also critically reexamined.

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

Thomas, Reshmi; Thomas, Anoop; Pullanchery, Saranya

Strong coupling interactions between plasmon and exciton-based excitations have been proposed to be useful in the design of optoelectronic systems. However, the role of various optical parameters dictating the plasmon-exciton (plexciton) interactions is less understood. Herein, we propose an inequality for achieving strong coupling between plasmons and excitons through appropriate variation of their oscillator strengths and spectral widths. These aspects are found to be consistent with experiments on two sets of free-standing plexcitonic systems obtained by (i) linking fluorescein isothiocyanate on Ag nanoparticles of varying sizes through silane coupling and (ii) electrostatic binding of cyanine dyes on polystyrenesulfonate-coated Au nanorodsmore » of varying aspect ratios. Being covalently linked on Ag nanoparticles, fluorescein isothiocyanate remains in monomeric state, and its high oscillator strength and narrow spectral width enable us to approach the strong coupling limit. In contrast, in the presence of polystyrenesulfonate, monomeric forms of cyanine dyes exist in equilibrium with their aggregates: Coupling is not observed for monomers and H-aggregates whose optical parameters are unfavorable. The large aggregation number, narrow spectral width, and extremely high oscillator strength of J-aggregates of cyanines permit effective delocalization of excitons along the linear assembly of chromophores, which in turn leads to efficient coupling with the plasmons. Further, the results obtained from experiments and theoretical models are jointly employed to describe the plexcitonic states, estimate the coupling strengths, and rationalize the dispersion curves. The experimental results and the theoretical analysis presented here portray a way forward to the rational design of plexcitonic systems attaining the strong coupling limits.« less

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

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

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

DOE PAGES

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel; ...

2018-04-13

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

White-Light Emission from Layered Halide Perovskites.

PubMed

Smith, Matthew D; Karunadasa, Hemamala I

2018-03-20

With nearly 20% of global electricity consumed by lighting, more efficient illumination sources can enable massive energy savings. However, effectively creating the high-quality white light required for indoor illumination remains a challenge. To accurately represent color, the illumination source must provide photons with all the energies visible to our eye. Such a broad emission is difficult to achieve from a single material. In commercial white-light sources, one or more light-emitting diodes, coated by one or more phosphors, yield a combined emission that appears white. However, combining emitters leads to changes in the emission color over time due to the unequal degradation rates of the emitters and efficiency losses due to overlapping absorption and emission energies of the different components. A single material that emits broadband white light (a continuous emission spanning 400-700 nm) would obviate these problems. In 2014, we described broadband white-light emission upon near-UV excitation from three new layered perovskites. To date, nine white-light-emitting perovskites have been reported by us and others, making this a burgeoning field of study. This Account outlines our work on understanding how a bulk material, with no obvious emissive sites, can emit every color of the visible spectrum. Although the initial discoveries were fortuitous, our understanding of the emission mechanism and identification of structural parameters that correlate with the broad emission have now positioned us to design white-light emitters. Layered hybrid halide perovskites feature anionic layers of corner-sharing metal-halide octahedra partitioned by organic cations. The narrow, room-temperature photoluminescence of lead-halide perovskites has been studied for several decades, and attributed to the radiative recombination of free excitons (excited electron-hole pairs). We proposed that the broad white emission we observed primarily stems from exciton self-trapping. Here, the exciton couples strongly to the lattice, creating transient elastic lattice distortions that can be viewed as "excited-state defects". These deformations stabilize the exciton affording a broad emission with a large Stokes shift. Although material defects very likely contribute to the emission width, our mechanistic studies suggest that the emission mostly arises from the bulk material. Ultrafast spectroscopic measurements support self-trapping, with new, transient, electronic states appearing upon photoexcitation. Importantly, the broad emission appears common to layered Pb-Br and Pb-Cl perovskites, albeit with a strong temperature dependence. Although the emission is attributed to light-induced defects, it still reflects changes in the crystal structure. We find that greater out-of-plane octahedral tilting increases the propensity for the broad emission, enabling synthetic control over the broad emission. Many of these perovskites have color rendering abilities that exceed commercial requirements and mixing halides affords both "warm" and "cold" white light. The most efficient white-light-emitting perovskite has a quantum efficiency of 9%. Improving this value will make these phosphors attractive for solid-state lighting, particularly as large-area coatings that can be deposited inexpensively. The emission mechanism can also be extended to other low-dimensional systems. We hope this Account aids in expanding the phase space of white-light emitters and controlling their exciton dynamics by the synthetic, spectroscopic, theoretical, and engineering communities.

Surface states in the photoionization of high-quality CdSe core/shell nanocrystals.

PubMed

Li, Shu; Steigerwald, Michael L; Brus, Louis E

2009-05-26

We use electric force microscopy (EFM) to study single nanocrystal photoionization in two classes of high-quality nanocrystals whose exciton luminescence quantum yields approach unity in solution. The CdSe/CdS/ZnS core/shell nanocrystals do not photoionize, while the CdSe/CdS nanocrystals do show substantial photoionization. This verifies the theoretical prediction that the ZnS shell confines the excited electron within the nanocrystal. Despite the high luminescence quantum yield, photoionization varies substantially among the CdSe/CdS nanocrystals. We have studied the nanocrystal photoionization with both UV (396 nm) and green (532 nm) light, and we have found that the magnitude of the charge due to photoionization per absorbed photon is greater for UV excitation than for green excitation. A fraction of the photoionization occurs directly via a "hot electron" process, using trap states that are either on the particle surface, within the ligand sphere, or within the silicon oxide layer. This must occur without relaxation to the thermalized, lowest-energy, emitting exciton. We discuss the occurrence of hot carrier processes that are common to photoionization, luminescence blinking, and the fast transient optical absorption that is associated with multiple exciton generation MEG studies.

Engineering of lead chalcogenide nanostructures for carrier multiplication: Core/shell, 1D, and 2D

NASA Astrophysics Data System (ADS)

Lin, Qianglu

Near infrared emitting semiconductors have been used widely in industry especially in solar-cell fabrications. The efficiency of single junction solar-cell can reach the Shockley-Queisser limit by using optimum band gap material such as silicon and cadmium telluride. The theoretical efficiency can be further enhanced through carrier multiplication, in which a high energy photon is absorbed and more than one electron-hole pair can be generated, reaching more than 100% quantum efficiency in the high energy region of sunlight. The realization of more than unity external quantum efficiency in lead selenide quantum dots solar cell has motivated vast investigation on lowering the carrier multiplication threshold and further improving the efficiency. This dissertation focuses on synthesis of lead chalcogenide nanostructures for their optical spectroscopy studies. PbSe/CdSe core/shell quantum dots were synthesized by cation exchange to obtain thick shells (up to 14 monolayers) for studies of visible and near infrared dual band emissions and carrier multiplication efficiency. By examining the reaction mechanism, a thermodynamic and a kinetic model are introduced to explain the vacancy driven cation exchange. As indicated by the effective mass model, PbSe/CdSe core/shell quantum dots has quasi-type-II band alignment, possessing electron delocalized through the entire quantum dot and hole localized in the core, which breaks down the symmetry of energy levels in the conduction and valence band, leading to hot-hole-assisted efficient multi-exciton generation and a lower carrier multiplication threshold to the theoretical value. For further investigation of carrier multiplication study, PbTe, possessing the highest efficiency among lead chalcogenides due to slow intraband cooling, is synthesized in one-dimensional and two-dimensional nanostructures. By using dodecanethiol as the surfactant, PbTe NRs can be prepared with high uniformity in width and resulted in fine quantum confinement features. The reaction can be explained by a soft-template assisted process, in which the lamellar lead-thiolate precursor transforms into rod-shape micelle in the existence of telluride anions by electrostatic attraction. Fine tuning the reaction condition by changing the solvent to oleylamine, lead telluride nanowires with length up to 200 nm can be prepared, which bundled together because of the strong dipole-dipole attraction between nanowires. Decreasing the amount of surfactant dodecanethiol in the synthesis produces lead telluride nanorings, which formed by attaching four small particles together, leaving the center void. To prepare two-dimensional nanoplatelets, mixture ligands containing two amines with different carbon chain length were used, which initiate oriented attachment of the nanoparticles to form square-shape nanoplatelets. By further adopting stronger binding ligands such as phosphonic acid, PbTe nanoplatelets with micrometer lateral dimension were prepared with extremely sharp near infrared photoluminescence (less than 40 meV), which has never be achieved in quantum dots and other nanostructures.

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

Butov, L. V., E-mail: lvbutov@physics.ucsd.edu

Due to their long lifetimes, indirect excitons can cool to below the temperature of quantum degeneracy. This gives an opportunity to experimentally study cold composite bosons. Both theoretically predicted phenomena and phenomena that have not been anticipated were observed in a cold gas of indirect excitons. In this contribution, we overview our studies of cold indirect excitons over the past decade, presenting spontaneous coherence and condensation of excitons, spatially modulated exciton state, long-range spin currents and spin textures, and exciton localization–delocalization transitions.

Cascaded exciton energy transfer in a monolayer semiconductor lateral heterostructure assisted by surface plasmon polariton.

PubMed

Shi, Jinwei; Lin, Meng-Hsien; Chen, I-Tung; Mohammadi Estakhri, Nasim; Zhang, Xin-Quan; Wang, Yanrong; Chen, Hung-Ying; Chen, Chun-An; Shih, Chih-Kang; Alù, Andrea; Li, Xiaoqin; Lee, Yi-Hsien; Gwo, Shangjr

2017-06-26

Atomically thin lateral heterostructures based on transition metal dichalcogenides have recently been demonstrated. In monolayer transition metal dichalcogenides, exciton energy transfer is typically limited to a short range (~1 μm), and additional losses may be incurred at the interfacial regions of a lateral heterostructure. To overcome these challenges, here we experimentally implement a planar metal-oxide-semiconductor structure by placing a WS 2 /MoS 2 monolayer heterostructure on top of an Al 2 O 3 -capped Ag single-crystalline plate. We find that the exciton energy transfer range can be extended to tens of microns in the hybrid structure mediated by an exciton-surface plasmon polariton-exciton conversion mechanism, allowing cascaded exciton energy transfer from one transition metal dichalcogenides region supporting high-energy exciton resonance to a different transition metal dichalcogenides region in the lateral heterostructure with low-energy exciton resonance. The realized planar hybrid structure combines two-dimensional light-emitting materials with planar plasmonic waveguides and offers great potential for developing integrated photonic and plasmonic devices.Exciton energy transfer in monolayer transition metal dichalcogenides is limited to short distances. Here, Shi et al. fabricate a planar metal-oxide-semiconductor structure and show that exciton energy transfer can be extended to tens of microns, mediated by an exciton-surface-plasmon-polariton-exciton conversion mechanism.

Brightened spin-triplet interlayer excitons and optical selection rules in van der Waals heterobilayers

NASA Astrophysics Data System (ADS)

Yu, Hongyi; Liu, Gui-Bin; Yao, Wang

2018-07-01

We investigate the optical properties of spin-triplet interlayer excitons in heterobilayer transition metal dichalcogenides in comparison with the spin-singlet ones. Surprisingly, the optical transition dipole of the spin-triplet exciton is found to be in the same order of magnitude to that of the spin-singlet exciton, in sharp contrast to the monolayer excitons where the spin-triplet species is considered as dark compared to the singlet. Unlike the monolayer excitons whose spin-conserved (spin-flip) transition dipole can only couple to light of in-plane (out-of-plane) polarisation, such restriction is removed for the interlayer excitons due to the breaking of the out-of-plane mirror symmetry. We find that as the interlayer atomic registry changes, the optical transition dipole of interlayer exciton crosses between in-plane ones of opposite circular polarizations and the out-of-plane one for both the spin-triplet and spin-singlet species. As a result, excitons of both species have non-negligible coupling into photon modes of both in-plane and out-of-plane propagations, another sharp difference from the monolayers where the exciton couples predominantly into the out-of-plane propagation channel. At given atomic registry, the spin-triplet and spin-singlet excitons have distinct valley polarisation selection rules, allowing the selective optical addressing of both the valley configuration and the spin-singlet/triplet configuration of interlayer excitons.

Exciton-phonon system on a star graph: A perturbative approach.

PubMed

Yalouz, Saad; Pouthier, Vincent

2016-05-01

Based on the operatorial formulation of the perturbation theory, the properties of an exciton coupled with optical phonons on a star graph are investigated. Within this method, the dynamics is governed by an effective Hamiltonian, which accounts for exciton-phonon entanglement. The exciton is dressed by a virtual phonon cloud whereas the phonons are clothed by virtual excitonic transitions. In spite of the coupling with the phonons, it is shown that the energy spectrum of the dressed exciton resembles that of a bare exciton. The only differences originate in a polaronic mechanism that favors an energy shift and a decay of the exciton hopping constant. By contrast, the motion of the exciton allows the phonons to propagate over the graph so that the dressed normal modes drastically differ from the localized modes associated to bare phonons. They define extended vibrations whose properties depend on the state occupied by the exciton that accompanies the phonons. It is shown that the phonon frequencies, either red shifted or blue shifted, are very sensitive to the model parameter in general, and to the size of the graph in particular.

Exciton intrachain transport induced by interchain packing configurations in conjugated polymers.

PubMed

Meng, Ruixuan; Gao, Kun; Zhang, Gaiyan; Han, Shixuan; Yang, Fujiang; Li, Yuan; Xie, Shijie

2015-07-28

Based on a tight binding model combined with a nonadiabatic dynamics approach, we theoretically investigate the exciton intrachain transport in conjugated polymers with different interchain packing configurations. We construct two different interchain packing configurations, i.e. linear and exponential forms, and simulate the dynamical processes of the exciton transport in these systems. We find that, in both cases, there exists a distribution of driving force for exciton transport, which stems from the gradient of the exciton creation energy along the chains. This finding enriches the picture of exciton transport in polymers and provides a new idea to improve the exciton transport length in polymeric photovoltaic devices.

Even exciton series in Cu2O

NASA Astrophysics Data System (ADS)

Schweiner, Frank; Main, Jörg; Wunner, Günter; Uihlein, Christoph

2017-05-01

Recent investigations of excitonic absorption spectra in cuprous oxide (Cu2O ) have shown that it is indispensable to account for the complex valence-band structure in the theory of excitons. In Cu2O , parity is a good quantum number and thus the exciton spectrum falls into two parts: the dipole-active exciton states of negative parity and odd angular momentum, which can be observed in one-photon absorption (Γ4- symmetry), and the exciton states of positive parity and even angular momentum, which can be observed in two-photon absorption (Γ5+ symmetry). The unexpected observation of D excitons in two-photon absorption has given first evidence that the dispersion properties of the Γ5+ orbital valence band are giving rise to a coupling of the yellow and green exciton series. However, a first theoretical treatment by Uihlein et al. [Phys. Rev. B 23, 2731 (1981), 10.1103/PhysRevB.23.2731] was based on a simplified spherical model. The observation of F excitons in one-photon absorption is a further proof of a coupling between yellow and green exciton states. Detailed investigations on the fine structure splitting of the F exciton by F. Schweiner et al. [Phys. Rev. B 93, 195203 (2016), 10.1103/PhysRevB.93.195203] have proved the importance of a more realistic theoretical treatment including terms with cubic symmetry. In this paper we show that the even and odd parity exciton system can be consistently described within the same theoretical approach. However, the Hamiltonian of the even parity system needs, in comparison to the odd exciton case, modifications to account for the very small radius of the yellow and green 1 S exciton. In the presented treatment, we take special care of the central-cell corrections, which comprise a reduced screening of the Coulomb potential at distances comparable to the polaron radius, the exchange interaction being responsible for the exciton splitting into ortho and para states, and the inclusion of terms in the fourth power of p in the kinetic energy being consistent with Oh symmetry. Since the yellow 1 S exciton state is coupled to all other states of positive parity, we show how the central-cell corrections affect the whole even exciton series. The close resonance of the 1 S green exciton with states of the yellow exciton series has a strong impact on the energies and oscillator strengths of all implied states. The consistency between theory and experiment with respect to energies and oscillator strengths for the even and odd exciton system in Cu2O is a convincing proof for the validity of the applied theory.

Interlayer Exciton Optoelectronics in a 2D Heterostructure p-n Junction.

PubMed

Ross, Jason S; Rivera, Pasqual; Schaibley, John; Lee-Wong, Eric; Yu, Hongyi; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jiaqiang; Mandrus, David; Cobden, David; Yao, Wang; Xu, Xiaodong

2017-02-08

Semiconductor heterostructures are backbones for solid-state-based optoelectronic devices. Recent advances in assembly techniques for van der Waals heterostructures have enabled the band engineering of semiconductor heterojunctions for atomically thin optoelectronic devices. In two-dimensional heterostructures with type II band alignment, interlayer excitons, where Coulomb bound electrons and holes are confined to opposite layers, have shown promising properties for novel excitonic devices, including a large binding energy, micron-scale in-plane drift-diffusion, and a long population and valley polarization lifetime. Here, we demonstrate interlayer exciton optoelectronics based on electrostatically defined lateral p-n junctions in a MoSe 2 -WSe 2 heterobilayer. Applying a forward bias enables the first observation of electroluminescence from interlayer excitons. At zero bias, the p-n junction functions as a highly sensitive photodetector, where the wavelength-dependent photocurrent measurement allows the direct observation of resonant optical excitation of the interlayer exciton. The resulting photocurrent amplitude from the interlayer exciton is about 200 times smaller than the resonant excitation of intralayer exciton. This implies that the interlayer exciton oscillator strength is 2 orders of magnitude smaller than that of the intralayer exciton due to the spatial separation of electron and hole to the opposite layers. These results lay the foundation for exploiting the interlayer exciton in future 2D heterostructure optoelectronic devices.

Optical Properties of Gallium Arsenide and Indium Gallium Arsenide Quantum Wells and Their Applications to Opto-Electronic Devices.

NASA Astrophysics Data System (ADS)

Huang, Daming

1990-01-01

In this thesis we investigate the optical properties of modulation doped GaAs/AlGaAs and strained-layer undoped InGaAs/GaAs multiple quantum well structures (MQWS). The phenomena studied are the effects of carrier, strain, and the electric field on the absorption of excitons. For GaAs/AlGaAs modulation doped MQWS, the quenching of excitons by free carriers has been demonstrated. The comparison of the experimental results with calculations which consider phase space filling, screening, and exchange interaction showed the phase space filling to be the dominant mechanism responsible for the change of oscillator strength and binding energy of excitons associated with partially filled subband. On the other hand, the screening and exchange interaction are equally important to excitons associated with empty subbands. For InGaAs/GaAs strained-layer MQWS, we have demonstrated that the band edges are dramatically modified by strain. We determined the band discontinuities at InGaAs/GaAs interfaces using optical absorption, and showed that in this structure the heavy holes are confined in InGaAs layers while the light holes are in GaAs layers, in contrast to GaAs/AlGaAs MQWS. We also explore applications of GaAs/AlGaAs and InGaAs/GaAs MQWS to opto-electronic devices. The principle of devices investigated is mainly based on the electric field effect on the excitonic absorption in MQWS (the quantum confined Stark effect). Two examples presented in this thesis are the strained-layer InGaAs/GaAs MQWS electroabsorption modulators grown on GaAs substrates and the GaAs/AlGaAs MQWS reflection modulators grown on Si substrates. The large modulation observed in the absorption coefficient by an electric field is expected to facilitate opto-electronic integration.

I. Excitonic Phase Diagram in Silicon: Evidence for Two Condensed Phases. I. Motion of Photoexcited Carriers in GALLIUM-ARSENIDE/ALUMINUM(X)GALLIUM(1-X)ARSENIDE Multiple Quantum Wells-Anomalous Confinement at High Densities.

NASA Astrophysics Data System (ADS)

Smith, Leigh Morris

This thesis describes work on the thermodynamics and transport properties of photoexcited carriers in bulk and two-dimensional semiconductors. Two major topics are addressed. I. Photoluminescence experiments of excitons in unstressed silicon are presented which indicate the existence of a new non-degenerate condensed phase of plasma. This new liquid has a density one-tenth that of the ground state electron-hole liquid and is observed both above and below the liquid-gas critical point (~24.5K). A new phase diagram of excitons in silicon is presented which includes these two condensed plasmas. Consistent with the Gibbs phase rule, a triple point at 18.5 K is inferred from the luminescence data as the only temperature where the exciton gas, condensed plasma (CP) and electron-hole liquid (EHL) coexist. The low density condensed plasma persists up to a second critical point at 45 +/- 5K, above which the photoexcited carriers are observed to continuously decay into a partially ionized excitonic gas. II. We have measured the in-plane motion of photoexcited carriers in semiconductor quantum wells with 5 μm spatial and 10 ps temporal resolution and have discovered several surprising results. The effective diffusivity of the carriers at densities below n = 2 times 10^{11}cm ^{-2} is found to depend upon excitation level, possibly indicating defect-limited diffusion or phonon-wind effects. Above this density the spatial profiles exhibit two distinct components with widely differing diffusivities. This remarkable behavior may be understood with consideration of the interactions of non-equilibrium phonons with the photoexcited carriers. We postulate that the slowly diffusing component represents carriers which are "thermally confined" to a phonon hot spot, while the rapidly moving component is driven by the flux of non-equilibrium phonons away from the excitation region.

Communication: Broad manifold of excitonic states in light-harvesting complex 1 promotes efficient unidirectional energy transfer in vivo

NASA Astrophysics Data System (ADS)

Sohail, Sara H.; Dahlberg, Peter D.; Allodi, Marco A.; Massey, Sara C.; Ting, Po-Chieh; Martin, Elizabeth C.; Hunter, C. Neil; Engel, Gregory S.

2017-10-01

In photosynthetic organisms, the pigment-protein complexes that comprise the light-harvesting antenna exhibit complex electronic structures and ultrafast dynamics due to the coupling among the chromophores. Here, we present absorptive two-dimensional (2D) electronic spectra from living cultures of the purple bacterium, Rhodobacter sphaeroides, acquired using gradient assisted photon echo spectroscopy. Diagonal slices through the 2D lineshape of the LH1 stimulated emission/ground state bleach feature reveal a resolvable higher energy population within the B875 manifold. The waiting time evolution of diagonal, horizontal, and vertical slices through the 2D lineshape shows a sub-100 fs intra-complex relaxation as this higher energy population red shifts. The absorption (855 nm) of this higher lying sub-population of B875 before it has red shifted optimizes spectral overlap between the LH1 B875 band and the B850 band of LH2. Access to an energetically broad distribution of excitonic states within B875 offers a mechanism for efficient energy transfer from LH2 to LH1 during photosynthesis while limiting back transfer. Two-dimensional lineshapes reveal a rapid decay in the ground-state bleach/stimulated emission of B875. This signal, identified as a decrease in the dipole strength of a strong transition in LH1 on the red side of the B875 band, is assigned to the rapid localization of an initially delocalized exciton state, a dephasing process that frustrates back transfer from LH1 to LH2.

Nanoimprinting-induced nanomorphological transition in polymer solar cells: enhanced electrical and optical performance.

PubMed

Jeong, Seonju; Cho, Changsoon; Kang, Hyunbum; Kim, Ki-Hyun; Yuk, Youngji; Park, Jeong Young; Kim, Bumjoon J; Lee, Jung-Yong

2015-03-24

We have investigated the effects of a directly nanopatterned active layer on the electrical and optical properties of inverted polymer solar cells (i-PSCs). The capillary force in confined molds plays a critical role in polymer crystallization and phase separation of the film. The nanoimprinting process induced improved crystallization and multidimensional chain alignment of polymers for more effective charge transfer and a fine phase-separation between polymers and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) to favor exciton dissociation and increase the generation rate of charge transfer excitons. Consequently, the power conversion efficiency with a periodic nanostructure was enhanced from 7.40% to 8.50% and 7.17% to 9.15% in PTB7 and PTB7-Th based i-PSCs, respectively.

Visualization of nucleic acids with synthetic exciton-controlled fluorescent oligonucleotide probes.

PubMed

Wang, Dan Ohtan; Okamoto, Akimitsu

2015-01-01

Engineered probes to adapt new photochemical properties upon recognition of target nucleic acids offer powerful tools to DNA and RNA visualization technologies. Herein, we describe a rapid and effective visualization method of nucleic acids in both fixed and living cells with hybridization-sensitive fluorescent oligonucleotide probes. These probes are efficiently quenched in an aqueous environment due to the homodimeric, excitonic interactions between fluorophores but become highly fluorescent upon hybridization to DNA or RNA with complementary sequences. The fast hybridization kinetics and quick fluorescence activation of the new probes allow applications to simplify the conventional fluorescent in situ hybridization protocols and reduce the amount of time to process the samples. Furthermore, hybridization-sensitive fluorescence emission of the probes allows monitoring dynamic behaviors of RNA in living cells.

Organic photovoltaic cells based on unconventional electron donor fullerene and electron acceptor copper hexadecafluorophthalocyanine

NASA Astrophysics Data System (ADS)

Yang, J. L.; Sullivan, P.; Schumann, S.; Hancox, I.; Jones, T. S.

2012-01-01

We demonstrate organic discrete heterojunction photovoltaic cells based on fullerene (C60) and copper hexadecafluorophthalocyanine (F16CuPc), in which the C60 and F16CuPc act as the electron donor and the electron acceptor, respectively. The C60/F16CuPc cells fabricated with conventional and inverted architectures both exhibit comparable power conversion efficiencies. Furthermore, we show that the photocurrent in both cells is generated by a conventional exciton dissociation mechanism rather than the exciton recombination mechanism recently proposed for a similar C60/F16ZnPc system [Song et al., J. Am. Chem. Soc. 132, 4554 (2010)]. These results demonstrate that new unconventional material systems are a potential way to fabricate organic photovoltaic cells with inverted as well as conventional architectures.

Nonlocal Response in Infrared Detector with Semiconducting Carbon Nanotubes and Graphdiyne

PubMed Central

Zheng, Zhe; Fang, Hehai; Liu, Dan; Tan, Zhenjun; Gao, Xin; Hu, Weida; Peng, Hailin; Tong, Lianming

2017-01-01

Abstract Semiconducting single‐walled carbon nanotubes (s‐SWNTs) are regarded as an important candidate for infrared (IR) optical detection due to their excellent intrinsic properties. However, the strong binding energy of excitons in s‐SWNTs seriously impedes the development of s‐SWNTs IR photodetector. This Communication reports an IR photodetector with highly pure s‐SWNTs and γ‐graphdiyne. The heterojunctions between the two materials can efficiently separate the photogenerated excitons. In comparison to device fabricated only with s‐SWNTs, this IR detector shows a uniform response in the whole channel of the device. The response time is demonstrated to be below 1 ms. The optimal responsivity and detectivity approximately reach 0.4 mA W−1 and 5 × 106 cmHz1/2 W−1, respectively. PMID:29270354

Generation and decay dynamics of triplet excitons in Alq3 thin films under high-density excitation conditions.

PubMed

Watanabe, Sadayuki; Furube, Akihiro; Katoh, Ryuzi

2006-08-31

We studied the generation and decay dynamics of triplet excitons in tris-(8-hydroxyquinoline) aluminum (Alq3) thin films by using transient absorption spectroscopy. Absorption spectra of both singlet and triplet excitons in the film were identified by comparison with transient absorption spectra of the ligand molecule (8-hydroxyquinoline) itself and the excited triplet state in solution previously reported. By measuring the excitation light intensity dependence of the absorption, we found that exciton annihilation dominated under high-density excitation conditions. Annihilation rate constants were estimated to be gammaSS = (6 +/- 3) x 10(-11) cm3 s(-1) for single excitons and gammaTT = (4 +/- 2) x 10(-13) cm3 s(-1) for triplet excitons. From detailed analysis of the light intensity dependence of the quantum yield of triplet excitons under high-density conditions, triplet excitons were mainly generated through fission from highly excited singlet states populated by singlet-singlet exciton annihilation. We estimated that 30% of the highly excited states underwent fission.

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.

Exciton enhancement and exciplex quenching by plasmonic effect of Aluminum nanoparticle arrays in a blue organic light emitting diode.

PubMed

Khadir, Samira; Diallo, AmadouThierno; Chakaroun, Mahmoud; Boudrioua, Azzedine

2017-05-01

We report the investigation of plasmonic effect of array of aluminum nanoparticles (Al-NPs) on blue micro-OLED subject to exciplex emission. N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB) andcarbazol derivative 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) have been used as the emitting layer (EML) and hole transport layer (HTL), respectively. For the reference µ-OLED without Al-NPs, we observed two emission peaks attributed to CBP emission and exciplex emission formed at the NPB/CBP (EML/HTL) interface. By the incorporation of the Al-NPs array, obtained by e-beam lithography technique on the ITO anode, the exciplex emission has been widely depressed. Moreover, thanks to localized surface plasmon resonance (LSPR), an enhancement of the CBP emission has been achieved indicating an efficient energy coupling between the LSPR of the Al-NPs and the CBP excitons. Thus, an enhancement of about 20% of the efficiency of the µ-OLED with Al-NPs in comparison to the reference device has been obtained.

Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites.

PubMed

Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

2018-02-01

The performance of lead-halide perovskites in optoelectronic devices is due to a unique combination of factors, including highly efficient generation, transport, and collection of photogenerated charge carriers. The mechanism behind efficient charge generation in lead-halide perovskites is still largely unknown. Here, we investigate the factors that influence the exciton binding energy (E b ) in a series of metal-halide perovskites using accurate first-principles calculations based on solution of the Bethe-Salpeter equation, coupled to ab initio molecular dynamics simulations. We find that E b is strongly modulated by screening from low-energy phonons, which account for a factor ∼2 E b reduction, while dynamic disorder and rotational motion of the organic cations play a minor role. We calculate E b = 15 meV for MAPbI 3 , in excellent agreement with recent experimental estimates. We then explore how different material combinations (e.g., replacing Pb → Pb:Sn→ Sn; and MA → FA → Cs) may lead to different E b values and highlight the mechanisms underlying E b tuning.

Ultrafast carrier dynamics and optical pumping of lasing from Ar-plasma treated ZnO nanoribbons

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

Sarkar, Ketaki; Mukherjee, Souvik; Wiederrecht, Gary

We report that it is a well-known fact that ZnO has been one of the most studied wide bandgap II-VI materials by the scientific community specifically due to its potential for being used as exciton-related optical devices. Hence, realizing ways to increase the efficiency of these devices is important. We discuss a plasma treatment technique to enhance the near-band-edge (NBE) excitonic emission from ZnO based nanoribbons. We observed an enhancement of the NBE peak and simultaneous quenching of the visible emission peak resulting from the removal of surface traps on these ZnO nanoribbons. More importantly, we report here the associatedmore » ultrafast carrier dynamics resulting from this surface treatment. Femtosecond transient absorption spectroscopy was performed using pump-probe differential transmission measurements shedding new light on these improved dynamics with faster relaxation times. The knowledge obtained is important for improving the application of ZnO based optoelectronic devices. Finally, we also observed how these improved carrier dynamics have a direct effect on the threshold and efficiency of random lasing from the material.« less

Ultrafast carrier dynamics and optical pumping of lasing from Ar-plasma treated ZnO nanoribbons

DOE PAGES

Sarkar, Ketaki; Mukherjee, Souvik; Wiederrecht, Gary; ...

2018-01-04

We report that it is a well-known fact that ZnO has been one of the most studied wide bandgap II-VI materials by the scientific community specifically due to its potential for being used as exciton-related optical devices. Hence, realizing ways to increase the efficiency of these devices is important. We discuss a plasma treatment technique to enhance the near-band-edge (NBE) excitonic emission from ZnO based nanoribbons. We observed an enhancement of the NBE peak and simultaneous quenching of the visible emission peak resulting from the removal of surface traps on these ZnO nanoribbons. More importantly, we report here the associatedmore » ultrafast carrier dynamics resulting from this surface treatment. Femtosecond transient absorption spectroscopy was performed using pump-probe differential transmission measurements shedding new light on these improved dynamics with faster relaxation times. The knowledge obtained is important for improving the application of ZnO based optoelectronic devices. Finally, we also observed how these improved carrier dynamics have a direct effect on the threshold and efficiency of random lasing from the material.« less

Tuning Singlet Fission in π-Bridge-π Chromophores

DOE PAGES

Kumarasamy, Elango; Sanders, Samuel N.; Tayebjee, Murad J. Y.; ...

2017-08-11

For this study, we have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constantsmore » for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet–triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.« less

Quantum dots as optical labels for ultrasensitive detection of polyphenols.

PubMed

Akshath, Uchangi Satyaprasad; Shubha, Likitha R; Bhatt, Praveena; Thakur, Munna Singh

2014-07-15

Considering the fact that polyphenols have versatile activity in-vivo, its detection and quantification is very much important for a healthy diet. Laccase enzyme can convert polyphenols to yield mono/polyquinones which can quench Quantum dots fluorescence. This phenomenon of charge transfer from quinones to QDs was exploited as optical labels to detect polyphenols. CdTe QD may undergo dipolar interaction with quinones as a result of broad spectral absorption due to multiple excitonic states resulting from quantum confinement effects. Thus, "turn-off" fluorescence method was applied for ultrasensitive detection of polyphenols by using laccase. We observed proportionate quenching of QDs fluorescence with respect to polyphenol concentration in the range of 100 µg to 1 ng/mL. Also, quenching of the photoluminescence was highly efficient and stable and could detect individual and total polyphenols with high sensitivity (LOD-1 ng/mL). Moreover, proposed method was highly efficient than any other reported methods in terms of sensitivity, specificity and selectivity. Therefore, a novel optical sensor was developed for the detection of polyphenols at a sensitive level based on the charge transfer mechanism. Copyright © 2014 Elsevier B.V. All rights reserved.

Theory for electric dipole superconductivity with an application for bilayer excitons.

PubMed

Jiang, Qing-Dong; Bao, Zhi-qiang; Sun, Qing-Feng; Xie, X C

2015-07-08

Exciton superfluid is a macroscopic quantum phenomenon in which large quantities of excitons undergo the Bose-Einstein condensation. Recently, exciton superfluid has been widely studied in various bilayer systems. However, experimental measurements only provide indirect evidence for the existence of exciton superfluid. In this article, by viewing the exciton in a bilayer system as an electric dipole, we derive the London-type and Ginzburg-Landau-type equations for the electric dipole superconductors. By using these equations, we discover the Meissner-type effect and the electric dipole current Josephson effect. These effects can provide direct evidence for the formation of the exciton superfluid state in bilayer systems and pave new ways to drive an electric dipole current.

Observation of interlayer excitons in MoSe2 single crystals

NASA Astrophysics Data System (ADS)

Horng, Jason; Stroucken, Tineke; Zhang, Long; Paik, Eunice Y.; Deng, Hui; Koch, Stephan W.

2018-06-01

Interlayer excitons with direct optical transitions are observed coexisting with intralayer excitons in the same K valleys in bilayer, few-layer, and bulk MoSe2 single crystals by confocal reflection contrast spectroscopy. Quantitative analysis using the Dirac-Bloch equations provides unambiguous state assignment of all the measured resonances. The interlayer excitons in bilayer MoSe2 have a large binding energy of 153 meV and a narrow linewidth of 20 meV. Their spectral weight is comparable to the commonly studied higher-order intralayer excitons. At the same time, the interlayer excitons are characterized by distinct transition energies and permanent dipole moments, providing a promising high temperature and optically accessible platform for dipolar exciton physics.