Magnetic brightening and control of dark excitons in monolayer WSe2.

PubMed

Zhang, Xiao-Xiao; Cao, Ting; Lu, Zhengguang; Lin, Yu-Chuan; Zhang, Fan; Wang, Ying; Li, Zhiqiang; Hone, James C; Robinson, Joshua A; Smirnov, Dmitry; Louie, Steven G; Heinz, Tony F

2017-09-01

Monolayer transition metal dichalcogenide crystals, as direct-gap materials with strong light-matter interactions, have attracted much recent attention. Because of their spin-polarized valence bands and a predicted spin splitting at the conduction band edges, the lowest-lying excitons in WX 2 (X = S, Se) are expected to be spin-forbidden and optically dark. To date, however, there has been no direct experimental probe of these dark excitons. Here, we show how an in-plane magnetic field can brighten the dark excitons in monolayer WSe 2 and permit their properties to be observed experimentally. Precise energy levels for both the neutral and charged dark excitons are obtained and compared with ab initio calculations using the GW-BSE approach. As a result of their spin configuration, the brightened dark excitons exhibit much-increased emission and valley lifetimes. These studies directly probe the excitonic spin manifold and reveal the fine spin-splitting at the conduction band edges.

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.

Direct Imaging of Long-Range Exciton Transport in Quantum Dot Superlattices by Ultrafast Microscopy.

PubMed

Yoon, Seog Joon; Guo, Zhi; Dos Santos Claro, Paula C; Shevchenko, Elena V; Huang, Libai

2016-07-26

Long-range charge and exciton transport in quantum dot (QD) solids is a crucial challenge in utilizing QDs for optoelectronic applications. Here, we present a direct visualization of exciton diffusion in highly ordered CdSe QDs superlattices by mapping exciton population using ultrafast transient absorption microscopy. A temporal resolution of ∼200 fs and a spatial precision of ∼50 nm of this technique provide a direct assessment of the upper limit for exciton transport in QD solids. An exciton diffusion length of ∼125 nm has been visualized in the 3 ns experimental time window and an exciton diffusion coefficient of (2.5 ± 0.2) × 10(-2) cm(2) s(-1) has been measured for superlattices constructed from 3.6 nm CdSe QDs with center-to-center distance of 6.7 nm. The measured exciton diffusion constant is in good agreement with Förster resonance energy transfer theory. We have found that exciton diffusion is greatly enhanced in the superlattices over the disordered films with an order of magnitude higher diffusion coefficient, pointing toward the role of disorder in limiting transport. This study provides important understandings on energy transport mechanisms in both the spatial and temporal domains in QD solids.

Topological Exciton Bands in Moire Heterojunctions.

DOE PAGES

Wu, Fengcheng; Lovorn, Timothy; MacDonald, A. H.

2017-04-05

Moire patterns are common in Van der Waals heterostructures and can be used to apply periodic potentials to elementary excitations. Here, we show that the optical absorption spectrum of transition metal dichalcogenide bilayers is profoundly altered by long period moire patterns that introduce twist-angle dependent satellite excitonic peaks. Topological exciton bands with non-zero Chern numbers that support chiral excitonic edge states can be engineered by combining three ingredients: i) the valley Berry phase induced by electron-hole exchange interactions, ii) the moire potential, and iii) the valley Zeeman field.

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.

Direct Evidence of Exciton-Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies.

PubMed

Ma, Ying-Zhong; Lin, Haoran; Du, Mao-Hua; Doughty, Benjamin; Ma, Biwu

2018-05-03

Excitons in low-dimensional organic-inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton-phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C 6 H 13 N 4 ) 3 Pb 2 Br 7 . Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton-exciton annihilation process, a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. We further identify a fast and dominant PL decay component with a lifetime of ∼2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.

Bose-Einstein condensation and superfluidity of dipolar excitons in a phosphorene double layer

NASA Astrophysics Data System (ADS)

Berman, Oleg L.; Gumbs, Godfrey; Kezerashvili, Roman Ya.

2017-07-01

We study the formation of dipolar excitons and their superfluidity in a phosphorene double layer. The analytical expressions for the single dipolar exciton energy spectrum and wave function are obtained. It is predicted that a weakly interacting gas of dipolar excitons in a double layer of black phosphorus exhibits superfluidity due to the dipole-dipole repulsion between the dipolar excitons. In calculations are employed the Keldysh and Coulomb potentials for the interaction between the charge carriers to analyze the influence of the screening effects on the studied phenomena. It is shown that the critical velocity of superfluidity, the spectrum of collective excitations, concentrations of the superfluid and normal component, and mean-field critical temperature for superfluidity are anisotropic and demonstrate the dependence on the direction of motion of dipolar excitons. The critical temperature for superfluidity increases if the exciton concentration and the interlayer separation increase. It is shown that the dipolar exciton binding energy and mean-field critical temperature for superfluidity are sensitive to the electron and hole effective masses. The proposed experiment to observe a directional superfluidity of excitons is addressed.

Direct determination of exciton wavefunction amplitudes by the momentum-resolved photo-electron emission experiment

NASA Astrophysics Data System (ADS)

Ohnishi, Hiromasa; Tomita, Norikazu; Nasu, Keiichiro

2018-03-01

We study conceptional problems of a photo-electron emission (PEE) process from a free exciton in insulating crystals. In this PEE process, only the electron constituting the exciton is suddenly emitted out of the crystal, while the hole constituting the exciton is still left inside and forced to be recoiled back to its original valence band. This recoil on the hole is surely reflected in the spectrum of the PEE with a statistical distribution along the momentum-energy curve of the valence band. This distribution is nothing but the square of the exciton wavefunction amplitude, since it shows how the electron and the hole are originally bound together. Thus, the momentum-resolved PEE can directly determine the exciton wavefunction. These problems are clarified, taking the Γ and the saddle point excitons in GaAs, as typical examples. New PEE experiments are also suggested.

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

Magnetic brightening and control of dark excitons in monolayer WSe 2

DOE PAGES

Zhang, Xiao -Xiao; Cao, Ting; Lu, Zhengguang; ...

2017-06-26

Monolayer transition metal dichalcogenide crystals, as direct-gap materials with strong light–matter interactions, have attracted much recent attention. Because of their spin-polarized valence bands and a predicted spin splitting at the conduction band edges, the lowest-lying excitons in WX 2 (X = S, Se) are expected to be spin-forbidden and optically dark. To date, however, there has been no direct experimental probe of these dark excitons. Here, we show how an in-plane magnetic field can brighten the dark excitons in monolayer WSe2 and permit their properties to be observed experimentally. Precise energy levels for both the neutral and charged dark excitonsmore » are obtained and compared with ab initio calculations using the GW-BSE approach. As a result of their spin configuration, the brightened dark excitons exhibit much-increased emission and valley lifetimes. Furthermore, these studies directly probe the excitonic spin manifold and reveal the fine spin-splitting at the conduction band edges.« less

Optical spectroscopy of excited exciton states in MoS2 monolayers in van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Robert, C.; Semina, M. A.; Cadiz, F.; Manca, M.; Courtade, E.; Taniguchi, T.; Watanabe, K.; Cai, H.; Tongay, S.; Lassagne, B.; Renucci, P.; Amand, T.; Marie, X.; Glazov, M. M.; Urbaszek, B.

2018-01-01

The optical properties of MoS2 monolayers are dominated by excitons, but for spectrally broad optical transitions in monolayers exfoliated directly onto SiO2 substrates detailed information on excited exciton states is inaccessible. Encapsulation in hexagonal boron nitride (hBN) allows approaching the homogenous exciton linewidth, but interferences in the van der Waals heterostructures make direct comparison between transitions in optical spectra with different oscillator strength more challenging. Here we reveal in reflectivity and in photoluminescence excitation spectroscopy the presence of excited states of the A exciton in MoS2 monolayers encapsulated in hBN layers of calibrated thickness, allowing us to extrapolate an exciton binding energy of ≈220 meV. We theoretically reproduce the energy separations and oscillator strengths measured in reflectivity by combining the exciton resonances calculated for a screened two-dimensional Coulomb potential with transfer matrix calculations of the reflectivity for the van der Waals structure. Our analysis shows a very different evolution of the exciton oscillator strength with principal quantum number for the screened Coulomb potential as compared to the ideal two-dimensional hydrogen model.

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

Abdel-Baki, K.; Boitier, F.; Diab, H.

Due to their high potentiality for photovoltaic applications or coherent light sources, a renewed interest in hybrid organic perovskites has emerged for few years. When they are arranged in two dimensions, these materials can be considered as hybrid quantum wells. One consequence of the unique structure of 2D hybrid organic perovskites is a huge exciton binding energy that can be tailored through chemical engineering. We present experimental investigations of the exciton non-linearities by means of femtosecond pump-probe spectroscopy. The exciton dynamics is fitted with a bi-exponential decay with a free exciton life-time of ∼100 ps. Moreover, an ultrafast intraband relaxation (<150 fs)more » is also reported. Finally, the transient modification of the excitonic line is analyzed through the moment analysis and described in terms of reduction of the oscillator strength and linewidth broadening. We show that excitonic non-linearities in 2D hybrid organic perovskites share some behaviours of inorganic semiconductors despite their high exciton binding energy.« less

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

Dynamics of charge-transfer excitons in type-II semiconductor heterostructures

NASA Astrophysics Data System (ADS)

Stein, M.; Lammers, C.; Richter, P.-H.; Fuchs, C.; Stolz, W.; Koch, M.; Vänskä, O.; Weseloh, M. J.; Kira, M.; Koch, S. W.

2018-03-01

The formation, decay, and coherence properties of charge-transfer excitons in semiconductor heterostructures are investigated by applying four-wave-mixing and terahertz spectroscopy in combination with a predictive microscopic theory. A charge-transfer process is identified where the optically induced coherences decay directly into a charge-transfer electron-hole plasma and exciton states. It is shown that charge-transfer excitons are more sensitive to the fermionic electron-hole substructure than regular excitons.

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.

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 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.

Large Excitonic Reflectivity of Monolayer MoSe2 Encapsulated in Hexagonal Boron Nitride

NASA Astrophysics Data System (ADS)

Scuri, Giovanni; Zhou, You; High, Alexander A.; Wild, Dominik S.; Shu, Chi; De Greve, Kristiaan; Jauregui, Luis A.; Taniguchi, Takashi; Watanabe, Kenji; Kim, Philip; Lukin, Mikhail D.; Park, Hongkun

2018-01-01

We demonstrate that a single layer of MoSe2 encapsulated by hexagonal boron nitride can act as an electrically switchable mirror at cryogenic temperatures, reflecting up to 85% of incident light at the excitonic resonance. This high reflectance is a direct consequence of the excellent coherence properties of excitons in this atomically thin semiconductor. We show that the MoSe2 monolayer exhibits power-and wavelength-dependent nonlinearities that stem from exciton-based lattice heating in the case of continuous-wave excitation and exciton-exciton interactions when fast, pulsed laser excitation is used.

DNA-bridged Chiroplasmonic Assemblies of Nanoparticles

NASA Astrophysics Data System (ADS)

Kotov, Nicholas

2015-03-01

Chirality at nanoscale attracts a lot of attention during the last decade. A number of chiral nanoscale systems had been discovered ranging from individual nanoparticles to helical nanowires and from lithographically defined substrates. DNA bridges make possible in-silico engineering and practical construction of complex assemblies of nanoparticles with of both plasmonic and excitonic nature. In this presentation, expected and unexpected optical effects that we observed in chiral plasmonic and excitonic systems will be demonstrated. Special effort will be placed on the transitioning of theoretical and experimental knowledge about chiral nanoscale systems to applications. The most obvious direction for practical targets was so far, the design of metamaterials for negative refractive index optics. The results describing the 3D materials with the highest experimentally observed chiral anisotropy factor will be presented. It will be followed by the discussion of the recent developments in analytical application of chiral assemblies for detection of cancer and bacterial contamination.

Graphene quantum dot (GQD)-induced photovoltaic and photoelectric memory elements in a pentacene/GQD field effect transistor as a probe of functional interface

NASA Astrophysics Data System (ADS)

Kim, Youngjun; Cho, Seongeun; Kim, Hyeran; Seo, Soonjoo; Lee, Hyun Uk; Lee, Jouhahn; Ko, Hyungduk; Chang, Mincheol; Park, Byoungnam

2017-09-01

Electric field-induced charge trapping and exciton dissociation were demonstrated at a penatcene/grapheme quantum dot (GQD) interface using a bottom contact bi-layer field effect transistor (FET) as an electrical nano-probe. Large threshold voltage shift in a pentacene/GQD FET in the dark arises from field-induced carrier trapping in the GQD layer or GQD-induced trap states at the pentacene/GQD interface. As the gate electric field increases, hysteresis characterized by the threshold voltage shift depending on the direction of the gate voltage scan becomes stronger due to carrier trapping associated with the presence of a GQD layer. Upon illumination, exciton dissociation and gate electric field-induced charge trapping simultaneously contribute to increase the threshold voltage window, which can potentially be exploited for photoelectric memory and/or photovoltaic devices through interface engineering.

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.

Pressure-Dependent Light Emission of Charged and Neutral Excitons in Monolayer MoSe 2

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

Fu, Xinpeng; Li, Fangfei; Lin, Jung-Fu

Tailoring the excitonic properties in two-dimensional monolayer transition metal dichalcogenides (TMDs) through strain engineering is an effective means to explore their potential applications in optoelectronics and nanoelectronics. Here we report pressure-tuned photon emission of trions and excitons in monolayer MoSe2 via a diamond anvil cell (DAC) through photoluminescence measurements and theoretical calculations. Under quasi-hydrostatic compressive strain, our results show neutral (X0) and charged (X–) exciton emission of monolayer MoSe2 can be effectively tuned by alcohol mixture vs inert argon pressure transmitting media (PTM). During this process, X– emission undergoes a continuous blue shift until reaching saturation, while X0 emission turnsmore » up splitting. The pressure-dependent charging effect observed in alcohol mixture PTM results in the increase of the X– exciton component and facilitates the pressure-tuned emission of X– excitons. This substantial tunability of X– and X0 excitons in MoSe2 can be extended to other 2D TMDs, which holds potential for developing strained and optical sensing devices.« less

Relative ordering between bright and dark excitons in single-walled carbon nanotubes.

PubMed

Zhou, Weihang; Nakamura, Daisuke; Liu, Huaping; Kataura, Hiromichi; Takeyama, Shojiro

2014-11-11

The ordering and relative energy splitting between bright and dark excitons are critical to the optical properties of single-walled carbon nanotubes (SWNTs), as they eventually determine the radiative and non-radiative recombination processes of generated carriers. In this work, we report systematic high-field magneto-optical study on the relative ordering between bright and dark excitons in SWNTs. We identified the relative energy position of the dark exciton unambiguously by brightening it in ultra-high magnetic field. The bright-dark excitonic ordering was found to depend not only on the tube structure, but also on the type of transitions. For the 1(st) sub-band transition, the bright exciton appears to be higher in energy than its dark counterpart for any chiral species and is robust against environmental effect. While for the 2(nd) sub-band, their relative ordering was found to be chirality-sensitive: the bright exciton can be either higher or lower than the dark one, depending on the specific nanotube structures. These findings provide new clues for engineering the optical and electronic properties of SWNTs.

Unusual exciton–phonon interactions at van der Waals engineered interfaces

DOE PAGES

Chow, Colin M.; Yu, Hongyi; Jones, Aaron M.; ...

2017-01-13

Raman scattering is a ubiquitous phenomenon in light–matter interactions, which reveals a material’s electronic, structural, and thermal properties. Controlling this process would enable new ways of studying and manipulating fundamental material properties. Here, we report a novel Raman scattering process at the interface between different van der Waals (vdW) materials as well as between a monolayer semiconductor and 3D crystalline substrates. We find that interfacing a WSe 2 monolayer with materials such as SiO 2, sapphire, and hexagonal boron nitride (hBN) enables Raman transitions with phonons that are either traditionally inactive or weak. This Raman scattering can be amplified bymore » nearly 2 orders of magnitude when a foreign phonon mode is resonantly coupled to the A exciton in WSe 2 directly or via an A 1' optical phonon from WSe 2. We further showed that the interfacial Raman scattering is distinct between hBN-encapsulated and hBN-sandwiched WSe 2 sample geometries. Finally, this cross-platform electron–phonon coupling, as well as the sensitivity of 2D excitons to their phononic environments, will prove important in the understanding and engineering of optoelectronic devices based on vdW heterostructures.« less

Unusual exciton–phonon interactions at van der Waals engineered interfaces

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

Chow, Colin M.; Yu, Hongyi; Jones, Aaron M.

Raman scattering is a ubiquitous phenomenon in light–matter interactions, which reveals a material’s electronic, structural, and thermal properties. Controlling this process would enable new ways of studying and manipulating fundamental material properties. Here, we report a novel Raman scattering process at the interface between different van der Waals (vdW) materials as well as between a monolayer semiconductor and 3D crystalline substrates. We find that interfacing a WSe 2 monolayer with materials such as SiO 2, sapphire, and hexagonal boron nitride (hBN) enables Raman transitions with phonons that are either traditionally inactive or weak. This Raman scattering can be amplified bymore » nearly 2 orders of magnitude when a foreign phonon mode is resonantly coupled to the A exciton in WSe 2 directly or via an A 1' optical phonon from WSe 2. We further showed that the interfacial Raman scattering is distinct between hBN-encapsulated and hBN-sandwiched WSe 2 sample geometries. Finally, this cross-platform electron–phonon coupling, as well as the sensitivity of 2D excitons to their phononic environments, will prove important in the understanding and engineering of optoelectronic devices based on vdW heterostructures.« less

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

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.

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.

Theory for electric dipole superconductivity with an application for bilayer excitons

PubMed Central

Jiang, Qing-Dong; Bao, Zhi-qiang; Sun, Qing-Feng; Xie, X. C.

2015-01-01

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. PMID:26154838

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.

Competing role of Interactions in Synchronization of Exciton-Polariton condensates

NASA Astrophysics Data System (ADS)

Khan, Saeed; Tureci, Hakan E.

We present a theoretical study of synchronization dynamics in incoherently pumped exciton-polariton condensates in coupled traps. Our analysis is based on an expansion in non-Hermitian modes that take into account the trapping potential and the pump-induced complex-valued potential. We find that polariton-polariton and reservoir-polariton interactions play competing roles in the emergence of a synchronized phase as pumping power is increased, leading to qualitatively different synchronized phases. Crucially, these interactions can also act against each other to hinder synchronization. We present a phase diagram and explain the general characteristics of these phases using a generalized Adler equation. Our work sheds light on dynamics strongly influenced by competing interactions particular to incoherently pumped exciton-polariton condensates, which can lead to interesting features in recently engineered polariton lattices. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering.

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.

Photoinduced Bandgap Renormalization and Exciton Binding Energy Reduction in WS2.

PubMed

Cunningham, Paul D; Hanbicki, Aubrey T; McCreary, Kathleen M; Jonker, Berend T

2017-12-26

Strong Coulomb attraction in monolayer transition metal dichalcogenides gives rise to tightly bound excitons and many-body interactions that dominate their optoelectronic properties. However, this Coulomb interaction can be screened through control of the surrounding dielectric environment as well as through applied voltage, which provides a potential means of tuning the bandgap, exciton binding energy, and emission wavelength. Here, we directly show that the bandgap and exciton binding energy can be optically tuned by means of the intensity of the incident light. Using transient absorption spectroscopy, we identify a sub-picosecond decay component in the excited-state dynamics of WS 2 that emerges for incident photon energies above the A-exciton resonance, which originates from a nonequilibrium population of charge carriers that form excitons as they cool. The generation of this charge-carrier population exhibits two distinct energy thresholds. The higher threshold is coincident with the onset of continuum states and therefore provides a direct optical means of determining both the bandgap and exciton binding energy. Using this technique, we observe a reduction in the exciton binding energy from 310 ± 30 to 220 ± 20 meV as the excitation density is increased from 3 × 10 11 to 1.2 × 10 12 photons/cm 2 . This reduction is due to dynamic dipolar screening of Coulomb interactions by excitons, which is the underlying physical process that initiates bandgap renormalization and leads to the insulator-metal transition in monolayer transition metal dichalcogenides.

Excitonic linewidth and coherence lifetime in monolayer transition metal dichalcogenides

DOE PAGES

Selig, Malte; Berghäuser, Gunnar; Raja, Archana; ...

2016-11-07

Atomically thin transition metal dichalcogenides are direct-gap semiconductors with strong light–matter and Coulomb interactions. The latter accounts for tightly bound excitons, which dominate their optical properties. Besides the optically accessible bright excitons, these systems exhibit a variety of dark excitonic states. They are not visible in the optical spectra, but can strongly influence the coherence lifetime and the linewidth of the emission from bright exciton states. We investigate the microscopic origin of the excitonic coherence lifetime in two representative materials (WS 2 and MoSe 2) through a study combining microscopic theory with spectroscopic measurements. We also show that the excitonicmore » coherence lifetime is determined by phonon-induced intravalley scattering and intervalley scattering into dark excitonic states. Particularly, we identify exciton relaxation processes involving phonon emission into lower-lying dark states that are operative at all temperatures, in WS 2.« less

Probing exciton density of states through phonon-assisted emission in GaN epilayers: A and B exciton contributions

NASA Astrophysics Data System (ADS)

Cavigli, Lucia; Gabrieli, Riccardo; Gurioli, Massimo; Bogani, Franco; Feltin, Eric; Carlin, Jean-François; Butté, Raphaël; Grandjean, Nicolas; Vinattieri, Anna

2010-09-01

A detailed experimental investigation of the phonon-assisted emission in a high-quality c -plane GaN epilayer is presented up to 200 K. By performing photoluminescence and reflectivity measurements, we find important etaloning effects in the phonon-replica spectra, which have to be corrected before addressing the lineshape analysis. Direct experimental evidence for free exciton thermalization is found for the whole temperature range investigated. A close comparison with existing models for phonon replicas originating from a thermalized free exciton distribution shows that the simplified and commonly adopted description of the exciton-phonon interaction with a single excitonic band leads to a large discrepancy with experimental data. Only the consideration of the complex nature of the excitonic band in GaN, including A and B exciton contributions, allows accounting for the temperature dependence of the peak energy, intensity, and lineshape of the phonon replicas.

States of direct and indirect excitons in strained zinc-blende GaN/InGaN asymmetric quantum wells

NASA Astrophysics Data System (ADS)

Rojas-Briseño, J. G.; Martínez-Orozco, J. C.; Mora-Ramos, M. E.

2017-12-01

The total and binding energies of excitons in step-like asymmetric quantum wells made of zincblende GaN/InxlGa(1-xl)N/InxrGa(1-xr)N/GaN are theoretically reported. It is discussed how the asymmetry in the carrier confinement leads to singular behaviors in the exciton binding energy, allowing to observe both direct and indirect exciton states in the heterostructure. The study is carried out with the use of the effective mass approximation. The effects of strain are taken into account and a comparison of the results obtained for both strained and unstrained situations is presented. Exciton energy shows a decreasing behavior when the size of the effective confinement region is augmented. The total exciton energy as well as the binding energy are reported as functions of the indium concentration and quantum well width. In addition, the results of the calculation of the photoluminescence peak are presented. For this latter quantity, our results for the limiting case of a single zinc-blende GaN/InGaN quantum well show very good agreement with published experimental ones.

Direct Evidence of Exciton–Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies

DOE PAGES

Ma, Ying -Zhong; Lin, Haoran; Du, Mao -Hua; ...

2018-04-11

Excitons in low-dimensional organic–inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton–phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton–exciton annihilation process,more » a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. As a result, we further identify a fast and dominant PL decay component with a lifetime of ~2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.« less

Direct Evidence of Exciton–Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies

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

Ma, Ying -Zhong; Lin, Haoran; Du, Mao -Hua

Excitons in low-dimensional organic–inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton–phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton–exciton annihilation process,more » a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. As a result, we further identify a fast and dominant PL decay component with a lifetime of ~2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.« less

Exciton confinement in strain-engineered metamorphic InAs/I nxG a1 -xAs quantum dots

NASA Astrophysics Data System (ADS)

Khattak, S. A.; Hayne, M.; Huang, J.; Vanacken, J.; Moshchalkov, V. V.; Seravalli, L.; Trevisi, G.; Frigeri, P.

2017-11-01

We report a comprehensive study of exciton confinement in self-assembled InAs quantum dots (QDs) in strain-engineered metamorphic I nxG a1 -xAs confining layers on GaAs using low-temperature magnetophotoluminescence. As the lattice mismatch (strain) between QDs and confining layers (CLs) increases from 4.8% to 5.7% the reduced mass of the exciton increases, but saturates at higher mismatches. At low QD-CL mismatch there is clear evidence of spillover of the exciton wave function due to small localization energies. This is suppressed as the In content x in the CLs decreases (mismatch and localization energy increasing). The combined effects of low effective mass and wave-function spillover at high x result in a diamagnetic shift coefficient that is an order of magnitude larger than for samples where In content in the barrier is low (mismatch is high and localization energy is large). Finally, an anomalously small measured Bohr radius in samples with the highest x is attributed to a combination of thermalization due to low localization energy, and its enhancement with magnetic field, a mechanism which results in small dots in the ensemble dominating the measured Bohr radius.

Interlayer excitons in MoSe2/WSe2 heterostructures from first principles

NASA Astrophysics Data System (ADS)

Gillen, Roland; Maultzsch, Janina

2018-04-01

Based on ab initio theoretical calculations of the optical spectra of vertical heterostructures of MoSe2 (or MoS2) and WSe2 sheets, we reveal two spin-orbit-split Rydberg series of excitonic states below the A excitons of MoSe2 and WSe2 with a significant binding energy on the order of 250 meV for the first excitons in the series. At the same time, we predict from accurate many-body G0W0 calculations that crystallographically aligned MoSe2/WSe2 heterostructures exhibit an indirect fundamental band gap. Due to the type-II nature of the MoSe2/WSe2 heterostructure, the indirect transition and the exciton Rydberg series corresponding to a direct transition exhibit a distinct interlayer nature with spatial charge separation of the coupled electrons and holes. Our calculations confirm the recent experimental observation of a doublet nature of the long-lived states in photoluminescence spectra of Mo X2/W Y2 heterostructures, and we attribute these two contributions to momentum-direct interlayer excitons at the K point of the hexagonal Brillouin zone and to momentum-indirect excitons at the indirect fundamental band gap. Our calculations further suggest a noticeable effect of stacking order on the electronic band gaps and on the peak energies of the interlayer excitons and their oscillation strengths.

Tailorable Exciton Transport in Doped Peptide–Amphiphile Assemblies

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

Solomon, Lee A.; Sykes, Matthew E.; Wu, Yimin A.

Light-harvesting biomaterials are an attractive target in photovoltaics, photocatalysis, and artificial photosynthesis. Through peptide self-assembly, complex nanostructures can be engineered to study the role of chromophore organization during light absorption and energy transport. To this end, we demonstrate the one-dimensional transport of excitons along naturally occurring, light-harvesting, Zn-protoporphyrin IX chromophores within self-assembled peptide-amphiphile nanofibers. The internal structure of the nanofibers induces packing of the porphyrins into linear chains. We find that this peptide assembly can enable long-range exciton diffusion, yet it also induces the formation of excimers between adjacent molecules, which serve as exciton traps. Electronic coupling between neighboring porphyrinmore » molecules is confirmed by various spectroscopic methods. The exciton diffusion process is then probed through transient photoluminescence and absorption measurements and fit to a model for one-dimensional hopping. Because excimer formation impedes exciton hopping, increasing the interchromophore spacing allows for improved diffusivity, which we control through porphyrin doping levels. We show that diffusion lengths of over 60 nm are possible at low porphyrin doping, representing an order of magnitude improvement over the highest doping fractions.« less

Exciton-Polariton Dynamics of a Monolayer Semiconductor Coupled to a Microcavity

NASA Astrophysics Data System (ADS)

Chen, Yen-Jung; Stanev, Teodor K.; Stern, Nathaniel P.; Cain, Jeffrey D.; Dravid, Vinayak P.

Strong light-matter interactions, evidenced by exciton-polariton states, have been observed in the two-dimensional limit with monolayer transition metal dichalcogenides (TMDs) embedded in a microcavity. Because of the valley degree of freedom in monolayer TMDs, these hybrid light-matter states can exhibit valley polarization as in a bare monolayer, with strongly-coupled dynamics determined by the relative rates of exciton relaxation and intervalley scattering, which can be highly modified in on-resonant cavities. Here, we test this intuitive picture of the polarized exciton-polariton dynamics with monolayer MoS2 coupled to detuned cavities. Upper and lower polariton branches exhibit distinct decay rates indicative of different cavity dynamics. As with on-resonant, strongly-coupled exciton-polaritons, the weakly-coupled regime causes exciton-polariton valley polarization to persist at room temperature, demonstrating that dynamics of valley-polarized excitations can be controlled by engineering light-matter interactions. This work is supported by the U.S. Department of Energy (BES DE-SC0012130) and the National Science Foundation MRSEC program (DMR-1121262). N.P.S. is an Alfred P. Sloan Research Fellow.

Tailorable Exciton Transport in Doped Peptide-Amphiphile Assemblies.

PubMed

Solomon, Lee A; Sykes, Matthew E; Wu, Yimin A; Schaller, Richard D; Wiederrecht, Gary P; Fry, H Christopher

2017-09-26

Light-harvesting biomaterials are an attractive target in photovoltaics, photocatalysis, and artificial photosynthesis. Through peptide self-assembly, complex nanostructures can be engineered to study the role of chromophore organization during light absorption and energy transport. To this end, we demonstrate the one-dimensional transport of excitons along naturally occurring, light-harvesting, Zn-protoporphyrin IX chromophores within self-assembled peptide-amphiphile nanofibers. The internal structure of the nanofibers induces packing of the porphyrins into linear chains. We find that this peptide assembly can enable long-range exciton diffusion, yet it also induces the formation of excimers between adjacent molecules, which serve as exciton traps. Electronic coupling between neighboring porphyrin molecules is confirmed by various spectroscopic methods. The exciton diffusion process is then probed through transient photoluminescence and absorption measurements and fit to a model for one-dimensional hopping. Because excimer formation impedes exciton hopping, increasing the interchromophore spacing allows for improved diffusivity, which we control through porphyrin doping levels. We show that diffusion lengths of over 60 nm are possible at low porphyrin doping, representing an order of magnitude improvement over the highest doping fractions.

Dynamics in terahertz semiconductor microcavity: quantum noise spectra

NASA Astrophysics Data System (ADS)

Jabri, H.; Eleuch, H.

2018-05-01

We investigate the physics of an optical semiconductor microcavity containing a coupled double quantum well interacting with cavity photons. The photon statistics of the transmitted light by the cavity is explored. We show that the nonlinear interactions in the direct and indirect excitonic modes generate an important squeezing despite the weak nonlinearities. When the strong coupling regime is achieved, the noise spectra of the system is dominated by the indirect exciton distribution. At the opposite, in the weak regime, direct excitons contribute much larger in the noise spectra.

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.

Spatially resolved and time-resolved imaging of transport of indirect excitons in high magnetic fields

NASA Astrophysics Data System (ADS)

Dorow, C. J.; Hasling, M. W.; Calman, E. V.; Butov, L. V.; Wilkes, J.; Campman, K. L.; Gossard, A. C.

2017-06-01

We present the direct measurements of magnetoexciton transport. Excitons give the opportunity to realize the high magnetic-field regime for composite bosons with magnetic fields of a few tesla. Long lifetimes of indirect excitons allow the study of kinetics of magnetoexciton transport with time-resolved optical imaging of exciton photoluminescence. We performed spatially, spectrally, and time-resolved optical imaging of transport of indirect excitons in high magnetic fields. We observed that an increasing magnetic field slows down magnetoexciton transport. The time-resolved measurements of the magnetoexciton transport distance allowed for an experimental estimation of the magnetoexciton diffusion coefficient. An enhancement of the exciton photoluminescence energy at the laser excitation spot was found to anticorrelate with the exciton transport distance. A theoretical model of indirect magnetoexciton transport is presented and is in agreement with the experimental data.

Magnetooptics of Exciton Rydberg States in a Monolayer Semiconductor

NASA Astrophysics Data System (ADS)

Stier, A. V.; Wilson, N. P.; Velizhanin, K. A.; Kono, J.; Xu, X.; Crooker, S. A.

2018-02-01

We report 65 T magnetoabsorption spectroscopy of exciton Rydberg states in the archetypal monolayer semiconductor WSe2 . The strongly field-dependent and distinct energy shifts of the 2 s , 3 s , and 4 s excited neutral excitons permits their unambiguous identification and allows for quantitative comparison with leading theoretical models. Both the sizes (via low-field diamagnetic shifts) and the energies of the n s exciton states agree remarkably well with detailed numerical simulations using the nonhydrogenic screened Keldysh potential for 2D semiconductors. Moreover, at the highest magnetic fields, the nearly linear diamagnetic shifts of the weakly bound 3 s and 4 s excitons provide a direct experimental measure of the exciton's reduced mass mr=0.20 ±0.01 m0.

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

Robust tunable excitonic features in monolayer transition metal dichalcogenide quantum dots

NASA Astrophysics Data System (ADS)

Fouladi-Oskouei, J.; Shojaei, S.; Liu, Z.

2018-04-01

The effects of quantum confinement on excitons in parabolic quantum dots of monolayer transition metal dichalcogenides (TMDC QDs) are investigated within a massive Dirac fermion model. A giant spin-valley coupling of the TMDC QDs is obtained, larger than that of monolayer TMDC sheets and consistent with recent experimental measurements. The exciton transition energy and the binding energy are calculated, and it is found that the strong quantum confinement results in extremely high exciton binding energies. The enormously large exciton binding energy in TMDC QDs (({{E}{{B2D}}}∼ 500 meV)<{{E}{{BQD}}}~≲ 1800 meV for different kinds of TMDC QDs) ensures that the many body interactions play a significant role in the investigation of the optical properties of these novel nanostructures. The estimated oscillator strength and radiative lifetime of excitons are strongly size-dependent and indicate a giant oscillator strength enhancement and ultrafast radiative annihilation of excitons, varying from a few tens of femtoseconds to a few picoseconds. We found that the spin-dependent band gap, spin-valley coupling, binding energy and excitonic effects can be tuned by quantum confinements, leading to tunable quantum dots in monolayer TMDCs. This finding offers new functionality in engineering the interaction of a 2D material with light and creates promise for the quantum manipulation of spin and valley degrees of freedom in TMDC nanostructures, enabling versatile novel 2D quantum photonic and optoelectronic nanodevices.

Surface photovoltage in exciton absorption range in CdS

NASA Technical Reports Server (NTRS)

Morawski, A.; Banisch, R.; Lagowski, J.

1977-01-01

The high resolution, intrinsic spectra of surface photovoltage are reported for semiconducting n-type CdS single crystals. At reduced temperatures (120-160 K) the spectra exhibit three sharp maxima due to A, B and C free exciton transitions. Energy positions of these lines and valence band parameters (spin-orbit and crystal field splittings) estimated from surface photovoltage are in good agreement with values obtained by other methods. The excitonic transitions are very sensitive to surface treatment, i.e. polishing, etching, background illumination and surface doping. The mechanism of direct interaction of free excitons with surface states is proposed to explain exciton lines in surface photovoltage.

Strain-Gradient Modulated Exciton Emission in Bent ZnO Wires Probed by Cathodoluminescence.

PubMed

Fu, Xue-Wen; Li, Cai-Zhen; Fang, Liang; Liu, Da-Meng; Xu, Jun; Yu, Da-Peng; Liao, Zhi-Min

2016-12-27

Photoelectrical properties of semiconductor nanostructures are expected to be improved significantly by strain engineering. Besides the local strain, the strain gradient is promising to tune the luminescence properties by modifying the crystal symmetry. Here, we report the investigation of strain-gradient induced symmetry-breaking effect on excitonic states in pure bending ZnO microwires by high spatial-resolved cathodoluminescence at low temperature of 80 K. In addition to the local-strain induced light emission peak shift, the bound exciton emission photon energy shows an extraordinary jump of ∼16.6 meV at a high strain-gradient of 1.22% μm -1 , which is ascribed to the strain gradient induced symmetry-breaking. Such a symmetry-breaking lifts the energy degeneracy of the electronic band structures, which significantly modifies the electron-hole interactions and the fine structures of the bound exciton states. These results provide a further understanding of the strain gradient effect on the excitonic states and possess a potential for the applications in optoelectronic devices.

Polarization of the photoluminescence of quantum dots incorporated into quantum wires

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

Platonov, A. V., E-mail: alexei.platonov@mail.ioffe.ru; Kochereshko, V. P.; Kats, V. N.

The photoluminescence spectra of individual quantum dots incorporated into a quantum wire are studied. From the behavior of the spectra in a magnetic field, it is possible to estimate the exciton binding energy in a quantum dot incorporated into a quantum wire. It is found that the exciton photoluminescence signal emitted from a quantum dot along the direction of the nanowire axis is linearly polarized. At the same time, the photoluminescence signal propagating in the direction orthogonal to the nanowire axis is practically unpolarized. The experimentally observed effect is attributed to the nonaxial arrangement of the dot in the wiremore » under conditions of a huge increase in the exciton binding energy due to the effect of the image potential on the exciton.« less

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.

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

Park, Jaehong; Reid, Obadiah G.; Blackburn, Jeffrey L.

The strong quantum confinement and low dielectric screening impart single-walled carbon nanotubes with exciton-binding energies substantially exceeding kBT at room temperature. Despite these large binding energies, reported photoluminescence quantum yields are typically low and some studies suggest that photoexcitation of carbon nanotube excitonic transitions can produce free charge carriers. Here we report the direct measurement of long-lived free-carrier generation in chirality-pure, single-walled carbon nanotubes in a low dielectric solvent. Time-resolved microwave conductivity enables contactless and quantitative measurement of the real and imaginary photoconductance of individually suspended nanotubes. We found that the conditions of the microwave conductivity measurement allow us tomore » avoid the complications of most previous measurements of nanotube free-carrier generation, including tube–tube/tube–electrode contact, dielectric screening by nearby excitons and many-body interactions. At low photon fluence (approximately 0.05 excitons per μm length of tubes), we directly observe free carriers on excitation of the first and second carbon nanotube exciton transitions.« less

Photoinduced Spontaneous Free-Carrier Generation in Semiconducting Single-Walled Carbon Nanotubes

DOE PAGES

Park, Jaehong; Reid, Obadiah G.; Blackburn, Jeffrey L.; ...

2015-11-04

The strong quantum confinement and low dielectric screening impart single-walled carbon nanotubes with exciton-binding energies substantially exceeding kBT at room temperature. Despite these large binding energies, reported photoluminescence quantum yields are typically low and some studies suggest that photoexcitation of carbon nanotube excitonic transitions can produce free charge carriers. Here we report the direct measurement of long-lived free-carrier generation in chirality-pure, single-walled carbon nanotubes in a low dielectric solvent. Time-resolved microwave conductivity enables contactless and quantitative measurement of the real and imaginary photoconductance of individually suspended nanotubes. We found that the conditions of the microwave conductivity measurement allow us tomore » avoid the complications of most previous measurements of nanotube free-carrier generation, including tube–tube/tube–electrode contact, dielectric screening by nearby excitons and many-body interactions. At low photon fluence (approximately 0.05 excitons per μm length of tubes), we directly observe free carriers on excitation of the first and second carbon nanotube exciton transitions.« less

Spontaneous and superfluid chiral edge states in exciton-polariton condensates

NASA Astrophysics Data System (ADS)

Sigurdsson, H.; Li, G.; Liew, T. C. H.

2017-09-01

We present a scheme of interaction-induced topological band structures based on the spin anisotropy of exciton-polaritons in semiconductor microcavities. We predict theoretically that this scheme allows the engineering of topological gaps, without requiring a magnetic field or strong spin-orbit interaction (transverse electric-transverse magnetic splitting). Under nonresonant pumping we find that an initially topologically trivial system undergoes a topological transition upon the spontaneous breaking of phase symmetry associated with polariton condensation. Under either nonresonant or resonant coherent pumping we find that it is also possible to engineer a topological dispersion that is linear in wave vector—a property associated with polariton superfluidity.

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.

Independent tuning of excitonic emission energy and decay time in single semiconductor quantum dots

NASA Astrophysics Data System (ADS)

Höfer, B.; Zhang, J.; Wildmann, J.; Zallo, E.; Trotta, R.; Ding, F.; Rastelli, A.; Schmidt, O. G.

2017-04-01

Independent tuning of emission energy and decay time of neutral excitons confined in single self-assembled In(Ga)As/GaAs quantum dots is achieved by simultaneously employing vertical electric fields and lateral biaxial strain fields. By locking the emission energy via a closed-loop feedback on the piezoelectric actuator used to control the strain in the quantum dot, we continuously decrease the decay time of an exciton from 1.4 to 0.7 ns. Both perturbations are fully electrically controlled and their combination offers a promising route to engineer the indistinguishability of photons emitted from spatially separated single photon sources.

Rapid calculation method for Frenkel-type two-exciton states in one to three dimensions

NASA Astrophysics Data System (ADS)

Ajiki, Hiroshi

2014-07-01

Biexciton and two-exciton dissociated states of Frenkel-type excitons are well described by a tight-binding model with a nearest-neighbor approximation. Such two-exciton states in a finite-size lattice are usually calculated by numerical diagonalization of the Hamiltonian, which requires an increasing amount of computational time and memory as the lattice size increases. I develop here a rapid, memory-saving method to calculate the energies and wave functions of two-exciton states by employing a bisection method. In addition, an attractive interaction between two excitons in the tight-binding model can be obtained directly so that the biexciton energy agrees with the observed energy, without the need for the trial-and-error procedure implemented in the numerical diagonalization method.

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 multiplication from first principles.

PubMed

Jaeger, Heather M; Hyeon-Deuk, Kim; Prezhdo, Oleg V

2013-06-18

Third-generation photovolatics require demanding cost and power conversion efficiency standards, which may be achieved through efficient exciton multiplication. Therefore, generating more than one electron-hole pair from the absorption of a single photon has vast ramifications on solar power conversion technology. Unlike their bulk counterparts, irradiated semiconductor quantum dots exhibit efficient exciton multiplication, due to confinement-enhanced Coulomb interactions and slower nonradiative losses. The exact characterization of the complicated photoexcited processes within quantum-dot photovoltaics is a work in progress. In this Account, we focus on the photophysics of nanocrystals and investigate three constituent processes of exciton multiplication, including photoexcitation, phonon-induced dephasing, and impact ionization. We quantify the role of each process in exciton multiplication through ab initio computation and analysis of many-electron wave functions. The probability of observing a multiple exciton in a photoexcited state is proportional to the magnitude of electron correlation, where correlated electrons can be simultaneously promoted across the band gap. Energies of multiple excitons are determined directly from the excited state wave functions, defining the threshold for multiple exciton generation. This threshold is strongly perturbed in the presence of surface defects, dopants, and ionization. Within a few femtoseconds following photoexcitation, the quantum state loses coherence through interactions with the vibrating atomic lattice. The phase relationship between single excitons and multiple excitons dissipates first, followed by multiple exciton fission. Single excitons are coupled to multiple excitons through Coulomb and electron-phonon interactions, and as a consequence, single excitons convert to multiple excitons and vice versa. Here, exciton multiplication depends on the initial energy and coupling magnitude and competes with electron-phonon energy relaxation. Multiple excitons are generated through impact ionization within picoseconds. The basis of exciton multiplication in quantum dots is the collective result of photoexcitation, dephasing, and nonadiabatic evolution. Each process is characterized by a distinct time-scale, and the overall multiple exciton generation dynamics is complete by about 10 ps. Without relying on semiempirical parameters, we computed quantum mechanical probabilities of multiple excitons for small model systems. Because exciton correlations and coherences are microscopic, quantum properties, results for small model systems can be extrapolated to larger, realistic quantum dots.

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.

Analytic derivative couplings and first-principles exciton/phonon coupling constants for an ab initio Frenkel-Davydov exciton model: Theory, implementation, and application to compute triplet exciton mobility parameters for crystalline tetracene.

PubMed

Morrison, Adrian F; Herbert, John M

2017-06-14

Recently, we introduced an ab initio version of the Frenkel-Davydov exciton model for computing excited-state properties of molecular crystals and aggregates. Within this model, supersystem excited states are approximated as linear combinations of excitations localized on molecular sites, and the electronic Hamiltonian is constructed and diagonalized in a direct-product basis of non-orthogonal configuration state functions computed for isolated fragments. Here, we derive and implement analytic derivative couplings for this model, including nuclear derivatives of the natural transition orbital and symmetric orthogonalization transformations that are part of the approximation. Nuclear derivatives of the exciton Hamiltonian's matrix elements, required in order to compute the nonadiabatic couplings, are equivalent to the "Holstein" and "Peierls" exciton/phonon couplings that are widely discussed in the context of model Hamiltonians for energy and charge transport in organic photovoltaics. As an example, we compute the couplings that modulate triplet exciton transport in crystalline tetracene, which is relevant in the context of carrier diffusion following singlet exciton fission.

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.

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.

Interwell exciton dispersion engineering, coherent phonons generation and optical detectionof exciton condensate

NASA Astrophysics Data System (ADS)

Hildebrandt, Stefan

2004-01-01

Conference Reports are meant to offer an authoritative view on a recently held scientific meeting rather than a comprehensive list of the conference presentations. Authors are invited to describe what they feel were the most interesting contributions.Changing the culture of science and publication was the tenor at the IUPAP Workshop on Scientific Misconduct and the Role of Physics Journals in its Investigation and Prevention, recently held in London.

Radiative decay rate of excitons in square quantum wells: Microscopic modeling and experiment

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

Khramtsov, E. S.; Grigoryev, P. S.; Ignatiev, I. V.

The binding energy and the corresponding wave function of excitons in GaAs-based finite square quantum wells (QWs) are calculated by the direct numerical solution of the three-dimensional Schrödinger equation. The precise results for the lowest exciton state are obtained by the Hamiltonian discretization using the high-order finite-difference scheme. The microscopic calculations are compared with the results obtained by the standard variational approach. The exciton binding energies found by two methods coincide within 0.1 meV for the wide range of QW widths. The radiative decay rate is calculated for QWs of various widths using the exciton wave functions obtained by direct andmore » variational methods. The radiative decay rates are confronted with the experimental data measured for high-quality GaAs/AlGaAs and InGaAs/GaAs QW heterostructures grown by molecular beam epitaxy. The calculated and measured values are in good agreement, though slight differences with earlier calculations of the radiative decay rate are observed.« less

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.

Diabatization for Time-Dependent Density Functional Theory: Exciton Transfers and Related Conical Intersections.

PubMed

Tamura, Hiroyuki

2016-11-23

Intermolecular exciton transfers and related conical intersections are analyzed by diabatization for time-dependent density functional theory. The diabatic states are expressed as a linear combination of the adiabatic states so as to emulate the well-defined reference states. The singlet exciton coupling calculated by the diabatization scheme includes contributions from the Coulomb (Förster) and electron exchange (Dexter) couplings. For triplet exciton transfers, the Dexter coupling, charge transfer integral, and diabatic potentials of stacked molecules are calculated for analyzing direct and superexchange pathways. We discuss some topologies of molecular aggregates that induce conical intersections on the vanishing points of the exciton coupling, namely boundary of H- and J-aggregates and T-shape aggregates, as well as canceled exciton coupling to the bright state of H-aggregate, i.e., selective exciton transfer to the dark state. The diabatization scheme automatically accounts for the Berry phase by fixing the signs of reference states while scanning the coordinates.

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

Synthetic Control of Exciton Behavior in Colloidal Quantum Dots.

PubMed

Pu, Chaodan; Qin, Haiyan; Gao, Yuan; Zhou, Jianhai; Wang, Peng; Peng, Xiaogang

2017-03-08

Colloidal quantum dots are promising optical and optoelectronic materials for various applications, whose performance is dominated by their excited-state properties. This article illustrates synthetic control of their excited states. Description of the excited states of quantum-dot emitters can be centered around exciton. We shall discuss that, different from conventional molecular emitters, ground-state structures of quantum dots are not necessarily correlated with their excited states. Synthetic control of exciton behavior heavily relies on convenient and affordable monitoring tools. For synthetic development of ideal optical and optoelectronic emitters, the key process is decay of band-edge excitons, which renders transient photoluminescence as important monitoring tool. On the basis of extensive synthetic developments in the past 20-30 years, synthetic control of exciton behavior implies surface engineering of quantum dots, including surface cation/anion stoichiometry, organic ligands, inorganic epitaxial shells, etc. For phosphors based on quantum dots doped with transition metal ions, concentration and location of the dopant ions within a nanocrystal lattice are found to be as important as control of the surface states in order to obtain bright dopant emission with monoexponential yet tunable photoluminescence decay dynamics.

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

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

Photonic Devices Based on Surface and Composition-Engineered Infrared Colloidal Nanocrystals

DTIC Science & Technology

2012-01-27

NQD/P3HT solar cells , the need for submicron-phase-separated polymer-NQD blends is therefore expressed by the limiting exciton diffusion length ...P3HT:PbSe are very critical in designing the PM-HJ solar cells : The thickness of P3HT should approximate to the thickness of exciton diffuse length in... cells , luminescent solar concentrators, light emitting diodes, lasers, photonic crystals, CdSe, PbSe, Germanium Jian Xu Pennsylvania State University

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.

Magnetic control of dipolaritons in quantum dots.

PubMed

Rojas-Arias, J S; Rodríguez, B A; Vinck-Posada, H

2016-12-21

Dipolaritons are quasiparticles that arise in coupled quantum wells embedded in a microcavity, they are a superposition of a photon, a direct exciton and an indirect exciton. We propose the existence of dipolaritons in a system of two coupled quantum dots inside a microcavity in direct analogy with the quantum well case and find that, despite some similarities, dipolaritons in quantum dots have different properties and can lead to true dark polariton states. We use a finite system theory to study the effects of the magnetic field on the system, including the emission, and find that it can be used as a control parameter of the properties of excitons and dipolaritons, and the overall magnetic behaviour of the structure.

Decay channels of Al L sub 2,3 excitons and the absence of O K excitons in. alpha. -Al sub 2 O sub 3

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

O'Brien, W.L.; Jia, J.; Dong, Q.

1991-12-15

The Al {ital L}{sub 2,3} and O {ital K} thresholds for single-crystal {alpha}-Al{sub 2}O{sub 3} have been studied by photoemission. Energy-distribution curves, constant-initial-state (CIS), and constant-final-state (CFS) spectra are reported and compared to the absorption spectrum reported previously. An exciton appears as a doublet at threshold in the Al {ital L}{sub 2,3} CFS, CIS, and absorption spectra. The details of the Al {ital L}{sub 2,3} CFS spectrum and absorption spectrum are similar, while the exciton is the only feature present in the CIS spectrum. Comparisons of the various Al {ital L}{sub 2,3} spectra allow the probabilities of different exciton decaymore » channels to be determined. The probability for nonradiative direct recombination of the exciton is found to be (8{plus minus}1)% and the probability for Auger decay of the exciton is found to be (72{plus minus}20)%. Comparisons of the O {ital K} CIS and CFS spectra suggest that no O {ital K} exciton is formed.« less

Coulomb engineering of the bandgap and excitons in two-dimensional materials

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

Raja, Archana; Chaves, Andrey; Yu, Jaeeun

Here, the ability to control the size of the electronic bandgap is an integral part of solid-state technology. Atomically thin two-dimensional crystals offer a new approach for tuning the energies of the electronic states based on the unusual strength of the Coulomb interaction in these materials and its environmental sensitivity. Here, we show that by engineering the surrounding dielectric environment, one can tune the electronic bandgap and the exciton binding energy in monolayers of WS 2 and WSe 2 by hundreds of meV. We exploit this behaviour to present an in-plane dielectric heterostructure with a spatially dependent bandgap, as anmore » initial step towards the creation of diverse lateral junctions with nanoscale resolution.« less

Coulomb engineering of the bandgap and excitons in two-dimensional materials

DOE PAGES

Raja, Archana; Chaves, Andrey; Yu, Jaeeun; ...

2017-05-04

Here, the ability to control the size of the electronic bandgap is an integral part of solid-state technology. Atomically thin two-dimensional crystals offer a new approach for tuning the energies of the electronic states based on the unusual strength of the Coulomb interaction in these materials and its environmental sensitivity. Here, we show that by engineering the surrounding dielectric environment, one can tune the electronic bandgap and the exciton binding energy in monolayers of WS 2 and WSe 2 by hundreds of meV. We exploit this behaviour to present an in-plane dielectric heterostructure with a spatially dependent bandgap, as anmore » initial step towards the creation of diverse lateral junctions with nanoscale resolution.« less

Coulomb engineering of the bandgap and excitons in two-dimensional materials

PubMed Central

Raja, Archana; Chaves, Andrey; Yu, Jaeeun; Arefe, Ghidewon; Hill, Heather M.; Rigosi, Albert F.; Berkelbach, Timothy C.; Nagler, Philipp; Schüller, Christian; Korn, Tobias; Nuckolls, Colin; Hone, James; Brus, Louis E.; Heinz, Tony F.; Reichman, David R.; Chernikov, Alexey

2017-01-01

The ability to control the size of the electronic bandgap is an integral part of solid-state technology. Atomically thin two-dimensional crystals offer a new approach for tuning the energies of the electronic states based on the unusual strength of the Coulomb interaction in these materials and its environmental sensitivity. Here, we show that by engineering the surrounding dielectric environment, one can tune the electronic bandgap and the exciton binding energy in monolayers of WS2 and WSe2 by hundreds of meV. We exploit this behaviour to present an in-plane dielectric heterostructure with a spatially dependent bandgap, as an initial step towards the creation of diverse lateral junctions with nanoscale resolution. PMID:28469178

Dispersion and decay rate of exciton-polaritons and radiative modes in transition metal dichalcogenide monolayers

NASA Astrophysics Data System (ADS)

Alpeggiani, Filippo; Gong, Su-Hyun; Kuipers, L.

2018-05-01

The two-dimensional excitons of transition metal dichalcogenide (TMDC) monolayers make these materials extremely promising for optical and optoelectronic applications. When the excitons interact with the electromagnetic field, they will give rise to exciton-polaritons, i.e., modes that propagate in the material plane while being confined in the out-of-plane direction. In this work, we derive the characteristic equations that determine both radiative and polaritonic modes in TMDC monolayers and we analyze the dispersion and decay rate of the modes. The condition for the existence of exciton-polaritons can be described in terms of a strong-coupling regime for the interaction between the exciton and the three-dimensional continuum of free-space electromagnetic modes. We show that the threshold for the strong-coupling regime critically depends on the interplay between nonradiative losses and the dielectric function imbalance at the two sides of the monolayer. Our results illustrate that a fine control of the dielectric function of the embedding media is essential for realizing exciton-polaritons in the strong-coupling regime.

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.

Quasiparticle Representation of Coherent Nonlinear Optical Signals of Multiexcitons

NASA Astrophysics Data System (ADS)

Fingerhut, Benjamin; Bennet, Kochise; Roslyak, Oleksiy; Mukamel, Shaul

2013-03-01

Elementary excitations of many-Fermion systems can be described within the quasiparticle approach which is widely used in the calculation of transport and optical properties of metals, semiconductors, molecular aggregates and strongly correlated quantum materials. The excitations are then viewed as independent harmonic oscillators where the many-body interactions between the oscillators are mapped into anharmonicities. We present a Green's function approach based on coboson algebra for calculating nonlinear optical signals and apply it onwards the study of two and three exciton states. The method only requires the diagonalization of the single exciton manifold and avoids equations of motion of multi-exciton manifolds. Using coboson algebra many body effects are recast in terms of tetradic exciton-exciton interactions: Coulomb scattering and Pauli exchange. The physical space of Fermions is recovered by singular-value decomposition of the over-complete coboson basis set. The approach is used to calculate third and fifth order quantum coherence optical signals that directly probe correlations in two- and three exciton states and their projections on the two and single exciton manifold.

Charge transfer excitons and image potential states on organic semiconductor surfaces

NASA Astrophysics Data System (ADS)

Yang, Qingxin; Muntwiler, Matthias; Zhu, X.-Y.

2009-09-01

We report two types of excited electronic states on organic semiconductor surfaces: image potential states (IPS) and charge transfer excitons (CTE). In the former, an excited electron is localized in the surface-normal direction by the image potential and delocalized in the surface plane. In the latter, the electron is localized in all directions by both the image potential and the Coulomb potential from a photogenerated hole on an organic molecule. We use crystalline pentacene and tetracene surfaces as model systems, and time- and angle-resolved two-photon photoemission spectroscopy to probe the energetics and dynamics of both the IPS and the CTE states. On either pentacene or tetracene surfaces, we observe delocalized image bands and a series of CT excitons with binding energies <0.5eV below the image-band minimum. The binding energies of these CT excitons agree well with solutions to the atomic-H-like Schrödinger equation based on the image potential and the electron-hole Coulomb potential. We hypothesize that the formation of CT excitons should be general to the surfaces of organic semiconductors where the relatively narrow valance-band width facilitates the localization of the hole and the low dielectric constant ensures strong electron-hole attraction.

Anisotropy-Induced Quantum Interference and Population Trapping between Orthogonal Quantum Dot Exciton States in Semiconductor Cavity Systems

NASA Astrophysics Data System (ADS)

Hughes, Stephen; Agarwal, Girish S.

2017-02-01

We describe how quantum dot semiconductor cavity systems can be engineered to realize anisotropy-induced dipole-dipole coupling between orthogonal dipole states in a single quantum dot. Quantum dots in single-mode cavity structures as well as photonic crystal waveguides coupled to spin states or linearly polarized excitons are considered. We demonstrate how the dipole-dipole coupling can control the radiative decay rate of excitons and form pure entangled states in the long time limit. We investigate both field-free entanglement evolution and coherently pumped exciton regimes, and show how a double-field pumping scenario can completely eliminate the decay of coherent Rabi oscillations and lead to population trapping. In the Mollow triplet regime, we explore the emitted spectra from the driven dipoles and show how a nonpumped dipole can take on the form of a spectral triplet, quintuplet, or a singlet, which has applications for producing subnatural linewidth single photons and more easily accessing regimes of high-field quantum optics and cavity-QED.

Anisotropy-Induced Quantum Interference and Population Trapping between Orthogonal Quantum Dot Exciton States in Semiconductor Cavity Systems.

PubMed

Hughes, Stephen; Agarwal, Girish S

2017-02-10

We describe how quantum dot semiconductor cavity systems can be engineered to realize anisotropy-induced dipole-dipole coupling between orthogonal dipole states in a single quantum dot. Quantum dots in single-mode cavity structures as well as photonic crystal waveguides coupled to spin states or linearly polarized excitons are considered. We demonstrate how the dipole-dipole coupling can control the radiative decay rate of excitons and form pure entangled states in the long time limit. We investigate both field-free entanglement evolution and coherently pumped exciton regimes, and show how a double-field pumping scenario can completely eliminate the decay of coherent Rabi oscillations and lead to population trapping. In the Mollow triplet regime, we explore the emitted spectra from the driven dipoles and show how a nonpumped dipole can take on the form of a spectral triplet, quintuplet, or a singlet, which has applications for producing subnatural linewidth single photons and more easily accessing regimes of high-field quantum optics and cavity-QED.

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

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.

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.

Investigation of indirect excitons in bulk 2H-MoS2 using transmission electron energy-loss spectroscopy

NASA Astrophysics Data System (ADS)

Habenicht, Carsten; Schuster, Roman; Knupfer, Martin; Büchner, Bernd

2018-05-01

We have investigated indirect excitons in bulk 2H-MoS2 using transmission electron energy-loss spectroscopy. The electron energy-loss spectra were measured for various momentum transfer values parallel to the and directions of the Brillouin zone. The results allowed the identification of the indirect excitons between the valence band K v and conduction band Λc points, the Γv and K c points as well as adjacent K v and points. The energy-momentum dispersions for the K v-Λc, Γv-K c and K v1- excitons along the line are presented. The former two transitions exhibit a quadratic dispersion which allowed calculating their effective exciton masses based on the effective mass approximation. The K v1- transition follows a more linear dispersion relationship.

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.

How exciton-vibrational coherences control charge separation in the photosystem II reaction center.

PubMed

Novoderezhkin, Vladimir I; Romero, Elisabet; van Grondelle, Rienk

2015-12-14

In photosynthesis absorbed sun light produces collective excitations (excitons) that form a coherent superposition of electronic and vibrational states of the individual pigments. Two-dimensional (2D) electronic spectroscopy allows a visualization of how these coherences are involved in the primary processes of energy and charge transfer. Based on quantitative modeling we identify the exciton-vibrational coherences observed in 2D photon echo of the photosystem II reaction center (PSII-RC). We find that the vibrations resonant with the exciton splittings can modify the delocalization of the exciton states and produce additional states, thus promoting directed energy transfer and allowing a switch between the two charge separation pathways. We conclude that the coincidence of the frequencies of the most intense vibrations with the splittings within the manifold of exciton and charge-transfer states in the PSII-RC is not occurring by chance, but reflects a fundamental principle of how energy conversion in photosynthesis was optimized.

Trion fine structure and coupled spin–valley dynamics in monolayer tungsten disulfide

PubMed Central

Plechinger, Gerd; Nagler, Philipp; Arora, Ashish; Schmidt, Robert; Chernikov, Alexey; del Águila, Andrés Granados; Christianen, Peter C.M.; Bratschitsch, Rudolf; Schüller, Christian; Korn, Tobias

2016-01-01

Monolayer transition-metal dichalcogenides have recently emerged as possible candidates for valleytronic applications, as the spin and valley pseudospin are directly coupled and stabilized by a large spin splitting. The optical properties of these two-dimensional crystals are dominated by tightly bound electron–hole pairs (excitons) and more complex quasiparticles such as charged excitons (trions). Here we investigate monolayer WS2 samples via photoluminescence and time-resolved Kerr rotation. In photoluminescence and in energy-dependent Kerr rotation measurements, we are able to resolve two different trion states, which we interpret as intravalley and intervalley trions. Using time-resolved Kerr rotation, we observe a rapid initial valley polarization decay for the A exciton and the trion states. Subsequently, we observe a crossover towards exciton–exciton interaction-related dynamics, consistent with the formation and decay of optically dark A excitons. By contrast, resonant excitation of the B exciton transition leads to a very slow decay of the Kerr signal. PMID:27586517

Novel exciton systems in 2D TMD monolayers and heterobilayers

NASA Astrophysics Data System (ADS)

Yu, Hongyi

In this talk, two exciton systems in transition metal dichalcogenides (TMDs) monolayer and heterobilayer will be discussed. In TMD monolayers, the strong e-h Coulomb exchange interaction splits the exciton and trion dispersions into two branches with zero and finite gap, respectively. Each branch is a center-of-mass wave vector dependent coherent superposition of the two valleys, which leads to a valley-orbit coupling and possibly a trion valley Hall effect. The exchange interaction also eliminates the linear polarization of the negative trion PL emission. In TMD heterobilayers with a type-II band alignment, the low energy exciton has an interlayer configuration with the e and h localized in opposite layers. Because of the inevitable twist or/and lattice mismatch between the two layers, the bright interlayer excitons are located at finite center-of-mass velocities with a six-fold degeneracy. The corresponding photon emission is elliptically polarized, with the major axis locked to the direction of exciton velocity, and helicity determined by the valley indices of the e and h. Some experimental results on the interlayer excitons in the WSe2-MoSe2 heterobilayers will also be presented. The interlayer exciton exhibits a long lifetime as well as a long depolarization time, which facilitate the observation of a PL polarization ring pattern due to the valley dependent exciton-exciton interaction induced expansion. The works were supported by the Research Grant Council of Hong Kong (HKU17305914P, HKU705513P), the Croucher Foundation, and the HKU OYRA and ROP.

Excitonic quantum interference in a quantum dot chain with rings.

PubMed

Hong, Suc-Kyoung; Nam, Seog Woo; Yeon, Kyu-Hwang

2008-04-16

We demonstrate excitonic quantum interference in a closely spaced quantum dot chain with nanorings. In the resonant dipole-dipole interaction model with direct diagonalization method, we have found a peculiar feature that the excitation of specified quantum dots in the chain is completely inhibited, depending on the orientational configuration of the transition dipole moments and specified initial preparation of the excitation. In practice, these excited states facilitating quantum interference can provide a conceptual basis for quantum interference devices of excitonic hopping.

Exciton properties in zincblende InGaN-GaN quantum wells under the effects of intense laser fields

PubMed Central

2012-01-01

In this work, we study the exciton states in a zincblende InGaN/GaN quantum well using a variational technique. The system is considered under the action of intense laser fields with the incorporation of a direct current electric field as an additional external probe. The effects of these external influences as well as of the changes in the geometry of the heterostructure on the exciton binding energy are discussed in detail. PMID:22937963

Exciton properties in zincblende InGaN-GaN quantum wells under the effects of intense laser fields.

PubMed

Duque, Carlos M; Mora-Ramos, Miguel E; Duque, Carlos A

2012-08-31

: In this work, we study the exciton states in a zincblende InGaN/GaN quantum well using a variational technique. The system is considered under the action of intense laser fields with the incorporation of a direct current electric field as an additional external probe. The effects of these external influences as well as of the changes in the geometry of the heterostructure on the exciton binding energy are discussed in detail.

Double-quantum resonances and exciton-scattering in coherent 2D spectroscopy of photosynthetic complexes

PubMed Central

Abramavicius, Darius; Voronine, Dmitri V.; Mukamel, Shaul

2008-01-01

A simulation study demonstrates how the nonlinear optical response of the Fenna–Matthews–Olson photosynthetic light-harvesting complex may be explored by a sequence of laser pulses specifically designed to probe the correlated dynamics of double excitations. Cross peaks in the 2D correlation plots of the spectra reveal projections of the double-exciton wavefunctions onto a basis of direct products of single excitons. An alternative physical interpretation of these signals in terms of quasiparticle scattering is developed. PMID:18562293

Band-to-band transitions, selection rules, effective mass, and excitonic contributions in monoclinic β -Ga2O3

NASA Astrophysics Data System (ADS)

Mock, Alyssa; Korlacki, Rafał; Briley, Chad; Darakchieva, Vanya; Monemar, Bo; Kumagai, Yoshinao; Goto, Ken; Higashiwaki, Masataka; Schubert, Mathias

2017-12-01

We employ an eigenpolarization model including the description of direction dependent excitonic effects for rendering critical point structures within the dielectric function tensor of monoclinic β -Ga2O3 yielding a comprehensive analysis of generalized ellipsometry data obtained from 0.75-9 eV. The eigenpolarization model permits complete description of the dielectric response. We obtain, for single-electron and excitonic band-to-band transitions, anisotropic critical point model parameters including their polarization vectors within the monoclinic lattice. We compare our experimental analysis with results from density functional theory calculations performed using the Gaussian-attenuation-Perdew-Burke-Ernzerhof hybrid density functional. We present and discuss the order of the fundamental direct band-to-band transitions and their polarization selection rules, the electron and hole effective mass parameters for the three lowest band-to-band transitions, and their excitonic contributions. We find that the effective masses for holes are highly anisotropic and correlate with the selection rules for the fundamental band-to-band transitions. The observed transitions are polarized close to the direction of the lowest hole effective mass for the valence band participating in the transition.

Real-Time Observation of Exciton-Phonon Coupling Dynamics in Self-Assembled Hybrid Perovskite Quantum Wells.

PubMed

Ni, Limeng; Huynh, Uyen; Cheminal, Alexandre; Thomas, Tudor H; Shivanna, Ravichandran; Hinrichsen, Ture F; Ahmad, Shahab; Sadhanala, Aditya; Rao, Akshay

2017-11-28

Self-assembled hybrid perovskite quantum wells have attracted attention due to their tunable emission properties, ease of fabrication, and device integration. However, the dynamics of excitons in these materials, especially how they couple to phonons, remains an open question. Here, we investigate two widely used materials, namely, butylammonium lead iodide (CH 3 (CH 2 ) 3 NH 3 ) 2 PbI 4 and hexylammonium lead iodide (CH 3 (CH 2 ) 5 NH 3 ) 2 PbI 4 , both of which exhibit broad photoluminescence tails at room temperature. We performed femtosecond vibrational spectroscopy to obtain a real-time picture of the exciton-phonon interaction and directly identified the vibrational modes that couple to excitons. We show that the choice of the organic cation controls which vibrational modes the exciton couples to. In butylammonium lead iodide, excitons dominantly couple to a 100 cm -1 phonon mode, whereas in hexylammonium lead iodide, excitons interact with phonons with frequencies of 88 and 137 cm -1 . Using the determined optical phonon energies, we analyzed photoluminescence broadening mechanisms. At low temperatures (<100 K), the broadening is due to acoustic phonon scattering, whereas at high temperatures, LO phonon-exciton coupling is the dominant mechanism. Our results help explain the broad photoluminescence line shape observed in hybrid perovskite quantum wells and provide insights into the mechanism of exciton-phonon coupling in these materials.

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

PubMed

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

2016-05-17

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

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

PubMed Central

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

2016-01-01

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

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.

Measuring Exciton Diffusion in Conjugated Polymer Films with Super-resolution Microscopy

NASA Astrophysics Data System (ADS)

Penwell, Samuel; Ginsberg, Lucas; Noriega Manez, Rodrigo; Ginsberg, Naomi

2015-03-01

Conjugated polymers are highly tunable organic semiconductors, which can be solution processed to form thin films, making them prime candidates for organic photovoltaic devices. One of the most important parameters in a conjugated polymer solar cell is the exciton diffusion length, which depends on intermolecular couplings, and is typically on the order of 10 nm. This mean exciton migration can vary dramatically between films and within a single film due to heterogeneities in morphology on length scales of 10's to 100's nm. To study the variability of exciton diffusion and morphology within individual conjugated polymer films, we are adapting stimulated emission depletion microscopy. STED is typically used in biology with well-engineered fluorescent labels or on NV-centers in diamond. I will, however, describe how we have demonstrated STED in conjugated polymer films of MEH-PPV and CN-PPV by taking care to first understand the film's photophysical properties. This new approach provides a way to study exciton diffusion by utilizing subdiffraction optical excitation volumes. In this way, we will obtain a spatiotemporal map of exciton distributions that will help to correlate the energetic landscape to film morphology at the nanoscale. This research is supported in part by the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under Contract No. DE-AC05-06.

Single-exciton optical gain in semiconductor nanocrystals.

PubMed

Klimov, Victor I; Ivanov, Sergei A; Nanda, Jagjit; Achermann, Marc; Bezel, Ilya; McGuire, John A; Piryatinski, Andrei

2007-05-24

Nanocrystal quantum dots have favourable light-emitting properties. They show photoluminescence with high quantum yields, and their emission colours depend on the nanocrystal size--owing to the quantum-confinement effect--and are therefore tunable. However, nanocrystals are difficult to use in optical amplification and lasing. Because of an almost exact balance between absorption and stimulated emission in nanoparticles excited with single electron-hole pairs (excitons), optical gain can only occur in nanocrystals that contain at least two excitons. A complication associated with this multiexcitonic nature of light amplification is fast optical-gain decay induced by non-radiative Auger recombination, a process in which one exciton recombines by transferring its energy to another. Here we demonstrate a practical approach for obtaining optical gain in the single-exciton regime that eliminates the problem of Auger decay. Specifically, we develop core/shell hetero-nanocrystals engineered in such a way as to spatially separate electrons and holes between the core and the shell (type-II heterostructures). The resulting imbalance between negative and positive charges produces a strong local electric field, which induces a giant ( approximately 100 meV or greater) transient Stark shift of the absorption spectrum with respect to the luminescence line of singly excited nanocrystals. This effect breaks the exact balance between absorption and stimulated emission, and allows us to demonstrate optical amplification due to single excitons.

Optically Discriminating Carrier-Induced Quasiparticle Band Gap and Exciton Energy Renormalization in Monolayer MoS2

NASA Astrophysics Data System (ADS)

Yao, Kaiyuan; Yan, Aiming; Kahn, Salman; Suslu, Aslihan; Liang, Yufeng; Barnard, Edward S.; Tongay, Sefaattin; Zettl, Alex; Borys, Nicholas J.; Schuck, P. James

2017-08-01

Optoelectronic excitations in monolayer MoS2 manifest from a hierarchy of electrically tunable, Coulombic free-carrier and excitonic many-body phenomena. Investigating the fundamental interactions underpinning these phenomena—critical to both many-body physics exploration and device applications—presents challenges, however, due to a complex balance of competing optoelectronic effects and interdependent properties. Here, optical detection of bound- and free-carrier photoexcitations is used to directly quantify carrier-induced changes of the quasiparticle band gap and exciton binding energies. The results explicitly disentangle the competing effects and highlight longstanding theoretical predictions of large carrier-induced band gap and exciton renormalization in two-dimensional semiconductors.

Optically Discriminating Carrier-Induced Quasiparticle Band Gap and Exciton Energy Renormalization in Monolayer MoS_{2}.

PubMed

Yao, Kaiyuan; Yan, Aiming; Kahn, Salman; Suslu, Aslihan; Liang, Yufeng; Barnard, Edward S; Tongay, Sefaattin; Zettl, Alex; Borys, Nicholas J; Schuck, P James

2017-08-25

Optoelectronic excitations in monolayer MoS_{2} manifest from a hierarchy of electrically tunable, Coulombic free-carrier and excitonic many-body phenomena. Investigating the fundamental interactions underpinning these phenomena-critical to both many-body physics exploration and device applications-presents challenges, however, due to a complex balance of competing optoelectronic effects and interdependent properties. Here, optical detection of bound- and free-carrier photoexcitations is used to directly quantify carrier-induced changes of the quasiparticle band gap and exciton binding energies. The results explicitly disentangle the competing effects and highlight longstanding theoretical predictions of large carrier-induced band gap and exciton renormalization in two-dimensional semiconductors.

Asymmetric photon transport in organic semiconductor nanowires through electrically controlled exciton diffusion

PubMed Central

Cui, Qiu Hong; Peng, Qian; Luo, Yi; Jiang, Yuqian; Yan, Yongli; Wei, Cong; Shuai, Zhigang; Sun, Cheng; Yao, Jiannian; Zhao, Yong Sheng

2018-01-01

The ability to steer the flow of light toward desired propagation directions is critically important for the realization of key functionalities in optical communication and information processing. Although various schemes have been proposed for this purpose, the lack of capability to incorporate an external electric field to effectively tune the light propagation has severely limited the on-chip integration of photonics and electronics. Because of the noninteractive nature of photons, it is only possible to electrically control the flow of light by modifying the refractive index of materials through the electro-optic effect. However, the weak optical effects need to be strongly amplified for practical applications in high-density photonic integrations. We show a new strategy that takes advantage of the strong exciton-photon coupling in active waveguides to effectively manipulate photon transport by controlling the interaction between excitons and the external electric field. Single-crystal organic semiconductor nanowires were used to generate highly stable Frenkel exciton polaritons with strong binding and diffusion abilities. By making use of directional exciton diffusion in an external electric field, we have realized an electrically driven asymmetric photon transport and thus directional light propagation in a single nanowire. With this new concept, we constructed a dual-output single wire–based device to build an electrically controlled single-pole double-throw optical switch with fast temporal response and high switching frequency. Our findings may lead to the innovation of concepts and device architectures for optical information processing. PMID:29556529

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.

Strain Gradient Modulated Exciton Evolution and Emission in ZnO Fibers

PubMed Central

Wei, Bin; Ji, Yuan; Gauvin, Raynald; Zhang, Ze; Zou, Jin; Han, Xiaodong

2017-01-01

One-dimensional semiconductor can undergo large deformation including stretching and bending. This homogeneous strain and strain gradient are an easy and effective way to tune the light emission properties and the performance of piezo-phototronic devices. Here, we report that with large strain gradients from 2.1–3.5% μm−1, free-exciton emission was intensified, and the free-exciton interaction (FXI) emission became a prominent FXI-band at the tensile side of the ZnO fiber. These led to an asymmetric variation in energy and intensity along the cross-section as well as a redshift of the total near-band-edge (NBE) emission. This evolution of the exciton emission was directly demonstrated using spatially resolved CL spectrometry combined with an in situ tensile-bending approach at liquid nitrogen temperature for individual fibers and nanowires. A distinctive mechanism of the evolution of exciton emission is proposed: the enhancement of the free-exciton-related emission is attributed to the aggregated free excitons and their interaction in the narrow bandgap in the presence of high bandgap gradients and a transverse piezoelectric field. These results might facilitate new approaches for energy conversion and sensing applications via strained nanowires and fibers. PMID:28084427

Strain Gradient Modulated Exciton Evolution and Emission in ZnO Fibers.

PubMed

Wei, Bin; Ji, Yuan; Gauvin, Raynald; Zhang, Ze; Zou, Jin; Han, Xiaodong

2017-01-13

One-dimensional semiconductor can undergo large deformation including stretching and bending. This homogeneous strain and strain gradient are an easy and effective way to tune the light emission properties and the performance of piezo-phototronic devices. Here, we report that with large strain gradients from 2.1-3.5% μm -1 , free-exciton emission was intensified, and the free-exciton interaction (FXI) emission became a prominent FXI-band at the tensile side of the ZnO fiber. These led to an asymmetric variation in energy and intensity along the cross-section as well as a redshift of the total near-band-edge (NBE) emission. This evolution of the exciton emission was directly demonstrated using spatially resolved CL spectrometry combined with an in situ tensile-bending approach at liquid nitrogen temperature for individual fibers and nanowires. A distinctive mechanism of the evolution of exciton emission is proposed: the enhancement of the free-exciton-related emission is attributed to the aggregated free excitons and their interaction in the narrow bandgap in the presence of high bandgap gradients and a transverse piezoelectric field. These results might facilitate new approaches for energy conversion and sensing applications via strained nanowires and fibers.

Exciton dynamics at a single dislocation in GaN probed by picosecond time-resolved cathodoluminescence

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

Liu, W., E-mail: we.liu@epfl.ch, E-mail: gwenole.jacopin@epfl.ch; Carlin, J.-F.; Grandjean, N.

2016-07-25

We investigate the dynamics of donor bound excitons (D°X{sub A}) at T = 10 K around an isolated single edge dislocation in homoepitaxial GaN, using a picosecond time-resolved cathodoluminescence (TR-CL) setup with high temporal and spatial resolutions. An ∼ 1.3 meV dipole-like energy shift of D°X{sub A} is observed around the dislocation, induced by the local strain fields. By simultaneously recording the variations of both the exciton lifetime and the CL intensity across the dislocation, we directly assess the dynamics of excitons around the defect. Our observations are well reproduced by a diffusion model. It allows us to deduce an exciton diffusion length ofmore » ∼24 nm as well as an effective area of the dislocation with a radius of ∼95 nm, where the recombination can be regarded as entirely non-radiative.« less

Investigation of indirect excitons in bulk 2H-MoS2 using transmission electron energy-loss spectroscopy.

PubMed

Habenicht, Carsten; Schuster, Roman; Knupfer, Martin; Büchner, Bernd

2018-05-23

We have investigated indirect excitons in bulk 2H-MoS 2 using transmission electron energy-loss spectroscopy. The electron energy-loss spectra were measured for various momentum transfer values parallel to the [Formula: see text] and [Formula: see text] directions of the Brillouin zone. The results allowed the identification of the indirect excitons between the valence band K v and conduction band Λ c points, the Γ v and K c points as well as adjacent K v and [Formula: see text] points. The energy-momentum dispersions for the K v -Λ c , Γ v -K c and K v1 -[Formula: see text] excitons along the [Formula: see text] line are presented. The former two transitions exhibit a quadratic dispersion which allowed calculating their effective exciton masses based on the effective mass approximation. The K v1 -[Formula: see text] transition follows a more linear dispersion relationship.

Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

PubMed

Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

2017-07-01

Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO 3 , SrTiO 3 , and BaTiO 3 , together with reference oxides, MgO, CaO, SrO, BaO, and TiO 2 , were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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

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.

Solid-State Solvation and Enhanced Exciton Diffusion in Doped Organic Thin Films under Mechanical Pressure.

PubMed

Chang, Wendi; Akselrod, Gleb M; Bulović, Vladimir

2015-04-28

Direct modification of exciton energy has been previously used to optimize the operation of organic optoelectronic devices. One demonstrated method for exciton energy modification is through the use of the solvent dielectric effects in doped molecular films. To gain a deeper appreciation of the underlying physical mechanisms, in this work we test the solid-state solvation effect in molecular thin films under applied external pressure. We observe that external mechanical pressure increases dipole-dipole interactions, leading to shifts in the Frenkel exciton energy and enhancement of the time-resolved spectral red shift associated with the energy-transfer-mediated exciton diffusion. Measurements are performed on host:dopant molecular thin films, which show bathochromic shifts in photoluminescence (PL) under increasing pressure. This is in agreement with a simple solvation theory model of exciton energetics with a fitting parameter based on the mechanical properties of the host matrix material. We measure no significant change in exciton lifetime with increasing pressure, consistent with unchanged aggregation in molecular films under compression. However, we do observe an increase in exciton spectral thermalization rate for compressed molecular films, indicating enhanced exciton diffusion for increased dipole-dipole interactions under pressure. The results highlight the contrast between molecular energy landscapes obtained when dipole-dipole interactions are increased by the pressure technique versus the conventional dopant concentration variation methods, which can lead to extraneous effects such as aggregation at higher doping concentrations. The present work demonstrates the use of pressure-probing techniques in studying energy disorder and exciton dynamics in amorphous molecular thin films.

Solid-State Solvation and Enhanced Exciton Diffusion in Doped Organic Thin Films under Mechanical Pressure

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

Chang, Wendi; Akselrod, Gleb M.; Bulović, Vladimir

2015-04-28

Direct modification of exciton energy has been previously used to optimize the operation of organic optoelectronic devices. One demonstrated method for exciton energy modification is through the use of the solvent dielectric effects in doped molecular films. To gain a deeper appreciation of the underlying physical mechanisms, in this work we test the solid-state solvation effect in molecular thin films under applied external pressure. We observe that external mechanical pressure increases dipole–dipole interactions, leading to shifts in the Frenkel exciton energy and enhancement of the time-resolved spectral red shift associated with the energy-transfer-mediated exciton diffusion. Measurements are performed on host:dopantmore » molecular thin films, which show bathochromic shifts in photoluminescence (PL) under increasing pressure. This is in agreement with a simple solvation theory model of exciton energetics with a fitting parameter based on the mechanical properties of the host matrix material. We measure no significant change in exciton lifetime with increasing pressure, consistent with unchanged aggregation in molecular films under compression. However, we do observe an increase in exciton spectral thermalization rate for compressed molecular films, indicating enhanced exciton diffusion for increased dipole–dipole interactions under pressure. The results highlight the contrast between molecular energy landscapes obtained when dipole–dipole interactions are increased by the pressure technique versus the conventional dopant concentration variation methods, which can lead to extraneous effects such as aggregation at higher doping concentrations. The present work demonstrates the use of pressure-probing techniques in studying energy disorder and exciton dynamics in amorphous molecular thin films.« less

Layer speciation and electronic structure investigation of freestanding hexagonal boron nitride nanosheets

NASA Astrophysics Data System (ADS)

WangEqual Contribution To This Work., Jian; Wang, Zhiqiang; Cho, Hyunjin; Kim, Myung Jong; Sham, T. K.; Sun, Xuhui

2015-01-01

Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared.Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04445b

Strong exciton-photon coupling in organic single crystal microcavity with high molecular orientation

NASA Astrophysics Data System (ADS)

Goto, Kaname; Yamashita, Kenichi; Yanagi, Hisao; Yamao, Takeshi; Hotta, Shu

2016-08-01

Strong exciton-photon coupling has been observed in a highly oriented organic single crystal microcavity. This microcavity consists of a thiophene/phenylene co-oligomer (TPCO) single crystal laminated on a high-reflection distributed Bragg reflector. In the TPCO crystal, molecular transition dipole was strongly polarized along a certain horizontal directions with respect to the main crystal plane. This dipole polarization causes significantly large anisotropies in the exciton transition and optical constants. Especially the anisotropic exciton transition was found to provide the strong enhancement in the coupling with the cavity mode, which was demonstrated by a Rabi splitting energy as large as ˜100 meV even in the "half-vertical cavity surface emitting lasing" microcavity structure.

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.

Probing the influence of dielectric environment on excitons in monolayer WSe 2: Insight from high magnetic fields

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

Stier, Andreas V.; Wilson, Nathan P.; Clark, Genevieve

Excitons in atomically thin semiconductors necessarily lie close to a surface, and therefore their properties are expected to be strongly influenced by the surrounding dielectric environment. However, systematic studies exploring this role are challenging, in part because the most readily accessible exciton parameter—the exciton’s optical transition energy—is largely unaffected by the surrounding medium. Here we show that the role of the dielectric environment is revealed through its systematic influence on the size of the exciton, which can be directly measured via the diamagnetic shift of the exciton transition in high magnetic fields. Using exfoliated WSe 2 monolayers affixed to single-modemore » optical fibers, we tune the surrounding dielectric environment by encapsulating the flakes with different materials and perform polarized low-temperature magneto-absorption studies to 65 T. The systematic increase of the exciton’s size with dielectric screening, and concurrent reduction in binding energy (also inferred from these measurements), is quantitatively compared with leading theoretical models. Furthermore, these results demonstrate how exciton properties can be tuned in future 2D optoelectronic devices.« less

Exciton Rydberg series in mono- and few-layer WS2

NASA Astrophysics Data System (ADS)

Chernikov, Alexey; Berkelbach, Timothy C.; Hill, Heather M.; Rigosi, Albert; Li, Yilei; Aslan, Özgur B.; Hybertsen, Mark S.; Reichman, David R.; Heinz, Tony F.

2014-03-01

Considered a long-awaited semiconducting analogue to graphene, the family of atomically thin transition metal dichalcogenides (TMDs) attracted intense interest in the scientific community due to their remarkable physical properties resulting from the reduced dimensionality. A fundamental manifestation of the two-dimensional nature is a strong increase in the Coulomb interaction. The resulting formation of tightly bound excitons plays a crucial role for a majority of optical and transport phenomena. In our work, we investigate the excitons in atomically thin TMDs by optical micro-spectroscopy and apply a microscopic, ab-initio theoretical approach. We observe a full sequence of excited exciton states, i.e., the Rydberg series, in the monolayer WS2, identifying tightly bound excitons with energies exceeding 0.3 eV - almost an order of magnitude higher than in the corresponding, three-dimensional crystal. We also find significant deviations of the excitonic properties from the conventional hydrogenic physics - a direct evidence of a non-uniform dielectric environment. Finally, an excellent quantitative agreement is obtained between the experimental findings and the developed theoretical approach.

Probing the influence of dielectric environment on excitons in monolayer WSe 2: Insight from high magnetic fields

DOE PAGES

Stier, Andreas V.; Wilson, Nathan P.; Clark, Genevieve; ...

2016-11-09

Excitons in atomically thin semiconductors necessarily lie close to a surface, and therefore their properties are expected to be strongly influenced by the surrounding dielectric environment. However, systematic studies exploring this role are challenging, in part because the most readily accessible exciton parameter—the exciton’s optical transition energy—is largely unaffected by the surrounding medium. Here we show that the role of the dielectric environment is revealed through its systematic influence on the size of the exciton, which can be directly measured via the diamagnetic shift of the exciton transition in high magnetic fields. Using exfoliated WSe 2 monolayers affixed to single-modemore » optical fibers, we tune the surrounding dielectric environment by encapsulating the flakes with different materials and perform polarized low-temperature magneto-absorption studies to 65 T. The systematic increase of the exciton’s size with dielectric screening, and concurrent reduction in binding energy (also inferred from these measurements), is quantitatively compared with leading theoretical models. Furthermore, these results demonstrate how exciton properties can be tuned in future 2D optoelectronic devices.« less

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.

Multidimensional Coherent Spectroscopy of GaAs Excitons and Quantum Microcavity Polaritons

NASA Astrophysics Data System (ADS)

Wilmer, Brian L.

Light-matter interactions associated with excitons and exciton related complexes are explored in bulk GaAs and semiconductor microcavities using multidimensional coherent spectroscopy (MDCS). This approach provides rich spectra determining quantum excitation pathways, structural influences on the excitons, and coherence times. Polarization, excitation density, and temperature-dependent MDCS is performed on excitons in strained bulk GaAs layers, probing the coherent response for differing amounts of strain. Biaxial tensile strain lifts the degeneracy of heavy-hole and light-hole valence states, leading to an observed splitting of the associated excitons at low temperature. Increasing the strain increases the magnitude of the heavy-/light- hole exciton peak splitting, induces an asymmetry in the off-diagonal interaction coherences, increases the difference in the heavy- and light- hole exciton homogenous linewidths, and increases the inhomogeneous broadening of both exciton species. All results arise from strain-induced variations in the local electronic environment, which is not uniform along the growth direction of the thin layers. For cross-linear polarized excitation, wherein excitonic signals give way to biexcitonic signals, the high-strain sample shows evidence of bound light-, heavy- and mixed- hole biexcitons. 2DCS maps the anticrossing associated with normal mode splitting in a semiconductor microcavity. For a detuning range near zero, it is observed that there are two diagonal features related to the intra-action of exciton-polariton branches and two off-diagonal features related to coherent interaction between the polaritons. At negative detuning, the line shape properties of the diagonal intra-action features are distinguishable and can be associated with cavity-like and exciton-like modes. A biexcitonic companion feature is observed, shifted from the exciton feature by the biexciton binding energy. Closer to zero detuning, all features are enhanced and the diagonal intra-action features become nearly equal in amplitude and linewidth. At positive detuning the exciton-like and cavity-like characteristics return to the diagonal intra-action features. Off-diagonal interaction features exhibit asymmetry in their amplitudes throughout the detuning range. The amplitudes are strongly modulated as the lower polariton branch crosses the bound biexciton energy determined from negatively detuned spectra.

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).

Exciton-dominated dielectric function of atomically thin MoS 2 films

DOE PAGES

Yu, Yiling; Yu, Yifei; Cai, Yongqing; ...

2015-11-24

We systematically measure the dielectric function of atomically thin MoS 2 films with different layer numbers and demonstrate that excitonic effects play a dominant role in the dielectric function when the films are less than 5–7 layers thick. The dielectric function shows an anomalous dependence on the layer number. It decreases with the layer number increasing when the films are less than 5–7 layers thick but turns to increase with the layer number for thicker films. We show that this is because the excitonic effect is very strong in the thin MoS 2 films and its contribution to the dielectricmore » function may dominate over the contribution of the band structure. We also extract the value of layer-dependent exciton binding energy and Bohr radius in the films by fitting the experimental results with an intuitive model. The dominance of excitonic effects is in stark contrast with what reported at conventional materials whose dielectric functions are usually dictated by band structures. Lastly, the knowledge of the dielectric function may enable capabilities to engineer the light-matter interactions of atomically thin MoS 2 films for the development of novel photonic devices, such as metamaterials, waveguides, light absorbers, and light emitters.« less

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.

Ultrafast spectroscopy of exciton and exciton dynamics in mono and few layers of WS2

NASA Astrophysics Data System (ADS)

Khadka, Sudiksha; Aleithan, Shrouq; Livshits, Max; Rack, Jeffrey J.; Kordesch, Martin; Stinaff, Eric

Single layer of Transitional metal dichalcogenides (MX2) are 2D semiconductors that have a direct band gap in visible spectrum and fill the gap in between 2D metallic and insulating materials. They have possible application in optoelectronic devices, photovoltaics and photodetection, molecular sensing, 'valleytronics', and flexible transparent electronics. Tungsten Disulphide (WS2), one of the member of MX2 family, has a direct band gap of 2.2 eV and a large valley splitting of about 0.4 eV. Here, we present a detailed study of exciton states and their decay mechanisms in mono and few layer WS2 using femto-second transient absorption spectroscopy. We report a new peak at 3.01+/-0.1 eV whose origin in k space is believed to be at or around K point and further investigation is under way. The exponential fitting of decay curve of the exciton A reveals three time components as 1.7+/-0.3 ps, 33.5+/-10 ps and 670+/-15 ps, most likely corresponding to carrier-carrier scattering, carrier-phonon scattering, and radiative relaxation respectively.

Ultrafast spectroscopy of exciton and exciton dynamics in mono and few layers of WS2

NASA Astrophysics Data System (ADS)

Khadka, Sudiksha; Aleithan, Shrouq; Livshits, Max; Rack, Jeffrey J.; Kordesch, Martin; Stinaff, Eric

Single layer of Transitional metal dichalcogenides (MX2) are 2D semiconductors that have a direct band gap in visible spectrum and fill the gap in between 2D metallic and insulating materials. They have possible application in optoelectronic devices, photovoltaics and photodetection, molecular sensing, 'valleytronics', and flexible transparent electronics. Tungsten Disulphide (WS2), one of the member of MX2 family, has a direct band gap of 2.2 eV and a large valley splitting of about 0.4 eV. Here, we present a detailed study of exciton states and their decay mechanisms in mono and few layer WS2 using femto-second transient absorption spectroscopy. We report a new peak at 3.01+/-0.1 eV whose origin in k space is believed to be at or around K point and further investigation is underway. The exponential fitting of decay curve of the exciton A reveals three time components as 1.7+/-0.3 ps, 33.5+/-10 ps and 670+/-15 ps, most likely corresponding to carrier-carrier scattering, carrier-phonon scattering, and radiative relaxation respectively.

Exciton Fine-Structure Splitting in Self-Assembled Lateral InAs/GaAs Quantum-Dot Molecular Structures.

PubMed

Fillipov, Stanislav; Puttisong, Yuttapoom; Huang, Yuqing; Buyanova, Irina A; Suraprapapich, Suwaree; Tu, Charles W; Chen, Weimin M

2015-06-23

Fine-structure splitting (FSS) of excitons in semiconductor nanostructures is a key parameter that has significant implications in photon entanglement and polarization conversion between electron spins and photons, relevant to quantum information technology and spintronics. Here, we investigate exciton FSS in self-organized lateral InAs/GaAs quantum-dot molecular structures (QMSs) including laterally aligned double quantum dots (DQDs), quantum-dot clusters (QCs), and quantum rings (QRs), by employing polarization-resolved microphotoluminescence (μPL) spectroscopy. We find a clear trend in FSS between the studied QMSs depending on their geometric arrangements, from a large FSS in the DQDs to a smaller FSS in the QCs and QRs. This trend is accompanied by a corresponding difference in the optical polarization directions of the excitons between these QMSs, namely, the bright-exciton lines are linearly polarized preferably along or perpendicular to the [11̅0] crystallographic axis in the DQDs that also defines the alignment direction of the two constituting QDs, whereas in the QCs and QRs, the polarization directions are randomly oriented. We attribute the observed trend in the FSS to a significant reduction of the asymmetry in the lateral confinement potential of the excitons in the QRs and QCs as compared with the DQDs, as a result of a compensation between the effects of lateral shape anisotropy and piezoelectric field. Our work demonstrates that FSS strongly depends on the geometric arrangements of the QMSs, which effectively tune the degree of the compensation effects and are capable of reducing FSS even in a strained QD system to a limit similar to strain-free QDs. This approach provides a pathway in obtaining high-symmetry quantum emitters desirable for realizing photon entanglement and spintronic devices based on such nanostructures, utilizing an uninterrupted epitaxial growth procedure without special requirements for lattice-matched materials combinations, specific substrate orientations, and nanolithography.

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.

Double Tryptophan Exciton Probe to Gauge Proximal Side Chains in Proteins- Augmentation at Low Temperature

PubMed Central

Gasymov, Oktay K.; Abduragimov, Adil R.; Glasgow, Ben J.

2015-01-01

The circular dichroic (CD) exciton couplet between tryptophans and/or tyrosines offers the potential to probe distances within 10Å in proteins. The exciton effect has been used with native chromophores in critical positions in a few proteins. Here, site-directed mutagenesis created double tryptophan probes for key sites of a protein (tear lipocalin). For tear lipocalin the crystal and solution structures are concordant in both apo- and holo-forms. Double tryptophan substitutions were performed at sites that could probe conformation and were likely within 10 Å. Far-UV CD spectra of double Trp mutants were performed with controls that had non-interacting substituted tryptophans. Low temperature (77K) was tested for augmentation of the exciton signal. Exciton coupling appeared with tryptophan substitutions at positions within loop A-B (28 and 31, 33), between loop A-B (28) and strand G (103 and 105), as well as between the strands B (35) and C (56). The CD exciton couplet signals were amplified 3–5 fold at 77K. The results were concordant with close distances in crystal and solution structures. The exciton couplets had functional significance and correctly assigned the holo-conformation. The methodology creates an effective probe to identify proximal amino acids in a variety of motifs. PMID:25693116

Measuring the Influence of Dielectric Environment on 2D Excitons in Monolayer Semiconductors: Insight from High Magnetic Fields1

NASA Astrophysics Data System (ADS)

Stier, Andreas

The relatively heavy electrons and holes in monolayer semiconductors such as MoS2 form tightly-bound excitons with large binding energies, thus motivating magneto-optical studies in high magnetic fields. Because 2D excitons in these materials necessarily lie close to a surface, their properties are expected to be strongly influenced by the surrounding dielectric environment. However, systematic studies exploring this role are challenging, in part because the most readily accessible exciton parameter - the exciton's optical transition energy - is largely unaffected by the surrounding medium. Here we show that the role of the dielectric environment can be revealed through its systematic influence on the size of the exciton, which can be directly measured via the diamagnetic shift of the exciton transition in high magnetic fields. Using exfoliated WSe2 monolayers affixed to single-mode optical fibers, we tune the surrounding dielectric environment by encapsulating the monolayers with different materials, and perform polarization resolved low-temperature magneto-absorption studies to 65 tesla. The systematic increase of the exciton's size with dielectric screening, and concurrent two-fold reduction in binding energy (also inferred from these measurements), is quantitatively compared with leading theoretical models based on the Keldysh potential. These results demonstrate how exciton properties can be tuned in future 2D devices and van der Waals heterostructures. 1In collaboration with S.A. Crooker (NHMFL); J. Kono (Rice University); K.M. McCreary, B.T. Jonker (Naval Research Lab); N.P. Wilson, G. Clark, X. Xu (University of Washington).

Long-range exciton transport in conjugated polymer nanofibers prepared by seeded growth

NASA Astrophysics Data System (ADS)

Jin, Xu-Hui; Price, Michael B.; Finnegan, John R.; Boott, Charlotte E.; Richter, Johannes M.; Rao, Akshay; Menke, S. Matthew; Friend, Richard H.; Whittell, George R.; Manners, Ian

2018-05-01

Easily processed materials with the ability to transport excitons over length scales of more than 100 nanometers are highly desirable for a range of light-harvesting and optoelectronic devices. We describe the preparation of organic semiconducting nanofibers comprising a crystalline poly(di-n-hexylfluorene) core and a solvated, segmented corona consisting of polyethylene glycol in the center and polythiophene at the ends. These nanofibers exhibit exciton transfer from the core to the lower-energy polythiophene coronas in the end blocks, which occurs in the direction of the interchain π-π stacking with very long diffusion lengths (>200 nanometers) and a large diffusion coefficient (0.5 square centimeters per second). This is made possible by the uniform exciton energetic landscape created by the well-ordered, crystalline nanofiber core.

Strong exciton-photon coupling in organic single crystal microcavity with high molecular orientation

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

Goto, Kaname; Yamashita, Kenichi, E-mail: yamasita@kit.ac.jp; Yanagi, Hisao

2016-08-08

Strong exciton-photon coupling has been observed in a highly oriented organic single crystal microcavity. This microcavity consists of a thiophene/phenylene co-oligomer (TPCO) single crystal laminated on a high-reflection distributed Bragg reflector. In the TPCO crystal, molecular transition dipole was strongly polarized along a certain horizontal directions with respect to the main crystal plane. This dipole polarization causes significantly large anisotropies in the exciton transition and optical constants. Especially the anisotropic exciton transition was found to provide the strong enhancement in the coupling with the cavity mode, which was demonstrated by a Rabi splitting energy as large as ∼100 meV even inmore » the “half-vertical cavity surface emitting lasing” microcavity structure.« less

Visualising Berry phase and diabolical points in a quantum exciton-polariton billiard

PubMed Central

Estrecho, E.; Gao, T.; Brodbeck, S.; Kamp, M.; Schneider, C.; Höfling, S.; Truscott, A. G.; Ostrovskaya, E. A.

2016-01-01

Diabolical points (spectral degeneracies) can naturally occur in spectra of two-dimensional quantum systems and classical wave resonators due to simple symmetries. Geometric Berry phase is associated with these spectral degeneracies. Here, we demonstrate a diabolical point and the corresponding Berry phase in the spectrum of hybrid light-matter quasiparticles—exciton-polaritons in semiconductor microcavities. It is well known that sufficiently strong optical pumping can drive exciton-polaritons to quantum degeneracy, whereby they form a macroscopically populated quantum coherent state similar to a Bose-Einstein condensate. By pumping a microcavity with a spatially structured light beam, we create a two-dimensional quantum billiard for the exciton-polariton condensate and demonstrate a diabolical point in the spectrum of the billiard eigenstates. The fully reconfigurable geometry of the potential walls controlled by the optical pump enables a striking experimental visualization of the Berry phase associated with the diabolical point. The Berry phase is observed and measured by direct imaging of the macroscopic exciton-polariton probability densities. PMID:27886222

Simulating Excitons in MoS2 with Time-Dependent Density Functional Theory

NASA Astrophysics Data System (ADS)

Flamant, Cedric; Kolesov, Grigory; Kaxiras, Efthimios

Monolayer molybdenum disulfide, owing to its graphene-like two-dimensional geometry whilst still having a finite bandgap, is a material of great interest in condensed matter physics and for potential application in electronic devices. In particular, MoS2 exhibits significant excitonic effects, a desirable quality for fundamental many-body research. Time-dependent density functional theory (TD-DFT) allows us to simulate dynamical effects as well as temperature-based effects in a natural way given the direct treatment of the time evolution of the system. We present a TD-DFT study of monolayer MoS2 exciton dynamics, examining various qualitative and quantitative predictions in pure samples and in the presence of defects. In particular, we generate an absorption spectrum through simulated pulse excitation for comparison to experiment and also analyze the response of the exciton in an external electric field.In this work we also discuss the electronic structure of the exciton in MoS2 with and without vacancies.

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.

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

Quantum chaos and breaking of all anti-unitary symmetries in Rydberg excitons.

PubMed

Aßmann, Marc; Thewes, Johannes; Fröhlich, Dietmar; Bayer, Manfred

2016-07-01

Symmetries are the underlying principles of fundamental interactions in nature. Chaos in a quantum system may emerge from breaking these symmetries. Compared to vacuum, crystals are attractive for studying quantum chaos, as they not only break spatial isotropy, but also lead to novel quasiparticles with modified interactions. Here we study yellow Rydberg excitons in cuprous oxide which couple strongly to the vacuum light field and interact significantly with crystal phonons, leading to inversion symmetry breaking. In a magnetic field, time-reversal symmetry is also broken and the exciton states show a complex splitting pattern, resulting in quadratic level repulsion for small splittings. In contrast to atomic chaotic systems in a magnetic field, which show only a linear level repulsion, this is a signature of a system where all anti-unitary symmetries are broken simultaneously. This behaviour can otherwise be found only for the electro-weak interaction or engineered billiards.

Plasmon-exciton polaritons in two-dimensional semiconductor/metal interfaces

NASA Astrophysics Data System (ADS)

Gonçalves, P. A. D.; Bertelsen, L. P.; Xiao, Sanshui; Mortensen, N. Asger

2018-01-01

The realization and control of polaritons is of paramount importance in the prospect of novel photonic devices. Here, we investigate the emergence of plasmon-exciton polaritons in hybrid structures consisting of a two-dimensional transition-metal dichalcogenide (TMDC) deposited onto a metal substrate or coating a metallic thin film. We determine the polaritonic spectrum and show that, in the former case, the addition of a top dielectric layer and, in the latter case, the thickness of the metal film can be used to tune and promote plasmon-exciton interactions well within the strong-coupling regime. Our results demonstrate that Rabi splittings exceeding 100 meV can readily be achieved in planar dielectric/TMDC/metal structures under ambient conditions. We thus believe that this Rapid Communication provides a simple and intuitive picture to tailor strong coupling in plexcitonics with potential applications for engineering compact photonic devices with tunable optical properties.

Subpicosecond Photoinduced Hole Transfer from a CdS Quantum Dot to a Molecular Acceptor Bound Through an Exciton-Delocalizing Ligand.

PubMed

Lian, Shichen; Weinberg, David J; Harris, Rachel D; Kodaimati, Mohamad S; Weiss, Emily A

2016-06-28

This paper describes the enhancement of the rate of hole transfer from a photoexcited CdS quantum dot (QD), with radius R = 2.0 nm, to a molecular acceptor, phenothiazine (PTZ), by linking the donor and acceptor through a phenyldithiocarbamate (PTC) linker, which is known to lower the confinement energy of the excitonic hole. Upon adsorption of PTC, the bandgap of the QD decreases due to delocalization of the exciton, primarily the excitonic hole, into interfacial states of mixed QD/PTC character. This delocalization enables hole transfer from the QD to PTZ in <300 fs (within the instrument response of the laser system) when linked by PTC, but not when linked by a benzoate group, which has a similar length and conjugation as PTC but does not delocalize the excitonic hole. Comparison of the two systems was aided by quantification of the surface coverage of benzoate and PTC-linked PTZ by (1)H NMR. This work provides direct spectroscopic evidence of the enhancement of the rate of hole extraction from a colloidal QD through covalent linkage of a hole acceptor through an exciton-delocalizing ligand.

Tunable optical and excitonic properties of phosphorene via oxidation

NASA Astrophysics Data System (ADS)

Sadki, S.; Drissi, L. B.

2018-06-01

The optical properties and excitonic wave function of phosphorene oxides (PO) are studied using the first principle many-body Green function and the Bethe–Salpeter equation formalism. In this work, the optical properties are determined using ab initio calculations of the dielectric function. At the long wavelength limit q of EM wave (i.e. ), the dielectric function, the absorption spectrum, the lectivity, the electron energy loss spectra (EELS) and the wave function are calculated. The results show an excitonic binding energy of 818 meV with a bright exciton located in the armchair direction in pristine phosphorene. For PO, the arrangement of the oxygen atoms significantly influences the optical properties. In particular, the absorption spectrum is extended along the solar spectrum, with a high absorption coefficient observed in the dangling structures. The maximum lectivity values are observed for the high energies of the light spectrum. Moreover, the first EELS peak is located in the visible region in all the structures except for one configuration that exhibits the same behavior as pure phosphorene. Finally, the exciton effect reveals that all PO conformers have a dark exciton state, which is suitable for long-lived applications.

Microscopic description of exciton polaritons in direct two-band semiconductors

NASA Astrophysics Data System (ADS)

Nguyen, Van Trong; Mahler, Günter

1999-07-01

Based on a quantum electrodynamical formulation, a microscopic description of exciton polaritons in a two-band semiconductor is presented. We show that the interband exchange Coulomb interaction, responsible for the coupling of the exciton with the longitudinal part of the induced field, should be treated on equal footing together with the coupling to the transverse part of the induced field (the photon field). The constitutive relation is established to connect the current density with the total electric field of polaritons. The classical Maxwell equations are derived from the quantum representation of photons to get a closed system of equations. The temporal evolution for an initial excited exciton state is studied in detail and an anisotropic polariton vacuum Rabi splitting is shown to occur. A number of up-to-now unresolved discrepancies in the literature are clarified.

Effect of confinement potential on exciton diamagnetism in the perspective of constituent carriers in a Quantum Well

NASA Astrophysics Data System (ADS)

Vignesh, G.; Nithiananthi, P.

2018-03-01

Diamagnetic susceptibility of excitons is investigated in the perspective of the electron and hole separation along the lateral (ρ) and normal direction (z) of a GaAs/AlxGa1-xAs quantum well. Using a variational technique, the spatial extensions of these carriers has been observed. The coulomb interaction of the carriers is investigated by subjecting the carriers to three confinement potentials, Square (SQW), Parabolic (PQW) and Triangular Quantum Wells (TQW). The stability of the exciton has been estimated by observing the diamagnetic susceptibility. The hole is very sensitive to confinement potential and has tremendous variations in spatial extension. Among the three confinements, TQW offers more localization and high stability to excitons. The anisotropy of band parameters and the dielectric constants of the well and barrier materials are taken into consideration.

Laser pulse induced multi-exciton dynamics in molecular systems

NASA Astrophysics Data System (ADS)

Wang, Luxia; May, Volkhard

2018-03-01

Ultrafast optical excitation of an arrangement of identical molecules is analyzed theoretically. The computations are particularly dedicated to molecules where the excitation energy into the second excited singlet state E(S 2) - E(S 0) is larger than twice the excitation energy into the first excited singlet state E(S 1) - E(S 0). Then, exciton-exciton annihilation is diminished and resonant and intensive excitation may simultaneously move different molecules into their first excited singlet state | {S}1> . To describe the temporal evolution of the thus created multi-exciton state a direct computation of the related wave function is circumvented. Instead, we derive equations of motion for expectation values formed by different arrangements of single-molecule transition operators | {S}1> < {S}0| . First simulation results are presented and the approximate treatment suggested recently in 2016 Phys. Rev. B 94 195413 is evaluated.

Polarized electrons, trions, and nuclei in charged quantum dots

NASA Astrophysics Data System (ADS)

Bracker, A. S.; Tischler, J. G.; Korenev, V. L.; Gammon, D.

2003-07-01

We have investigated spin polarization in GaAs quantum dots. Excitons and trions are polarized directly by optical excitation and studied through polarization of photoluminescence. Electrons and nuclei are polarized indirectly through subsequent relaxation processes. Polarized electrons are identified by the Hanle effect for exciton and trion photoluminescence, while polarized nuclei are identified through the Overhauser effect in individual charged quantum dots.

Excitons in strongly correlated oxide nanocrystals NicMg1-cO

NASA Astrophysics Data System (ADS)

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

2018-05-01

This paper reports about excitons in strongly correlated oxide nanocrystals NicMg1-cO (c = 0.008 and c = 1). At 8 K two weak peaks were firstly observed in the optical density spectrum of NiO nanocrystals at the energies of 3.510 eV and 3.543 eV. The intensity of the peaks subsides with an increase of temperature and a decrease of nanoparticle sizes from 25 nm to 10 nm. The peaks were attributed to the formation of p-d charge transfer excitons {d9h}. A tunneling annihilation for {d9h} excitons diminishes their lifetime drastically, even at low temperatures. This fact is considered as an inherent feature in the p-d charge transfer excitons {d9h}, which makes them significantly different from the Wannier-Mott excitons for semiconductors with direct allowed transitions. We believe that energy shift between two peaks originates due to the spin-orbit splitting of the top of the valence band, equals 33 meV. In p-d charge transfer photoluminescence excitation spectrum of NicMg1-cO (c = 0.008), we have revealed two [d9h] exciton lines near the charge transfer band edge. Energy shift of these lines (equals 25 meV) is due to the spin-orbit splitting of MgO valence band top.

Size-Dependent Biexciton Quantum Yields and Carrier Dynamics of Quasi-Two-Dimensional Core/Shell Nanoplatelets

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

Ma, Xuedan; Diroll, Benjamin T.; Cho, Wooje

Quasi-two-dimensional nanoplatelets (NPLs) possess fundamentally different excitonic properties from zero-dimensional quantum dots. We study lateral size-dependent photon emission statistics and carrier dynamics of individual NPLs using second-order photon correlation (g( 2)(τ)) spectroscopy and photoluminescence (PL) intensity-dependent lifetime analysis. Room-temperature radiative lifetimes of NPLs can be derived from maximum PL intensity periods in PL time traces. It first decreases with NPL lateral size and then stays constant, deviating from the electric dipole approximation. Analysis of the PL time traces further reveals that the single exciton quantum yield in NPLs decreases with NPL lateral size and increases with protecting shell thickness, indicatingmore » the importance of surface passivation on NPL emission quality. Second-order photon correlation (g( 2)(τ)) studies of single NPLs show that the biexciton quantum yield is strongly dependent on the lateral size and single exciton quantum yield of the NPLs. In large NPLs with unity single exciton quantum yield, the corresponding biexciton quantum yield can reach unity. In conclusion, these findings reveal that by careful growth control and core–shell material engineering, NPLs can be of great potential for light amplification and integrated quantum photonic applications.« less

Size-Dependent Biexciton Quantum Yields and Carrier Dynamics of Quasi-Two-Dimensional Core/Shell Nanoplatelets

DOE PAGES

Ma, Xuedan; Diroll, Benjamin T.; Cho, Wooje; ...

2017-08-08

Quasi-two-dimensional nanoplatelets (NPLs) possess fundamentally different excitonic properties from zero-dimensional quantum dots. We study lateral size-dependent photon emission statistics and carrier dynamics of individual NPLs using second-order photon correlation (g( 2)(τ)) spectroscopy and photoluminescence (PL) intensity-dependent lifetime analysis. Room-temperature radiative lifetimes of NPLs can be derived from maximum PL intensity periods in PL time traces. It first decreases with NPL lateral size and then stays constant, deviating from the electric dipole approximation. Analysis of the PL time traces further reveals that the single exciton quantum yield in NPLs decreases with NPL lateral size and increases with protecting shell thickness, indicatingmore » the importance of surface passivation on NPL emission quality. Second-order photon correlation (g( 2)(τ)) studies of single NPLs show that the biexciton quantum yield is strongly dependent on the lateral size and single exciton quantum yield of the NPLs. In large NPLs with unity single exciton quantum yield, the corresponding biexciton quantum yield can reach unity. In conclusion, these findings reveal that by careful growth control and core–shell material engineering, NPLs can be of great potential for light amplification and integrated quantum photonic applications.« less

Selective excitation of exciton transitions in PTCDA crystals and films

NASA Astrophysics Data System (ADS)

Gangilenka, V. R.; Titova, L. V.; Smith, L. M.; Wagner, H. P.; Desilva, L. A. A.; Gisslén, L.; Scholz, R.

2010-04-01

Photoluminescence excitation studies on 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) single crystals and polycrystalline PTCDA films are compared to the calculated excitonic dispersion deduced from an exciton model including the coupling between Frenkel and charge transfer (CT) excitons along the stacking direction. For excitation energies below the 0-0 Frenkel exciton absorption band at 5 K these measurements enable the selective excitation of several CT states. The CT2 state involving stacked PTCDA molecules reveals two excitation resonances originating from different vibronic sublevels. Moreover, the fundamental transition of the CT1 exciton state delocalized over both basis molecules in the crystal unit cell has been identified from the corresponding excitation resonance. From the excitation energy dependence the fundamental transition energies of the CT2 and CT1 excitons have been deduced to occur at 1.95 and 1.98 eV, respectively. When the excitation energy exceeds ˜2.08eV , we observe a strong emission channel which is related to the indirect minimum of the lowest dispersion branch dominated by Frenkel excitons. Photoluminescence excitation spectroscopy measurements on polycrystalline PTCDA films reveal a strong CT2 signal intensity which is attributed to an increased density of defect-related CT2 states that are preferentially formed by slightly deformed or compressed stacked PTCDA molecules in the vicinity of defects or at grain boundaries. Temperature-dependent PL measurements in polycrystalline PTCDA films between 10 and 300 K at an excitation of 1.88 eV further allow a detailed investigation of the CT2 transition and its vibronic subband.

Magneto-exciton transitions in laterally coupled quantum dots

NASA Astrophysics Data System (ADS)

Barticevic, Zdenka; Pacheco, Monica; Duque, Carlos A.; Oliveira, Luiz E.

2008-03-01

We present a study of the electronic and optical properties of laterally coupled quantum dots. The excitonic spectra of this system under the effects of an external magnetic field applied perpendicular to the plane of the dots is obtained, with the potential of every individual dot taken as the superposition of a quantum well potential along the axial direction with a lateral parabolic confinement potential, and the coupled two- dot system then modeled by a superposition of the potentials of each dot, with their minima at different positions and truncated at the intersection plane. The wave functions and eigenvalues are obtained in the effective-mass approximation by using an extended variational approach in which the magneto- exciton states are simultaneously obtained [1]. The allowed magneto-exciton transitions are investigated by using circularly polarized radiation in the plane perpendicular to the magnetic field. We present results on the excitonic absorption coefficient as a function of the photon energy for different geometric quantum-dot confinement and magnetic-field values. Reference: [1] Z. Barticevic, M. Pacheco, C. A. Duque and L. E. Oliveira, Phys. Rev. B 68, 073312 (2003).

Engineering the Charge Transfer in all 2D Graphene-Nanoplatelets Heterostructure Photodetectors

PubMed Central

Robin, A.; Lhuillier, E.; Xu, X. Z.; Ithurria, S.; Aubin, H.; Ouerghi, A.; Dubertret, B.

2016-01-01

Two dimensional layered (i.e. van der Waals) heterostructures open up great prospects, especially in photodetector applications. In this context, the control of the charge transfer between the constituting layers is of crucial importance. Compared to bulk or 0D system, 2D materials are characterized by a large exciton binding energy (0.1–1 eV) which considerably affects the magnitude of the charge transfer. Here we investigate a model system made from colloidal 2D CdSe nanoplatelets and epitaxial graphene in a phototransistor configuration. We demonstrate that using a heterostructured layered material, we can tune the magnitude and the direction (i.e. electron or hole) of the charge transfer. We further evidence that graphene functionalization by nanocrystals only leads to a limited change in the magnitude of the 1/f noise. These results draw some new directions to design van der Waals heterostructures with enhanced optoelectronic properties. PMID:27143413

Temperature-dependent excitonic effects in the optical properties of single-layer MoS2

NASA Astrophysics Data System (ADS)

Molina-Sánchez, Alejandro; Palummo, Maurizia; Marini, Andrea; Wirtz, Ludger

2016-04-01

Temperature influences the performance of two-dimensional (2D) materials in optoelectronic devices. Indeed, the optical characterization of these materials is usually realized at room temperature. Nevertheless, most ab initio studies are still performed without including any temperature effect. As a consequence, important features are thus overlooked, such as the relative height of the excitonic peaks and their broadening, directly related to the temperature and to the nonradiative exciton relaxation time. We present ab initio calculations of the optical response of single-layer MoS2, a prototype 2D material, as a function of temperature using density functional theory and many-body perturbation theory. We compute the electron-phonon interaction using the full spinorial wave functions, i.e., fully taking into account the effects of spin-orbit interaction. We find that bound excitons (A and B peaks) and resonant excitons (C peak) exhibit different behavior with temperature, displaying different nonradiative linewidths. We conclude that the inhomogeneous broadening of the absorption spectra is mainly due to electron-phonon scattering mechanisms. Our calculations explain the shortcomings of previous (zero-temperature) theoretical spectra and match well with the experimental spectra acquired at room temperature. Moreover, we disentangle the contributions of acoustic and optical phonon modes to the quasiparticles and exciton linewidths. Our model also allows us to identify which phonon modes couple to each exciton state, which is useful for the interpretation of resonant Raman-scattering experiments.

Giant Mechano-Optoelectronic Effect in an Atomically Thin Semiconductor

DOE PAGES

Wu, Wei; Wang, Jin; Ercius, Peter; ...

2018-03-20

Transition metal dichalcogenides (TMDs) are particularly sensitive to mechanical strain as they are capable of experiencing high atomic displacements without nucleating defects to release excess energy. Promising for photonic applications, it has been shown that as TMDs are scaled to a thickness of one monolayer, the photoluminescence response is dramatically enhanced due to the emergence of a direct electronic band gap, compared with multi-layer or bulk TMDs which typically exhibit indirect band gaps. Recently, mechanical strain has also been predicted to enable direct excitonic recombination in these materials, where large changes in the photoluminescence response will occur during an indirect-to-directmore » band gap transition brought on by elastic tensile strain. Here, we demonstrate a two orders of magnitude enhancement in the photoluminescence emission intensity in uniaxially strained single crystalline WSe 2 bilayers. Through a theoretical model which includes experimentally relevant system conditions, we determine this amplification to arise from a significant increase in direct excitonic recombination. Adding confidence to the high levels of elastic strain achieved in this report, we observe strain-independent mode-dependent Grüneisen parameters over the entire range of tensile strain (1– 3.59 %) which were obtained as 1.149±0.027, 0.307±0.061, and 0.357±0.103 for the E 2g, A 1g, and A 2 1g optical phonon modes, respectively. Lastly, these results can inform the predictive strain-engineered design of other atomically thin indirect semiconductors, where a decrease in out-of-plane bonding strength will lead to an increase in the strength of strain-coupled optoelectronic effects.« less

sp-d Exchange Interactions in Wave Function Engineered Colloidal CdSe/Mn:CdS Hetero-Nanoplatelets.

PubMed

Muckel, Franziska; Delikanli, Savas; Hernández-Martínez, Pedro Ludwig; Priesner, Tamara; Lorenz, Severin; Ackermann, Julia; Sharma, Manoj; Demir, Hilmi Volkan; Bacher, Gerd

2018-03-14

In two-dimensional (2D) colloidal semiconductor nanoplatelets, which are atomically flat nanocrystals, the precise control of thickness and composition on the atomic scale allows for the synthesis of heterostructures with well-defined electron and hole wave function distributions. Introducing transition metal dopants with a monolayer precision enables tailored magnetic exchange interactions between dopants and band states. Here, we use the absorption based technique of magnetic circular dichroism (MCD) to directly prove the exchange coupling of magnetic dopants with the band charge carriers in hetero-nanoplatelets with CdSe core and manganese-doped CdS shell (CdSe/Mn:CdS). We show that the strength of both the electron as well as the hole exchange interactions with the dopants can be tuned by varying the nanoplatelets architecture with monolayer accuracy. As MCD is highly sensitive for excitonic resonances, excited level spectroscopy allows us to resolve and identify, in combination with wave function calculations, several excited state transitions including spin-orbit split-off excitonic contributions. Thus, our study not only demonstrates the possibility to expand the extraordinary physical properties of colloidal nanoplatelets toward magneto-optical functionality by transition metal doping but also provides an insight into the excited state electronic structure in this novel two-dimensional material.

Defects activated photoluminescence in two-dimensional semiconductors: interplay between bound, charged, and free excitons

PubMed Central

Tongay, Sefaattin; Suh, Joonki; Ataca, Can; Fan, Wen; Luce, Alexander; Kang, Jeong Seuk; Liu, Jonathan; Ko, Changhyun; Raghunathanan, Rajamani; Zhou, Jian; Ogletree, Frank; Li, Jingbo; Grossman, Jeffrey C.; Wu, Junqiao

2013-01-01

Point defects in semiconductors can trap free charge carriers and localize excitons. The interaction between these defects and charge carriers becomes stronger at reduced dimensionalities, and is expected to greatly influence physical properties of the hosting material. We investigated effects of anion vacancies in monolayer transition metal dichalcogenides as two-dimensional (2D) semiconductors where the vacancies density is controlled by α-particle irradiation or thermal-annealing. We found a new, sub-bandgap emission peak as well as increase in overall photoluminescence intensity as a result of the vacancy generation. Interestingly, these effects are absent when measured in vacuum. We conclude that in opposite to conventional wisdom, optical quality at room temperature cannot be used as criteria to assess crystal quality of the 2D semiconductors. Our results not only shed light on defect and exciton physics of 2D semiconductors, but also offer a new route toward tailoring optical properties of 2D semiconductors by defect engineering. PMID:24029823

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.

Room temperature triplet state spectroscopy of organic semiconductors.

PubMed

Reineke, Sebastian; Baldo, Marc A

2014-01-21

Organic light-emitting devices and solar cells are devices that create, manipulate, and convert excited states in organic semiconductors. It is crucial to characterize these excited states, or excitons, to optimize device performance in applications like displays and solar energy harvesting. This is complicated if the excited state is a triplet because the electronic transition is 'dark' with a vanishing oscillator strength. As a consequence, triplet state spectroscopy must usually be performed at cryogenic temperatures to reduce competition from non-radiative rates. Here, we control non-radiative rates by engineering a solid-state host matrix containing the target molecule, allowing the observation of phosphorescence at room temperature and alleviating constraints of cryogenic experiments. We test these techniques on a wide range of materials with functionalities spanning multi-exciton generation (singlet exciton fission), organic light emitting device host materials, and thermally activated delayed fluorescence type emitters. Control of non-radiative modes in the matrix surrounding a target molecule may also have broader applications in light-emitting and photovoltaic devices.

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.

Direct determination of monolayer MoS2 and WSe2 exciton binding energies on insulating and metallic substrates

NASA Astrophysics Data System (ADS)

Park, Soohyung; Mutz, Niklas; Schultz, Thorsten; Blumstengel, Sylke; Han, Ali; Aljarb, Areej; Li, Lain-Jong; List-Kratochvil, Emil J. W.; Amsalem, Patrick; Koch, Norbert

2018-04-01

Understanding the excitonic nature of excited states in two-dimensional (2D) transition-metal dichalcogenides (TMDCs) is of key importance to make use of their optical and charge transport properties in optoelectronic applications. We contribute to this by the direct experimental determination of the exciton binding energy (E b,exc) of monolayer MoS2 and WSe2 on two fundamentally different substrates, i.e. the insulator sapphire and the metal gold. By combining angle-resolved direct and inverse photoelectron spectroscopy we measure the electronic band gap (E g), and by reflectance measurements the optical excitonic band gap (E exc). The difference of these two energies is E b,exc. The values of E g and E b,exc are 2.11 eV and 240 meV for MoS2 on sapphire, and 1.89 eV and 240 meV for WSe2 on sapphire. On Au E b,exc is decreased to 90 meV and 140 meV for MoS2 and WSe2, respectively. The significant E b,exc reduction is primarily due to a reduction of E g resulting from enhanced screening by the metal, while E exc is barely decreased for the metal support. Energy level diagrams determined at the K-point of the 2D TMDCs Brillouin zone show that MoS2 has more p-type character on Au as compared to sapphire, while WSe2 appears close to intrinsic on both. These results demonstrate that the impact of the dielectric environment of 2D TMDCs is more pronounced for individual charge carriers than for a correlated electron-hole pair, i.e. the exciton. A proper dielectric surrounding design for such 2D semiconductors can therefore be used to facilitate superior optoelectronic device function.

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

Alloying effect on bright-dark exciton states in ternary monolayer Mo x W1-x Se2

NASA Astrophysics Data System (ADS)

Liu, Yanping; Tom, Kyle; Zhang, Xiaowei; Lou, Shuai; Liu, Yin; Yao, Jie

2017-07-01

Binary transition metal dichalcogenides (TMDCs) in the class MX2 (M = Mo, W; X = S, Se) have been widely investigated for potential applications in optoelectronics and nanoelectronics. Recently, alloy-based monolayers of TMDCs have provided a stable and versatile technique to tune the physical properties and optimize them for potential applications. Here, we present experimental evidence for the existence of an intermediate alloy state between the MoSe2-like and the WSe2-like behavior of the neutral exciton (X 0) using temperature-dependent photoluminescence (PL) of the monolayer Mo x W1-x Se2 alloy. The existence of a maximum PL intensity around 120 K can be explained by the competition between the thermally activated bright states and the non-radiative quenching of the bright states. Moreover, we also measured localized exciton (XB ) PL peak in the alloy and the observed behavior agrees well with a model previously proposed for the 3D case, which indicates the theory also applies to 2D systems. Our results not only shed light on bright-dark states and localized exciton physics of 2D semiconductors, but also offer a new route toward the control of the bright-dark transition and tailoring optical properties of 2D semiconductors through defect engineering.

Engineering light emission of two-dimensional materials in both the weak and strong coupling regimes

NASA Astrophysics Data System (ADS)

Brotons-Gisbert, Mauro; Martínez-Pastor, Juan P.; Ballesteros, Guillem C.; Gerardot, Brian D.; Sánchez-Royo, Juan F.

2018-01-01

Two-dimensional (2D) materials have promising applications in optoelectronics, photonics, and quantum technologies. However, their intrinsically low light absorption limits their performance, and potential devices must be accurately engineered for optimal operation. Here, we apply a transfer matrix-based source-term method to optimize light absorption and emission in 2D materials and related devices in weak and strong coupling regimes. The implemented analytical model accurately accounts for experimental results reported for representative 2D materials such as graphene and MoS2. The model has been extended to propose structures to optimize light emission by exciton recombination in MoS2 single layers, light extraction from arbitrarily oriented dipole monolayers, and single-photon emission in 2D materials. Also, it has been successfully applied to retrieve exciton-cavity interaction parameters from MoS2 microcavity experiments. The present model appears as a powerful and versatile tool for the design of new optoelectronic devices based on 2D semiconductors such as quantum light sources and polariton lasers.

Exciton-polaritons in cuprous oxide: Theory and comparison with experiment

NASA Astrophysics Data System (ADS)

Schweiner, Frank; Ertl, Jan; Main, Jörg; Wunner, Günter; Uihlein, Christoph

2017-12-01

The observation of giant Rydberg excitons in cuprous oxide (Cu2O ) up to a principal quantum number of n =25 by T. Kazimierczuk et al. [Nature (London) 514, 343 (2014), 10.1038/nature13832] inevitably raises the question whether these quasiparticles must be described within a multipolariton framework since excitons and photons are always coupled in the solid. In this paper we present the theory of exciton-polaritons in Cu2O . To this end we extend the Hamiltonian which includes the complete valence-band structure, the exchange interaction, and the central-cell corrections effects, and which has been recently deduced by F. Schweiner et al. [Phys. Rev. B 95, 195201 (2017), 10.1103/PhysRevB.95.195201], for finite values of the exciton momentum ℏ K . We derive formulas to calculate not only dipole but also quadrupole oscillator strengths when using the complete basis of F. Schweiner et al., which has recently been proven as a powerful tool to calculate exciton spectra. Very complex polariton spectra for the three orientations of K along the axes [001 ] , [110 ] , and [111 ] of high symmetry are obtained and a strong mixing of exciton states is reported. The main focus is on the 1 S ortho-exciton-polariton, for which pronounced polariton effects have been measured in experiments. We set up a 5 ×5 matrix model, which accounts for both the polariton effect and the K -dependent splitting, and which allows treating the anisotropic polariton dispersion for any direction of K . We especially discuss the dispersions for K being oriented in the planes perpendicular to [1 1 ¯0 ] and [111 ] , for which experimental transmission spectra have been measured. Furthermore, we compare our results with experimental values of the K -dependent splitting, the group velocity, and the oscillator strengths of this exciton-polariton. The results are in good agreement. This proves the validity of the 5 ×5 matrix model as a useful theoretical model for further investigations on the 1 S ortho-exciton-polariton.

Charge-transfer contributions to the excitonic coupling matrix element in BODIPY-based energy transfer cassettes

NASA Astrophysics Data System (ADS)

Spiegel, J. Dominik; Lyskov, Igor; Kleinschmidt, Martin; Marian, Christel M.

2017-01-01

BODIPY-based dyads serve as model systems for the investigation of excitation energy transfer (EET). Through-space EET is brought about by direct and exchange interactions between the transition densities of donor and acceptor localized states. The presence of a molecular linker gives rise to additional charge transfer (CT) contributions. Here, we present a novel approach for the calculation of the excitonic coupling matrix element (ECME) including CT contributions which is based on supermolecular one-electron transition density matrices (STD). The validity of the approach is assessed for a model system of two π -stacked ethylene molecules at varying intermolecular separation. Wave functions and electronic excitation energies of five EET cassettes comprising anthracene as exciton donor and BODIPY as exciton acceptor are obtained by the redesigned combined density functional theory and multireference configuration interaction (DFT/MRCI-R) method. CT contributions to the ECME are shown to be important in the covalently linked EET cassettes.

Valley excitons in two-dimensional semiconductors

DOE PAGES

Yu, Hongyi; Cui, Xiaodong; Xu, Xiaodong; ...

2014-12-30

Monolayer group-VIB transition metal dichalcogenides have recently emerged as a new class of semiconductors in the two-dimensional limit. The attractive properties include: the visible range direct band gap ideal for exploring optoelectronic applications; the intriguing physics associated with spin and valley pseudospin of carriers which implies potentials for novel electronics based on these internal degrees of freedom; the exceptionally strong Coulomb interaction due to the two-dimensional geometry and the large effective masses. The physics of excitons, the bound states of electrons and holes, has been one of the most actively studied topics on these two-dimensional semiconductors, where the excitons exhibitmore » remarkably new features due to the strong Coulomb binding, the valley degeneracy of the band edges, and the valley dependent optical selection rules for interband transitions. Here we give a brief overview of the experimental and theoretical findings on excitons in two-dimensional transition metal dichalcogenides, with focus on the novel properties associated with their valley degrees of freedom.« less

Direct observation of ultrafast coherent exciton dynamics in helical π-stacks of self-assembled perylene bisimides

PubMed Central

Sung, Jooyoung; Kim, Pyosang; Fimmel, Benjamin; Würthner, Frank; Kim, Dongho

2015-01-01

Ever since the discovery of dye self-assemblies in nature, there have been tremendous efforts to exploit biomimetic supramolecular assemblies for tailored artificial photon processing materials. This feature necessarily has resulted in an increasing demand for understanding exciton dynamics in the dye self-assemblies. In a sharp contrast with J-type aggregates, however, the detailed observation of exciton dynamics in H-type aggregates has remained challenging. In this study, as we succeed in measuring transient fluorescence from Frenkel state of π-stacked perylene tetracarboxylic acid bisimide dimer and oligomer aggregates, we present an experimental demonstration on Frenkel exciton dynamics of archetypal columnar π–π stacks of dyes. The analysis of the vibronic peak ratio of the transient fluorescence spectra reveals that unlike the simple π-stacked dimer, the photoexcitation energy in the columnar π-stacked oligomer aggregates is initially delocalized over at least three molecular units and moves coherently along the chain in tens of femtoseconds, preceding excimer formation process. PMID:26492820

Magnetoreflection spectroscopy of monolayer transition-metal dichalcogenide semiconductors in pulsed magnetic fields

DOE PAGES

Stier, Andreas V.; McCreary, Kathleen M.; Jonker, Berend T.; ...

2016-05-13

The authors describe recent experimental efforts to perform polarization-resolved optical spectroscopy of monolayer transition-metal dichalcogenide semiconductors in very large pulsed magnetic fields to 65 T. The experimental setup and technical challenges are discussed in detail, and temperature-dependent magnetoreflection spectra from atomically thin tungsten disulphide are presented. The data clearly reveal not only the valley Zeeman effect in these two-dimensional semiconductors but also the small quadratic exciton diamagnetic shift from which the very small exciton size can be directly inferred. Lastly, the authors present model calculations that demonstrate how the measured diamagnetic shifts can be used to constrain estimates of themore » exciton binding energy in this new family of monolayer semiconductors.« less

Quasiparticle and excitonic gaps of one-dimensional carbon chains.

PubMed

Mostaani, E; Monserrat, B; Drummond, N D; Lambert, C J

2016-06-01

We report diffusion quantum Monte Carlo (DMC) calculations of the quasiparticle and excitonic gaps of hydrogen-terminated oligoynes and extended polyyne. The electronic gaps are found to be very sensitive to the atomic structure in these systems. We have therefore optimised the geometry of polyyne by directly minimising the DMC energy with respect to the lattice constant and the Peierls-induced carbon-carbon bond-length alternation. We find the bond-length alternation of polyyne to be 0.136(2) Å and the excitonic and quasiparticle gaps to be 3.30(7) and 3.4(1) eV, respectively. The DMC zone-centre longitudinal optical phonon frequency of polyyne is 2084(5) cm(-1), which is consistent with Raman spectroscopic measurements for large oligoynes.

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.

Electromodulation spectroscopy of excitons in simple cubic TlCl and TlBr

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

McClelland, J.F.; Lynch, D.W.

1979-03-15

Transmission and electromodulated transmission spectra have been measured in the direct Wannier exciton region for TlCl and TlBr. The spectra were obtained at a sample temperature between 5 and 6 K for a range of applied electric fields. The data have been reduced to obtain the electric-field-induced changes in the dielectric function and compared in detail to the calculations of Blossey. The experimental results support the trends predicted by the calculations.

Light-hole quantization in the optical response of ultra-wide GaAs/Al(x)Ga(1-x)As quantum wells.

PubMed

Solovyev, V V; Bunakov, V A; Schmult, S; Kukushkin, I V

2013-01-16

Temperature-dependent reflectivity and photoluminescence spectra are studied for undoped ultra-wide 150 and 250 nm GaAs quantum wells. It is shown that spectral features previously attributed to a size quantization of the exciton motion in the z-direction coincide well with energies of quantized levels for light holes. Furthermore, optical spectra reveal very similar properties at temperatures above the exciton dissociation point.

Optical properties of a-plane (Al, Ga)N/GaN multiple quantum wells grown on strain engineered Zn1-xMgxO layers by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Xia, Y.; Brault, J.; Nemoz, M.; Teisseire, M.; Vinter, B.; Leroux, M.; Chauveau, J.-M.

2011-12-01

Nonpolar (112¯0) Al0.2Ga0.8N/GaN multiple quantum wells (MQWs) have been grown by molecular beam epitaxy on (112¯0) Zn0.74Mg0.26O templates on r-plane sapphire substrates. The quantum wells exhibit well-resolved photoluminescence peaks in the ultra-violet region, and no sign of quantum confined Stark effect is observed in the complete multiple quantum well series. The results agree well with flat band quantum well calculations. Furthermore, we show that the MQW structures are strongly polarized along the [0001] direction. The origin of the polarization is discussed in terms of the strain anisotropy dependence of the exciton optical oscillator strengths.

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.

Crystallochromy of perylene pigments: Interference between Frenkel excitons and charge-transfer states

NASA Astrophysics Data System (ADS)

Gisslén, Linus; Scholz, Reinhard

2009-09-01

The optical properties of perylene-based pigments are arising from the interplay between neutral molecular excitations and charge transfer between adjacent molecules. In the crystalline phase, these excitations are coupled via electron and hole transfer, two quantities relating directly to the width of the conduction and valence band in the crystalline phase. Based on the crystal structure determined by x-ray diffraction, density-functional theory (DFT) and Hartree-Fock are used for the calculation of the electronic states of a dimer of stacked molecules. The resulting transfer parameters for electron and hole are used in an exciton model for the coupling between Frenkel excitons and charge-transfer states. The deformation of the positively or negatively charged molecular ions with respect to the neutral ground state is calculated with DFT and the geometry in the optically excited state is deduced from time-dependent DFT and constrained DFT. All of these deformations are interpreted in terms of the elongation of an effective internal vibration which is used subsequently in the exciton model for the crystalline phase. A comparison between the calculated dielectric function and the observed optical spectra allows to deduce the relative energetic position of Frenkel excitons and the charge-transfer state involving stack neighbors, a key parameter for various electronic and optoelectronic device applications. For five out of six perylene pigments studied in the present work, this exciton model results in excellent agreement between calculated and observed optical properties.

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.

Creation of Excitons Excited by Light with a Spatial Mode

NASA Astrophysics Data System (ADS)

Syouji, Atsushi; Saito, Shingo; Otomo, Akira

2017-12-01

When light is absorbed into matter, its degrees of freedom (i.e., energy, polarization, and phase) are transferred to the matter and conserved. In this study, we demonstrate that elementary excitations in matter, which are one-photon-forbidden transition states, become allowed states because of the phase conservation across the entire cross section of excitation light. In particular, when 1S orthoexcitons of the yellow series in the semiconductor cuprous oxide (Cu2O) were resonantly excited by light with a spatial mode, an increase in the Γ 3 - -phonon-emission peak intensity of the excitons was detected depending on the spatial mode. Using group-theory-based analysis, we show that the irreducible representation of a one-photon-forbidden exciton, which is one of the orthoexcitons, can be transmuted to an allowed state by taking the direct product with the polar vector produced from the spatial mode of the light. Although the transition process of the exciton is locally characterized by the usual quadrupole interaction, the phase conservation at each position at which the sample is irradiated causes the exciton to be in the same spatial-mode state. That causes a change in the transition selection rule. The selection rule relaxation due to the spatial mode of the light was also applied for paraexciton creation.

electric dipole superconductor in bilayer exciton system

NASA Astrophysics Data System (ADS)

Sun, Qing-Feng; Jiang, Qing-Dong; Bao, Zhi-Qiang; Xie, X. C.

Recently, it was reported that the bilayer exciton systems could exhibit many new phenomena, including the large bilayer counterflow conductivity, the Coulomb drag, etc. These phenomena imply the formation of exciton condensate superfluid state. On the other hand, it is now well known that the superconductor is the condensate superfluid state of the Cooper pairs, which can be viewed as electric monopoles. In other words, the superconductor state is the electric monopole condensate superfluid state. Thus, one may wonder whether there exists electric dipole superfluid state. In this talk, we point out that the exciton in a bilayer system can be considered as a charge neutral electric dipole. And we derive the London-type and Ginzburg-Landau-type equations of electric dipole superconductivity. From these equations, we discover the Meissner-type effect (against spatial variation of magnetic fields), and the dipole current Josephson effect. The frequency in the AC Josephson effect of the dipole current is equal to that in the normal (monopole) superconductor. These results can provide direct evidence for the formation of exciton superfluid state in the bilayer systems and pave new ways to obtain the electric dipole current. We gratefully acknowledge the financial support by NBRP of China (2012CB921303 and 2015CB921102) and NSF-China under Grants Nos. 11274364 and 11574007.

Single nanowire extinction spectroscopy.

PubMed

Giblin, Jay; Vietmeyer, Felix; McDonald, Matthew P; Kuno, Masaru

2011-08-10

Here we show the first direct extinction spectra of single one-dimensional (1D) semiconductor nanostructures obtained at room temperature utilizing a spatial modulation approach. (1) For these materials, ensemble averaging in conventional extinction spectroscopy has limited our understanding of the interplay between carrier confinement and their electrostatic interactions. (2-4) By probing individual CdSe nanowires (NWs), we have identified and assigned size-dependent exciton transitions occurring across the visible. In turn, we have revealed the existence of room temperature 1D excitons in the narrowest NWs.

Coherent quantum dynamics launched by incoherent relaxation in a quantum circuit simulator of a light-harvesting complex

NASA Astrophysics Data System (ADS)

Chin, A. W.; Mangaud, E.; Atabek, O.; Desouter-Lecomte, M.

2018-06-01

Engineering and harnessing coherent excitonic transport in organic nanostructures has recently been suggested as a promising way towards improving manmade light-harvesting materials. However, realizing and testing the dissipative system-environment models underlying these proposals is presently very challenging in supramolecular materials. A promising alternative is to use simpler and highly tunable "quantum simulators" built from programmable qubits, as recently achieved in a superconducting circuit by Potočnik et al. [A. Potočnik et al., Nat. Commun. 9, 904 (2018), 10.1038/s41467-018-03312-x]. We simulate the real-time dynamics of an exciton coupled to a quantum bath as it moves through a network based on the quantum circuit of Potočnik et al. Using the numerically exact hierarchical equations of motion to capture the open quantum system dynamics, we find that an ultrafast but completely incoherent relaxation from a high-lying "bright" exciton into a doublet of closely spaced "dark" excitons can spontaneously generate electronic coherences and oscillatory real-space motion across the network (quantum beats). Importantly, we show that this behavior also survives when the environmental noise is classically stochastic (effectively high temperature), as in present experiments. These predictions highlight the possibilities of designing matched electronic and spectral noise structures for robust coherence generation that do not require coherent excitation or cold environments.

Visualization of defect-induced excitonic properties of the edges and grain boundaries in synthesized monolayer molybdenum disulfide

NASA Astrophysics Data System (ADS)

Newaz, Akm; Yore, A. E.; Miller, A.; Crumrine, W.; Redd, B.; Tuck, J. A.; Wang, Bin; Smithe, K. K. H.; Pop, E.

Understanding nanoscale optical behavior of the edges and grain boundaries of synthetically grown transition metal dichalcogenides (TMDCs) is vital for optimizing their optoelectronic properties. Here we present our experimental work on spatial photoluminescence (PL) scanning of large size (>= 50 μ m) monolayer MoS2 grown by chemical vapor deposition (CVD) using a diffraction limited blue laser beam spot (wavelength 405 nm) with a beam diameter as small as 200 nm allowing us to probe nanoscale excitonic phenomena which was not observed before. We have found several important features: (i) there exists a sub-micron width strip ( 500 nm) along the edges that fluoresces 1000 % brighter than the region far inside; (ii) there is another brighter wide region consisting of parallel fluorescing lines ending at the corners of the zig-zag peripheral edges; (iii) there is a giant blue shifted A-excitonic peak, as large as 120 meV, in the PL spectra from the edges. Using density functional theory calculations, we attribute this giant blue shift to the adsorption of oxygen dimers at the edges, which reduces the excitonic binding energy. Our results offer an attractive route to tailor optical properties at the TMDC edges through defect engineering. AFOSR Grant FA9550-14-1-0251, NSF EFRI 2-DARE Grant 1542883, NSF Graduate Research Fellowship under Grant DGE-114747.

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

Two-dimensional multiferroics in monolayer group IV monochalcogenides

NASA Astrophysics Data System (ADS)

Wang, Hua; Qian, Xiaofeng

2017-03-01

Low-dimensional multiferroic materials hold great promises in miniaturized device applications such as nanoscale transducers, actuators, sensors, photovoltaics, and nonvolatile memories. Here, using first-principles theory we predict that two-dimensional (2D) monolayer group IV monochalcogenides including GeS, GeSe, SnS, and SnSe are a class of 2D semiconducting multiferroics with giant strongly-coupled in-plane spontaneous ferroelectric polarization and spontaneous ferroelastic lattice strain that are thermodynamically stable at room temperature and beyond, and can be effectively modulated by elastic strain engineering. Their optical absorption spectra exhibit strong in-plane anisotropy with visible-spectrum excitonic gaps and sizable exciton binding energies, rendering the unique characteristics of low-dimensional semiconductors. More importantly, the predicted low domain wall energy and small migration barrier together with the coupled multiferroic order and anisotropic electronic structures suggest their great potentials for tunable multiferroic functional devices by manipulating external electrical, mechanical, and optical field to control the internal responses, and enable the development of four device concepts including 2D ferroelectric memory, 2D ferroelastic memory, and 2D ferroelastoelectric nonvolatile photonic memory as well as 2D ferroelectric excitonic photovoltaics.

Polarization of stacking fault related luminescence in GaN nanorods

NASA Astrophysics Data System (ADS)

Pozina, G.; Forsberg, M.; Serban, E. A.; Hsiao, C.-L.; Junaid, M.; Birch, J.; Kaliteevski, M. A.

2017-01-01

Linear polarization properties of light emission are presented for GaN nanorods (NRs) grown along [0001] direction on Si(111) substrates by direct-current magnetron sputter epitaxy. The near band gap photoluminescence (PL) measured at low temperature for a single NR demonstrated an excitonic line at ˜3.48 eV and the stacking faults (SFs) related transition at ˜3.43 eV. The SF related emission is linear polarized in direction perpendicular to the NR growth axis in contrast to a non-polarized excitonic PL. The results are explained in the frame of the model describing basal plane SFs as polymorphic heterostructure of type II, where anisotropy of chemical bonds at the interfaces between zinc blende and wurtzite GaN subjected to in-built electric field is responsible for linear polarization parallel to the interface planes.

Nature of exciton transitions in hexagonal boron nitride

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

Li, J.; Cao, X. K.; Lin, J. Y.

2016-03-21

In contrast to other III-nitride semiconductors GaN and AlN, the intrinsic (or free) exciton transition in hexagonal boron nitride (h-BN) consists of rather complex fine spectral features (resolved into six sharp emission peaks) and the origin of which is still unclear. Here, the free exciton transition (FX) in h-BN bulk crystals synthesized by a solution method at atmospheric pressure has been probed by deep UV time-resolved photoluminescence (PL) spectroscopy. Based on the separations between the energy peak positions of the FX emission lines, the identical PL decay kinetics among different FX emission lines, and the known phonon modes in h-BN,more » we suggest that there is only one principal emission line corresponding to the direct intrinsic FX transition in h-BN, whereas all other fine features are a result of phonon-assisted transitions. The identified phonon modes are all associated with the center of the Brillouin zone. Our results offer a simple picture for the understanding of the fundamental exciton transitions in h-BN.« less

Quantum Yield of Single Surface Plasmons Generated by a Quantum Dot Coupled with a Silver Nanowire.

PubMed

Li, Qiang; Wei, Hong; Xu, Hongxing

2015-12-09

The interactions between surface plasmons (SPs) in metal nanostructures and excitons in quantum emitters (QEs) lead to many interesting phenomena and potential applications that are strongly dependent on the quantum yield of SPs. The difficulty in distinguishing all the possible exciton recombination channels hinders the experimental determination of SP quantum yield. Here, we experimentally measured for the first time the quantum yield of single SPs generated by the exciton-plasmon coupling in a system composed of a single quantum dot and a silver nanowire (NW). By utilizing the SP guiding property of the NW, the decay rates of all the exciton recombination channels, i.e., direct free space radiation channel, SP generation channel, and nonradiative damping channel, are quantitatively obtained. It is determined that the optimum emitter-NW coupling distance for the largest SP quantum yield is about 10 nm, resulting from the different distance-dependent decay rates of the three channels. These results are important for manipulating the coupling between plasmonic nanostructures and QEs and developing on-chip quantum plasmonic devices for potential nanophotonic and quantum information applications.

Exciton-polariton state in nanocrystalline SiC films

NASA Astrophysics Data System (ADS)

Semenov, A. V.; Lopin, A. V.

2016-05-01

We studied the features of optical absorption in the films of nanocrystalline SiC (nc-SiC) obtained on the sapphire substrates by the method of direct ion deposition. The optical absorption spectra of the films with a thickness less than ~500 nm contain a maximum which position and intensity depend on the structure and thickness of the nc-SiC films. The most intense peak at 2.36 eV is observed in the nc-SiC film with predominant 3C-SiC polytype structure and a thickness of 392 nm. Proposed is a resonance absorption model based on excitation of exciton polaritons in a microcavity. In the latter, under the conditions of resonance, there occurs strong interaction between photon modes of light with λph=521 nm and exciton of the 3С polytype with an excitation energy of 2.36 eV that results in the formation of polariton. A mismatch of the frequencies of photon modes of the cavity and exciton explains the dependence of the maximum of the optical absorption on the film thickness.

Strongly bound excitons in anatase TiO 2 single crystals and nanoparticles

DOE PAGES

Baldini, E.; Chiodo, L.; Dominguez, A.; ...

2017-04-13

Anatase TiO 2 is among the most studied materials for light-energy conversion applications, but the nature of its fundamental charge excitations is still unknown. Yet it is crucial to establish whether light absorption creates uncorrelated electron-hole pairs or bound excitons and, in the latter case, to determine their character. Here, by combining steady-state angle-resolved photoemission spectroscopy and spectroscopic ellipsometry with state-of-the-art ab initio calculations, we demonstrate that the direct optical gap of single crystals is dominated by a strongly bound exciton rising over the continuum of indirect interband transitions. This exciton possesses an intermediate character between the Wannier-Mott and Frenkelmore » regimes and displays a peculiar two-dimensional wavefunction in the three-dimensional lattice. The nature of the higher-energy excitations is also identified. Furthermore, the universal validity of our results is confirmed up to room temperature by observing the same elementary excitations in defect-rich samples (doped single crystals and nanoparticles) via ultrafast two-dimensional deep-ultraviolet spectroscopy.« less

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.

Defects Enable Dark Exciton Photoluminescence in Single-Walled Carbon Nanotubes

DOE PAGES

Amori, Amanda R.; Rossi, Jamie E.; Landi, Brian J.; ...

2018-01-24

Variable temperature photoluminescence excitation spectroscopy of three (n,m) species of single-walled carbon nanotubes revealed that at resonant S 22 excitation, in addition to allowed excitonic optical transitions, several sidebands that should be forbidden based on selection rules were observed and appeared to have a strong temperature dependence. In particular, we found that a sideband located approximately 130 meV away from the bright S 11 exciton peak relating to the K-momentum dark exciton state, called X 1, decreased in intensity five-fold as the samples were cooled. Direct optical excitation of this dark state is nominally forbidden, thus calling into question howmore » the state is populated, and why it is so prominent in the photoluminescence spectrum. Interestingly, the ratio of the integrated photoluminescence intensities of X 1 to S 11 scales with a Boltzmann factor unrelated to the phonon that is thought to be responsible for depopulating the K-momentum dark exciton state: an in-plane transverse optical phonon, A 1’. Furthermore, photoluminescence spectra from individual (7,5) nanotubes show that only a small fraction exhibit the X 1 feature, with varying oscillator strength, thus suggesting that intrinsic processes such as phonon scattering are not responsible for populating the dark state. Alternatively, we suggest that populating the K-momentum dark exciton state requires scattering from defects, which is consistent with the increased magnitude of the X 1 feature for samples with increased sample purification and processing. Thus, the presence of an X 1 peak in photoluminescence is an extremely sensitive spectroscopic indicator of defects on single-walled carbon nanotubes.« less

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.

Optical signature of Mg-doped GaN: Transfer processes

NASA Astrophysics Data System (ADS)

Callsen, G.; Wagner, M. R.; Kure, T.; Reparaz, J. S.; Bügler, M.; Brunnmeier, J.; Nenstiel, C.; Hoffmann, A.; Hoffmann, M.; Tweedie, J.; Bryan, Z.; Aygun, S.; Kirste, R.; Collazo, R.; Sitar, Z.

2012-08-01

Mg doping of high quality, metal organic chemical vapor deposition grown GaN films results in distinct traces in their photoluminescence and photoluminescence excitation spectra. We analyze GaN:Mg grown on sapphire substrates and identify two Mg related acceptor states, one additional acceptor state and three donor states that are involved in the donor-acceptor pair band transitions situated at 3.26-3.29 eV in GaN:Mg. The presented determination of the donor-acceptor pair band excitation channels by photoluminescence excitation spectroscopy in conjunction with temperature-dependent photoluminescence measurements results in a direct determination of the donor and acceptor binding, localization, and activation energies, which is put into a broader context based on Haynes's rule. Furthermore, we analyze the biexponential decay dynamics of the photoluminescence signal of the acceptor and donor bound excitons. As all observed lifetimes scale with the localization energy of the donor and acceptor related bound excitons, defect and complex bound excitons can be excluded as their origin. Detailed analysis of the exciton transfer processes in the close energetic vicinity of the GaN band edge reveals excitation via free and bound excitonic channels but also via an excited state as resolved for the deepest localized Mg related acceptor bound exciton. For the two Mg acceptor states, we determine binding energies of 164 ± 5 and 195 ± 5 meV, which is in good agreement with recent density functional theory results. This observation confirms and quantifies the general dual nature of acceptor states in GaN based on the presented analysis of the photoluminescence and photoluminescence excitation spectra.

Defects Enable Dark Exciton Photoluminescence in Single-Walled Carbon Nanotubes

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

Amori, Amanda R.; Rossi, Jamie E.; Landi, Brian J.

Variable temperature photoluminescence excitation spectroscopy of three (n,m) species of single-walled carbon nanotubes revealed that at resonant S 22 excitation, in addition to allowed excitonic optical transitions, several sidebands that should be forbidden based on selection rules were observed and appeared to have a strong temperature dependence. In particular, we found that a sideband located approximately 130 meV away from the bright S 11 exciton peak relating to the K-momentum dark exciton state, called X 1, decreased in intensity five-fold as the samples were cooled. Direct optical excitation of this dark state is nominally forbidden, thus calling into question howmore » the state is populated, and why it is so prominent in the photoluminescence spectrum. Interestingly, the ratio of the integrated photoluminescence intensities of X 1 to S 11 scales with a Boltzmann factor unrelated to the phonon that is thought to be responsible for depopulating the K-momentum dark exciton state: an in-plane transverse optical phonon, A 1’. Furthermore, photoluminescence spectra from individual (7,5) nanotubes show that only a small fraction exhibit the X 1 feature, with varying oscillator strength, thus suggesting that intrinsic processes such as phonon scattering are not responsible for populating the dark state. Alternatively, we suggest that populating the K-momentum dark exciton state requires scattering from defects, which is consistent with the increased magnitude of the X 1 feature for samples with increased sample purification and processing. Thus, the presence of an X 1 peak in photoluminescence is an extremely sensitive spectroscopic indicator of defects on single-walled carbon nanotubes.« less

Direct observation of the lowest indirect exciton state in the bulk of hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Schuster, R.; Habenicht, C.; Ahmad, M.; Knupfer, M.; Büchner, B.

2018-01-01

We combine electron energy-loss spectroscopy and first-principles calculations based on density-functional theory (DFT) to identify the lowest indirect exciton state in the in-plane charge response of hexagonal boron nitride (h-BN) single crystals. This remarkably sharp mode forms a narrow pocket with a dispersion bandwidth of ˜100 meV and, as we argue based on a comparison to our DFT calculations, is predominantly polarized along the Γ K direction of the hexagonal Brillouin zone. Our data support the recent report by Cassabois et al. [Nat. Photonics 10, 262 (2016), 10.1038/nphoton.2015.277] who indirectly inferred the existence of this mode from the photoluminescence signal, thereby establishing h-BN as an indirect semiconductor.

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.

Multiple Exciton Generation in Colloidal Nanocrystals

PubMed Central

Smith, Charles; Binks, David

2013-01-01

In a conventional solar cell, the energy of an absorbed photon in excess of the band gap is rapidly lost as heat, and this is one of the main reasons that the theoretical efficiency is limited to ~33%. However, an alternative process, multiple exciton generation (MEG), can occur in colloidal quantum dots. Here, some or all of the excess energy is instead used to promote one or more additional electrons to the conduction band, potentially increasing the photocurrent of a solar cell and thereby its output efficiency. This review will describe the development of this field over the decade since the first experimental demonstration of multiple exciton generation, including the controversies over experimental artefacts, comparison with similar effects in bulk materials, and the underlying mechanisms. We will also describe the current state-of-the-art and outline promising directions for further development. PMID:28348283

Colloidal InP/ZnS core shell nanocrystals studied by linearly and circularly polarized photoluminescence

NASA Astrophysics Data System (ADS)

Langof, L.; Fradkin, L.; Ehrenfreund, E.; Lifshitz, E.; Micic, O. I.; Nozik, A. J.

2004-02-01

The magneto-optical properties of InP/ZnS core-shell nanocrystals (NCs) were investigated by measuring the degree of linear and circular polarization of photoluminescence (PL) spectra, in the presence of an external magnetic field under resonant or non-resonant excitation. The linearly polarized PL data strongly indicate that InP/ZnS NCs have a prolongated shape. The resonant-excited circularly polarized PL decay curves indicate that the spin relaxation time of the studied samples is shorter than the radiative lifetime of their exciton. Furthermore, the magnetic field-induced circularly polarized PL process reveals an exciton g factor ( gex) of 0.55. Thus, such studies may serve as a tool to directly estimate the NC's shape anisotropy and to determine the g-factor of charge carriers and excitons in those NCs.

Strain-engineered growth of two-dimensional materials

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

Ahn, Geun Ho; Amani, Matin; Rasool, Haider

The application of strain to semiconductors allows for controlled modification of their band structure. This principle is employed for the manufacturing of devices ranging from high-performance transistors to solid-state lasers. Traditionally, strain is typically achieved via growth on lattice-mismatched substrates. For two-dimensional (2D) semiconductors, this is not feasible as they typically do not interact epitaxially with the substrate. Here in this paper, we demonstrate controlled strain engineering of 2D semiconductors during synthesis by utilizing the thermal coefficient of expansion mismatch between the substrate and semiconductor. Using WSe 2 as a model system, we demonstrate stable built-in strains ranging from 1%more » tensile to 0.2% compressive on substrates with different thermal coefficient of expansion. Consequently, we observe a dramatic modulation of the band structure, manifested by a strain-driven indirect-to-direct bandgap transition and brightening of the dark exciton in bilayer and monolayer WSe 2, respectively. The growth method developed here should enable flexibility in design of more sophisticated devices based on 2D materials.« less

Strain-engineered growth of two-dimensional materials

DOE PAGES

Ahn, Geun Ho; Amani, Matin; Rasool, Haider; ...

2017-09-20

The application of strain to semiconductors allows for controlled modification of their band structure. This principle is employed for the manufacturing of devices ranging from high-performance transistors to solid-state lasers. Traditionally, strain is typically achieved via growth on lattice-mismatched substrates. For two-dimensional (2D) semiconductors, this is not feasible as they typically do not interact epitaxially with the substrate. Here in this paper, we demonstrate controlled strain engineering of 2D semiconductors during synthesis by utilizing the thermal coefficient of expansion mismatch between the substrate and semiconductor. Using WSe 2 as a model system, we demonstrate stable built-in strains ranging from 1%more » tensile to 0.2% compressive on substrates with different thermal coefficient of expansion. Consequently, we observe a dramatic modulation of the band structure, manifested by a strain-driven indirect-to-direct bandgap transition and brightening of the dark exciton in bilayer and monolayer WSe 2, respectively. The growth method developed here should enable flexibility in design of more sophisticated devices based on 2D materials.« less

Non-resonant excitation of rare-earth ions via virtual Auger process

NASA Astrophysics Data System (ADS)

Yassievich, I. N.

2011-05-01

The luminescence of rare-earth ions (REI) is often intensified by defects associated with REIs or excitons bound to these defects. In this paper we show that the presence of such a state opens the possibility of non-resonance optical pumping via the process involving virtual Auger transition. It is the second order perturbation process when an electron arrives in an virtual intermediate state due to the optical transition (the first step) and the Auger transition is the second one. We have calculated the cross-section of such an excitation process when the optical transition is accompanied by creation of the exciton bound to the defect associated with REI and obtained a simple analytical expression for the cross-section. The excess energy of the excitation quanta is taken away by multiphonon emission. The electron-phonon interaction with local phonon vibrations of the bound exciton is assumed to determine the multiphonon process. It is shown that the probability of the process under study exceeds considerably the probability of direct optical 4f-4f absorption even in the case when the energy distance between the excitation quantum energy and the exciton energy is about 0.1 of the exciton energy. The excitation mechanism considered leads to the appearance of a broad unsymmetrical band in the excitation spectrum with the red side much wider and flatter than the blue one.

Rabi like angular splitting in Surface Plasmon Polariton - Exciton interaction in ATR configuration

NASA Astrophysics Data System (ADS)

Hassan, Heba; Abdallah, T.; Negm, S.; Talaat, H.

2018-05-01

We have studied the coupling of propagating Surface Plasmon Polaritons (SPP) on silver films and excitons in CdS quantum dots (QDs). We employed the Kretschmann-Raether configuration of the attenuated total reflection (ATR) to propagate the SPP on silver film of thickness 47.5 nm at three different wavelengths. The CdS QD have been chemically synthesized with particular size such that its exciton of energy would resonate with SPP. High resolution transmission electron microscopy (HRTEM) and scan tunneling microscopy (STM) were used to measure the corresponding QDs size and confirm its shape. Further confirmation of the size has been performed by the effective mass approximation (EMA) model utilizing the band gap of the prepared QDs. The band gaps have been measured through UV-vis absorption spectra as well as scan tunneling spectroscopy (STS). The coupling has been observed as two branching dips in the ATR spectra indicating Rabi like splitting. To the best of our knowledge, this is the first time that Rabi interaction is directly observed in an ATR angular spectra. This observation is attributed to the use a high resolution angular scan (±0.005°), in addition to the Doppler width of the laser line as well as the energy distribution of the excitons. The effect of three different linker molecules (TOPO, HDA), (Pyridine) and (Tri-butylamine) as surface ligands, on SPP-Exciton interaction has been examined.

Superconductivity could occur Na-supersaturated NaCl

NASA Astrophysics Data System (ADS)

Hanaki, Koji

1997-04-01

A flow-into electron and a flow-out hole mean flow-into of two unit electric c harges. Even if an exciton consisting of an electron and a hole is a neutral q uasi-particle, overlapping of excitons, namely, the bose condensation changes into a superconductor where half the electric current is due to holes moving t oward the reverse direction. The Meisner effect of the bose condensation comes from the precession of the each exciton under the magnetic field^1. Moreo ver, the present mechanism is supported with that superconducting material alw ays has two kinds of carriers. The superconductivity of NaCl comes from the ab ove-mentioned theory. Free stable holes at first and then electrons are produc ed in NaCl when considerable number of Cl^- lattice vacancies are brought in NaCl mainly because some electrons in the Cl-3p filled band fall into the v acancies. The coexistence of two kinds of stable carriers does not always mean the presence of excitons like VO with electrons not paired and localized in e ach V atom though. While, the absorption spectrum of the NaCl has already conf irmed the presence of excitons; the strength of the spectrum seems to indicate the formation of the bose condensation. Thus we could expect a new supercondu ctor. 1) Hanaki B.Am.P.Soc.,40-1(1995)568

Direct measurement of exciton dissociation energy in polymers

NASA Astrophysics Data System (ADS)

Toušek, J.; Toušková, J.; Chomutová, R.; Paruzel, B.; Pfleger, J.

2017-01-01

Exciton dissociation energy was obtained based on the comparison of thickness of the space charge region estimated from the measurement of capacitance of prepared Schottky diode and from the measurement of photovoltage spectra. While the capacitance measurements provide information about the total width of the space charge region (SCR) the surface photovoltaic effect brings information only about the part of the SCR where electric field is sufficiently high to cause dissociation. For determination of the dissociation energy it is sufficient to find the electric potential in the SCR where the process starts.

Workshop on New Directions in Solid State Power Switches Held at Farmingdale, New York on 28-30 August 1985.

DTIC Science & Technology

1985-12-24

of transitors . Using the data for these parameters, Johnson’s "figure of • merit" shows 8-SiC to be more than three orders of magnitude better than Si...34’ .- ompound may be statistically distributed in the lat- ./0 1N -lce taking an averaged structure. X-ray diffraction.-The results of the x-ray diffrac- 0...excitons, which are not electriclaly conducting because they have no net charge. Since the statistical factors favoring exciton formation go as the

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.

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.

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-exciton scattering: Composite boson versus elementary boson

NASA Astrophysics Data System (ADS)

Combescot, M.; Betbeder-Matibet, O.; Combescot, R.

2007-05-01

This paper shows the necessity of introducing a quantum object, the “coboson,” to properly describe, through a fermion scheme, any composite particle, such as the exciton, which is made of two fermions. Although commonly dealt with as elementary bosons, these composite bosons—cobosons in short—differ from them due to their composite nature which makes the handling of their many-body effects quite different from the existing treatments valid for elementary bosons. As a direct consequence of this composite nature, there is no correct way to describe the interaction between cobosons as a potential V . This is rather dramatic because, with the Hamiltonian not written as H=H0+V , all the usual approaches to many-body effects fail. In particular, the standard form of the Fermi golden rule, written in terms of V , cannot be used to obtain the transition rates of two cobosons. To get them, we have had to construct an unconventional expression for this Fermi golden rule in which H only appears. Making use of this expression, we give here a detailed calculation of the time evolution of two excitons. We compare the results of this exact approach with the ones obtained by using an effective bosonic Hamiltonian in which the excitons are considered as elementary bosons with effective scatterings between them, these scatterings resulting from an elaborate mapping between the two-fermion space and the ideal boson space. We show that the relation between the inverse lifetime and the sum of the transition rates for elementary bosons differs from the one of the composite bosons by a factor of 1/2 , so that it is impossible to find effective scatterings between bosonic excitons giving these two physical quantities correctly, whatever the mapping from composite bosons to elementary bosons is. The present paper thus constitutes a strong mathematical proof that, in spite of a widely spread belief, we cannot forget the composite nature of these cobosons, even in the extremely low-density limit of just two excitons. This paper also shows the (unexpected) cancellation in the Born approximation of the two-exciton transition rate for a finite value of the momentum transfer.

Exciton Transport and Perfect Coulomb Drag

NASA Astrophysics Data System (ADS)

Nandi, Debaleena

2013-03-01

Exciton condensation is realized in closely-spaced bilayer quantum Hall systems at νT = 1 when the total density in the two 2D electron layers matches the Landau level degeneracy. In this state, electrons in one layer become tightly bound to holes in the other layer, forming a condensate similar to the Cooper pairs in a superconductor. Being charge neutral, these excitons ought to be free to move throughout the bulk of the quantum Hall fluid. One therefore expects that electron current driven in one layer would spontaneously generate a ``hole'' current in the other layer, even in the otherwise insulating bulk of the 2D system. We demonstrate precisely this effect, using a Corbino geometry to defeat edge state transport. Our sample contains two essentially identical two-dimensional electron systems (2DES) in GaAs quantum wells separated by a thin AlGaAs barrier. It is patterned into an annulus with arms protruding from each rim that provide contact to each 2DES separately. A current drag geometry is realized by applying a drive voltage between the outer and inner rim on one 2DES layer while the two rims on the opposite layer are connected together in a closed loop. There is no direct electrical connection between the two layers. At νT = 1 the bulk of the Corbino annulus becomes insulating owing to the quantum Hall gap and net charge transport across the bulk is suppressed. Nevertheless, we find that in the drag geometry appreciable currents do flow in each layer. These currents are almost exactly equal magnitude but, crucially, flow in opposite directions. This phenomenon reflects exciton transport within the νT = 1 condensate, rather than its quasiparticle excitations. We find that quasiparticle transport competes with exciton transport at elevated temperatures, drive levels, and layer separations. This work represents a collaboration with A.D.K. Finck, J.P. Eisenstein, L.N. Pfeiffer and K.W. West. This work is supported by the NSF under grant DMR-1003080.

Many-body effects in valleytronics: direct measurement of valley lifetimes in single-layer MoS2.

PubMed

Mai, Cong; Barrette, Andrew; Yu, Yifei; Semenov, Yuriy G; Kim, Ki Wook; Cao, Linyou; Gundogdu, Kenan

2014-01-08

Single layer MoS2 is an ideal material for the emerging field of "valleytronics" in which charge carrier momentum can be finely controlled by optical excitation. This system is also known to exhibit strong many-body interactions as observed by tightly bound excitons and trions. Here we report direct measurements of valley relaxation dynamics in single layer MoS2, by using ultrafast transient absorption spectroscopy. Our results show that strong Coulomb interactions significantly impact valley population dynamics. Initial excitation by circularly polarized light creates electron-hole pairs within the K-valley. These excitons coherently couple to dark intervalley excitonic states, which facilitate fast electron valley depolarization. Hole valley relaxation is delayed up to about 10 ps due to nondegeneracy of the valence band spin states. Intervalley biexciton formation reveals the hole valley relaxation dynamics. We observe that biexcitons form with more than an order of magnitude larger binding energy compared to conventional semiconductors. These measurements provide significant insight into valley specific processes in 2D semiconductors. Hence they could be used to suggest routes to design semiconducting materials that enable control of valley polarization.

Excitation energy migration processes in various multi-porphyrin assemblies.

PubMed

Yang, Jaesung; Kim, Dongho

2012-08-13

The electronic interactions and excitation energy transfer (EET) processes of a variety of multi-porphyrin arrays with linear, cyclic and box architectures have been explored. Directly meso-meso linked linear arrays (Z(N)) exhibit strong excitonic coupling with an exciton coherence length of approximately 6 porphyrin units, while fused linear arrays (T(N)) exhibit extensive π-conjugation over the whole array. The excitonic coherence length in directly linked cyclic porphyrin rings (CZ(N)) was determined to be approximately 2.7 porphyrin units by simultaneous analysis of fluorescence intensities and lifetimes at the single-molecule level. By performing transient absorption (TA) and TA anisotropy decay measurements, the EET rates in m-phenylene linked cyclic porphyrin wheels C12ZA and C24ZB were determined to be 4 and 36 ps(-1), respectively. With increasing the size of C(N)ZA, the EET efficiencies decrease owing to the structural distortions that produce considerable non-radiative decay pathways. Finally, the EET rates of self-assembled porphyrin boxes consisting of directly linked diporphyrins, B1A, B2A and B3A, are 48, 98 and 361 ps(-1), respectively. The EET rates of porphyrin boxes consisting of alkynylene-bridged diporphyrins, B2B and B4B, depend on the conformation of building blocks (planar or orthogonal) rather than the length of alkynylene linkers.

Direct Measurements of Magnetic Polarons in Cd 1–xMn x Se Nanocrystals from Resonant Photoluminescence

DOE PAGES

Rice, W. D.; Liu, W.; Pinchetti, V.; ...

2017-04-07

In semiconductors, quantum confinement can greatly enhance the interaction between band carriers (electrons and holes) and dopant atoms. One manifestation of this enhancement is the increased stability of exciton magnetic polarons in magnetically doped nanostructures. In the limit of very strong 0D confinement that is realized in colloidal semiconductor nanocrystals, a single exciton can exert an effective exchange field B ex on the embedded magnetic dopants that exceeds several tesla. Here we use the very sensitive method of resonant photoluminescence (PL) to directly measure the presence and properties of exciton magnetic polarons in colloidal Cd 1–xMn xSe nanocrystals. Despite smallmore » Mn 2+ concentrations (x = 0.4–1.6%), large polaron binding energies up to ~26 meV are observed at low temperatures via the substantial Stokes shift between the pump laser and the resonant PL maximum, indicating nearly complete alignment of all Mn 2+ spins by B exex ≈ 10 T in these nanocrystals, in good agreement with theoretical estimates. Further, the emission line widths provide direct insight into the statistical fluctuations of the Mn 2+ spins. In conclusion, these resonant PL studies provide detailed insight into collective magnetic phenomena, especially in lightly doped nanocrystals where conventional techniques such as nonresonant PL or time-resolved PL provide ambiguous results.« less

Direct Measurements of Magnetic Polarons in Cd 1–xMn x Se Nanocrystals from Resonant Photoluminescence

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

Rice, W. D.; Liu, W.; Pinchetti, V.

In semiconductors, quantum confinement can greatly enhance the interaction between band carriers (electrons and holes) and dopant atoms. One manifestation of this enhancement is the increased stability of exciton magnetic polarons in magnetically doped nanostructures. In the limit of very strong 0D confinement that is realized in colloidal semiconductor nanocrystals, a single exciton can exert an effective exchange field B ex on the embedded magnetic dopants that exceeds several tesla. Here we use the very sensitive method of resonant photoluminescence (PL) to directly measure the presence and properties of exciton magnetic polarons in colloidal Cd 1–xMn xSe nanocrystals. Despite smallmore » Mn 2+ concentrations (x = 0.4–1.6%), large polaron binding energies up to ~26 meV are observed at low temperatures via the substantial Stokes shift between the pump laser and the resonant PL maximum, indicating nearly complete alignment of all Mn 2+ spins by B exex ≈ 10 T in these nanocrystals, in good agreement with theoretical estimates. Further, the emission line widths provide direct insight into the statistical fluctuations of the Mn 2+ spins. In conclusion, these resonant PL studies provide detailed insight into collective magnetic phenomena, especially in lightly doped nanocrystals where conventional techniques such as nonresonant PL or time-resolved PL provide ambiguous results.« less

Ultrashort Carbon Nanotubes That Fluoresce Brightly in the Near-Infrared.

PubMed

Danné, Noémie; Kim, Mijin; Godin, Antoine G; Kwon, Hyejin; Gao, Zhenghong; Wu, Xiaojian; Hartmann, Nicolai F; Doorn, Stephen K; Lounis, Brahim; Wang, YuHuang; Cognet, Laurent

2018-06-14

The intrinsic near-infrared photoluminescence observed in long single-walled carbon nanotubes is known to be quenched in ultrashort nanotubes due to their tiny size as compared to the exciton diffusion length in these materials (>100 nm). Here, we show that intense photoluminescence can be created in ultrashort nanotubes (∼40 nm length) upon incorporation of exciton-trapping sp 3 defect sites. Using super-resolution photoluminescence imaging at <25 nm resolution, we directly show the preferential localization of excitons at the nanotube ends, which separate by less than 40 nm and behave as independent emitters. This unexpected observation opens the possibility to synthesize fluorescent ultrashort nanotubes-a goal that has been long thought impossible-for bioimaging applications, where bright near-infrared photoluminescence and small size are highly desirable, and for quantum information science, where high quality and well-controlled near-infrared single photon emitters are needed.

Multiple exciton generation for photoelectrochemical hydrogen evolution reactions with quantum yields exceeding 100%

DOE PAGES

Yan, Yong; Crisp, Ryan W.; Gu, Jing; ...

2017-04-03

Multiple exciton generation (MEG) in quantum dots (QDs) has the potential to greatly increase the power conversion efficiency in solar cells and in solar-fuel production. During the MEG process, two electron-hole pairs (excitons) are created from the absorption of one high-energy photon, bypassing hot-carrier cooling via phonon emission. Here we demonstrate that extra carriers produced via MEG can be used to drive a chemical reaction with quantum efficiency above 100%. We developed a lead sulfide (PbS) QD photoelectrochemical cell that is able to drive hydrogen evolution from aqueous Na 2S solution with a peak external quantum efficiency exceeding 100%. QDmore » photoelectrodes that were measured all demonstrated MEG when the incident photon energy was larger than 2.7 times the bandgap energy. Finally, our results demonstrate a new direction in exploring high-efficiency approaches to solar fuels.« less

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

Oscillator strength and quantum-confined Stark effect of excitons in a thin PbS quantum disk

NASA Astrophysics Data System (ADS)

Oukerroum, A.; El-Yadri, M.; El Aouami, A.; Feddi, E.; Dujardin, F.; Duque, C. A.; Sadoqi, M.; Long, G.

2018-01-01

In this paper, we report a study of the effect of a lateral electric field on a quantum-confined exciton in a thin PbS quantum disk. Our approach was performed in the framework of the effective mass theory and adiabatic approximation. The ground state energy and the stark shift were determined by using a variational method with an adequate trial wavefunction, by investigating a 2D oscillator strength under simultaneous consideration of the geometrical confinement and the electric field strength. Our results showed a strong dependence of the exciton binding and the Stark shift on the disk dimensions in both axial and longitudinal directions. On the other hand, our results also showed that the Stark shift’s dependence on the electric field is not purely quadratic but the linear contribution is also important and cannot be neglected, especially when the confinement gets weaker.

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.

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

PubMed

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

2017-08-23

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

Prolonged photo-carriers generated in a massive-and-anisotropic Dirac material.

PubMed

Nurmamat, Munisa; Ishida, Yukiaki; Yori, Ryohei; Sumida, Kazuki; Zhu, Siyuan; Nakatake, Masashi; Ueda, Yoshifumi; Taniguchi, Masaki; Shin, Shik; Akahama, Yuichi; Kimura, Akio

2018-06-13

Transient electron-hole pairs generated in semiconductors can exhibit unconventional excitonic condensation. Anisotropy in the carrier mass is considered as the key to elongate the life time of the pairs, and hence to stabilize the condensation. Here we employ time- and angle-resolved photoemission spectroscopy to explore the dynamics of photo-generated carriers in black phosphorus. The electronic structure above the Fermi level has been successfully observed, and a massive-and-anisotropic Dirac-type dispersions are confirmed; more importantly, we directly observe that the photo-carriers generated across the direct band gap have the life time exceeding 400 ps. Our finding confirms that black phosphorus is a suitable platform for excitonic condensations, and also open an avenue for future applications in broadband mid-infrared BP-based optoelectronic devices.

A direct measurement of g-factors in II-VI and III-V core-shell nanocrystals

NASA Astrophysics Data System (ADS)

Fradkin, L.; Langof, L.; Lifshitz, E.; Gaponik, N.; Rogach, A.; Eychmüller, A.; Weller, H.; Micic, O. I.; Nozik, A. J.

2005-02-01

This study describes a direct measurement of spectroscopic g-factors of photo-generated carriers in InP/ZnS and HgTe/Hg xCd 1-xTe(S) core-shell nanocrystals. The g-factor of trapped electrons and their spin-lattice versus radiative relaxation ratio ( T1/ τ) were measured by the use of continuous-wave and time-resolved optically detected magnetic resonance (ODMR) spectroscopy. The g-factors of excitons and donor-hole pairs were derived by the use of field-induced circular-polarized photoluminescence (CP-PL) spectroscopy. The combined information enabled to determine the g-factors of the individual band-edge electrons and holes. The results suggested an increase of the g-factor of the exciton and conduction electron with a decrease of the nanocrystal size.

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.

Evidence of excited state localization and static disorder in LH2 investigated by 2D-polarization single-molecule imaging at room temperature.

PubMed

Tubasum, Sumera; Camacho, Rafael; Meyer, Matthias; Yadav, Dheerendra; Cogdell, Richard J; Pullerits, Tõnu; Scheblykin, Ivan G

2013-12-07

Two-dimensional polarization fluorescence imaging of single light harvesting complexes 2 (LH2) of Rps. acidophila was carried out to investigate the polarization properties of excitation and fluorescence emission simultaneously, at room temperature. In two separate experiments we excited LH2 with a spectrally narrow laser line matched to the absorption bands of the two chromophore rings, B800 and B850, thereby indirectly and directly triggering fluorescence of the B850 exciton state. A correlation analysis of the polarization modulation depths in excitation and emission for a large number of single complexes was performed. Our results show, in comparison to B800, that the B850 ring is a more isotropic absorber due to the excitonic nature of its excited states. At the same time, we observed a strong tendency for LH2 to emit with dipolar character, from which preferential localization of the emissive exciton, stable for minutes, is inferred. We argue that the observed effects can consistently be explained by static energetic disorder and/or deformation of the complex, with possible involvement of exciton self-trapping.

Spectroscopy of Single AlInAs Quantum Dots

NASA Astrophysics Data System (ADS)

Derebezov, I. A.; Gaisler, A. V.; Gaisler, V. A.; Dmitriev, D. V.; Toropov, A. I.; Kozhukhov, A. S.; Shcheglov, D. V.; Latyshev, A. V.; Aseev, A. L.

2018-03-01

A system of quantum dots based on Al x In1- x As/Al y Ga1- y As solid solutions is investigated. The use of Al x In1- x As wide-gap solid solutions as the basis of quantum dots substantially extends the spectral emission range to the short-wavelength region, including the wavelength region near 770 nm, which is of interest for the development of aerospace systems of quantum cryptography. The optical characteristics of Al x In1- x As single quantum dots grown by the Stranski-Krastanov mechanism were studied by cryogenic microphotoluminescence. The statistics of the emission of single quantum dot excitons was studied using a Hanbury Brown-Twiss interferometer. The pair photon correlation function indicates the sub-Poissonian nature of the emission statistics, which directly confirms the possibility of developing single-photon emitters based on Al x In1- x As quantum dots. The fine structure of quantum dot exciton states was investigated at wavelengths near 770 nm. The splitting of the exciton states is found to be similar to the natural width of exciton lines, which is of great interest for the development of entangled photon pair emitters based on Al x In1- x As quantum dots.

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.

Influence of the substrate material on the optical properties of tungsten diselenide monolayers

NASA Astrophysics Data System (ADS)

Lippert, Sina; Schneider, Lorenz Maximilian; Renaud, Dylan; Kang, Kyung Nam; Ajayi, Obafunso; Kuhnert, Jan; Halbich, Marc-Uwe; Abdulmunem, Oday M.; Lin, Xing; Hassoon, Khaleel; Edalati-Boostan, Saeideh; Duck Kim, Young; Heimbrodt, Wolfram; Yang, Eui-Hyeok; Hone, James C.; Rahimi-Iman, Arash

2017-06-01

Monolayers of transition-metal dichalcogenides such as WSe2 have become increasingly attractive due to their potential in electrical and optical applications. Because the properties of these 2D systems are known to be affected by their surroundings, we report how the choice of the substrate material affects the optical properties of monolayer WSe2. To accomplish this study, pump-density-dependent micro-photoluminescence measurements are performed with time-integrating and time-resolving acquisition techniques. Spectral information and power-dependent mode intensities are compared at 290 K and 10 K for exfoliated WSe2 on SiO2/Si, sapphire (Al2O3), hBN/Si3N4/Si, and MgF2, indicating substrate-dependent appearance and strength of exciton, trion, and biexciton modes. Additionally, one CVD-grown WSe2 monolayer on sapphire is included in this study for direct comparison with its exfoliated counterpart. Time-resolved micro-photoluminescence shows how radiative decay times strongly differ for different substrate materials. Our data indicates exciton-exciton annihilation as a shortening mechanism at room temperature, and subtle trends in the decay rates in correlation to the dielectric environment at cryogenic temperatures. On the measureable time scales, trends are also related to the extent of the respective 2D-excitonic modes’ appearance. This result highlights the importance of further detailed characterization of exciton features in 2D materials, particularly with respect to the choice of substrate.

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.

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.

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.

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.

Colloidal-Quantum-Dot Ring Lasers with Active Color Control.

PubMed

le Feber, Boris; Prins, Ferry; De Leo, Eva; Rabouw, Freddy T; Norris, David J

2018-02-14

To improve the photophysical performance of colloidal quantum dots for laser applications, sophisticated core/shell geometries have been developed. Typically, a wider bandgap semiconductor is added as a shell to enhance the gain from the quantum-dot core. This shell is designed to electronically isolate the core, funnel excitons to it, and reduce nonradiative Auger recombination. However, the shell could also potentially provide a secondary source of gain, leading to further versatility in these materials. Here we develop high-quality quantum-dot ring lasers that not only exhibit lasing from both the core and the shell but also the ability to switch between them. We fabricate ring resonators (with quality factors up to ∼2500) consisting only of CdSe/CdS/ZnS core/shell/shell quantum dots using a simple template-stripping process. We then examine lasing as a function of the optical excitation power and ring radius. In resonators with quality factors >1000, excitons in the CdSe cores lead to red lasing with thresholds at ∼25 μJ/cm 2 . With increasing power, green lasing from the CdS shell emerges (>100 μJ/cm 2 ) and then the red lasing begins to disappear (>250 μJ/cm 2 ). We present a rate-equation model that can explain this color switching as a competition between exciton localization into the core and stimulated emission from excitons in the shell. Moreover, by lowering the quality factor of the cavity we can engineer the device to exhibit only green lasing. The mechanism demonstrated here provides a potential route toward color-switchable quantum-dot lasers.

Recent Advances in Alternating Current-Driven Organic Light-Emitting Devices.

PubMed

Pan, Yufeng; Xia, Yingdong; Zhang, Haijuan; Qiu, Jian; Zheng, Yiting; Chen, Yonghua; Huang, Wei

2017-11-01

Organic light-emitting devices (OLEDs), typically operated with constant-voltage or direct-current (DC) power sources, are candidates for next-generation solid-state lighting and displays, as they are light, thin, inexpensive, and flexible. However, researchers have focused mainly on the device itself (e.g., development of novel materials, design of the device structure, and optical outcoupling engineering), and little attention has been paid to the driving mode. Recently, an alternative concept to DC-driven OLEDs by directly driving devices using time-dependent voltages or alternating current (AC) has been explored. Here, the effects of different device structures of AC-driven OLEDs, for example, double-insulation, single-insulation, double-injection, and tandem structure, on the device performance are systematically investigated. The formation of excitons and the dielectric layer, which are important to achieve high-performance AC-driven OLEDs, are carefully considered. The importance of gaining further understanding of the fundamental properties of AC-driven OLEDs is then discussed, especially as they relate to device physics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.).

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.

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

Phosphorene-AsP heterostructure as a potential excitonic solar cell material - A first principles study

NASA Astrophysics Data System (ADS)

Kishore, M. R. Ashwin; Ravindran, P.

2018-04-01

Solar energy conversion to produce electricity using photovoltaics is an emerging area in alternative energy research. Herein, we report on the basis of density functional calculations, phosphorene/AsP heterostructure could be a promising material for excitonic solar cells (XSCs). Our HSE06 functional calculations show that the band gap of both phosphorene and AsP fall exactly into the optimum value range according to XSCs requirement. The calculated effective mass of electrons and holes show anisotropic in nature with effective masses along Γ-X direction is lower than the Γ-Y direction and hence the charge transport will be faster along Γ-X direction. The wide energy range of light absorption confirms the potential use of these materials for solar cell applications. Interestingly, phosphorene and AsP monolayer forms a type-II band alignment which will enhance the separation of photogenerated charge carriers and hence the recombination rate will be lower which can further improve its photo-conversion efficiency if one use it in XSCs.

Photogenerated Intrinsic Free Carriers in Small-molecule Organic Semiconductors Visualized by Ultrafast Spectroscopy

PubMed Central

He, Xiaochuan; Zhu, Gangbei; Yang, Jianbing; Chang, Hao; Meng, Qingyu; Zhao, Hongwu; Zhou, Xin; Yue, Shuai; Wang, Zhuan; Shi, Jinan; Gu, Lin; Yan, Donghang; Weng, Yuxiang

2015-01-01

Confirmation of direct photogeneration of intrinsic delocalized free carriers in small-molecule organic semiconductors has been a long-sought but unsolved issue, which is of fundamental significance to its application in photo-electric devices. Although the excitonic description of photoexcitation in these materials has been widely accepted, this concept is challenged by recently reported phenomena. Here we report observation of direct delocalized free carrier generation upon interband photoexcitation in highly crystalline zinc phthalocyanine films prepared by the weak epitaxy growth method using ultrafast spectroscopy. Transient absorption spectra spanning the visible to mid-infrared region revealed the existence of short-lived free electrons and holes with a diffusion length estimated to cross at least 11 molecules along the π−π stacking direction that subsequently localize to form charge transfer excitons. The interband transition was evidenced by ultraviolet-visible absorption, photoluminescence and electroluminescence spectroscopy. Our results suggest that delocalized free carriers photogeneration can also be achieved in organic semiconductors when the molecules are packed properly. PMID:26611323

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

PubMed

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

2010-04-07

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

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.

h -AlN-Mg(OH)2 van der Waals bilayer heterostructure: Tuning the excitonic characteristics

NASA Astrophysics Data System (ADS)

Bacaksiz, C.; Dominguez, A.; Rubio, A.; Senger, R. T.; Sahin, H.

2017-02-01

Motivated by recent studies that reported the successful synthesis of monolayer Mg (OH) 2 [Suslu et al., Sci. Rep. 6, 20525 (2016), 10.1038/srep20525] and hexagonal (h -)AlN [Tsipas et al., Appl. Phys. Lett. 103, 251605 (2013), 10.1063/1.4851239], we investigate structural, electronic, and optical properties of vertically stacked h -AlN and Mg (OH) 2 , through ab initio density-functional theory (DFT), many-body quasiparticle calculations within the GW approximation and the Bethe-Salpeter equation (BSE). It is obtained that the bilayer heterostructure prefers the A B' stacking having direct band gap at the Γ with Type-II band alignment in which the valance band maximum and conduction band minimum originate from different layer. Regarding the optical properties, the imaginary part of the dielectric function of the individual layers and heterobilayer are investigated. The heterobilayer possesses excitonic peaks, which appear only after the construction of the heterobilayer. The lowest three exciton peaks are analyzed in detail by means of band decomposed charge density and the oscillator strength. Furthermore, the wave function calculation shows that the first peak of the heterobilayer originates from spatially indirect exciton where the electron and hole localized at h -AlN and Mg (OH) 2 , respectively, which is important for the light harvesting applications.

Workshop II: Nanotechnology and Advanced Cell Concepts

NASA Technical Reports Server (NTRS)

2007-01-01

Workshop focused on few emerging concepts(beyond tandem cells): 1. Engineering incident sun spectrum and transparency losses a) Nano emitters (dot concentrator); b) Surface plasmonics; c) Up converters; d) Down converter. 2. Intermediate band solar cells a) Efficiency projections (detail energy balance projections); b) Inserting 0,1 and 2D semiconductor structures in solar cells 3. Polymer and hybrid cells a) Nanotubes/dot polymers; b) Exciton dissociation.

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.

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.

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.

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.

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.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

NASA Astrophysics Data System (ADS)

Tiwari, Vivek; Peters, William K.; Jonas, David M.

2017-10-01

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer.

PubMed

Tiwari, Vivek; Peters, William K; Jonas, David M

2017-10-21

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

Excited About Excitons (A "Life at the Frontiers of Energy Research" contest entry from the 2011 Energy Frontier Research Centers (EFRCs) Summit and Forum)

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

Baldo, Marc

"Excited about Excitons" was submitted by the Center for Excitonics (CE) to the "Life at the Frontiers of Energy Research" video contest at the 2011 Science for Our Nation's Energy Future: Energy Frontier Research Centers (EFRCs) Summit and Forum. Twenty-six EFRCs created short videos to highlight their mission and their work. This video was selected as one of five winners by a distinguished panel of judges for its "outstanding portrayal of young scientists". The Center for Excitonics (CE), an EFRC directed by Marc Baldo at the Massachusetts Institute of Technology (MIT) is a partnership of scientists from three institutions: MITmore » (lead), Brookhaven National Laboratory, and Harvard University. The Office of Basic Energy Sciences in the U.S. Department of Energy's Office of Science established the 46 Energy Frontier Research Centers (EFRCs) in 2009. These collaboratively-organized centers conduct fundamental research focused on 'grand challenges' and use-inspired 'basic research needs' recently identified in major strategic planning efforts by the scientific community. The overall purpose is to accelerate scientific progress toward meeting the nation's critical energy challenges. The mission of the Center for Excitonics (CE) is 'to understand the transport of charge carriers in synthetic disordered systems, which hold promise as new materials for conversion of solar energy to electricity and electrical energy storage.' Research topics are: solar photovoltaic, photonic, solid state lighting, photosynthesis, novel materials synthesis, charge transport, defect tolerant materials, scalable processing, and self-assembly.« less

Electron-hole liquid in semiconductors and low-dimensional structures

NASA Astrophysics Data System (ADS)

Sibeldin, N. N.

2017-11-01

The condensation of excitons into an electron-hole liquid (EHL) and the main EHL properties in bulk semiconductors and low-dimensional structures are considered. The EHL properties in bulk materials are discussed primarily in qualitative terms based on the experimental results obtained for germanium and silicon. Some of the experiments in which the main EHL thermodynamic parameters (density and binding energy) have been obtained are described and the basic factors that determine these parameters are considered. Topics covered include the effect of external perturbations (uniaxial strain and magnetic field) on EHL stability; phase diagrams for a nonequilibrium exciton-gas-EHL system; information on the size and concentration of electron-hole drops (EHDs) under various experimental conditions; the kinetics of exciton condensation and of recombination in the exciton-gas-EHD system; dynamic EHD properties and the motion of EHDs under the action of external forces; the properties of giant EHDs that form in potential wells produced by applying an inhomogeneous strain to the crystal; and effects associated with the drag of EHDs by nonequilibrium phonons (phonon wind), including the dynamics and formation of an anisotropic spatial structure of the EHD cloud. In discussing EHLs in low-dimensional structures, a number of studies are reviewed on the observation and experimental investigation of phenomena such as spatially indirect (dipolar) electron-hole and exciton (dielectric) liquids in GaAs/AlGaAs structures with double quantum wells (QWs), EHDs containing only a few electron-hole pairs (dropletons), EHLs in type-I silicon QWs, and spatially direct and dipolar EHLs in type-II silicon-germanium heterostructures.

2D Ruddlesden-Popper Perovskites for Optoelectronics.

PubMed

Chen, Yani; Sun, Yong; Peng, Jiajun; Tang, Junhui; Zheng, Kaibo; Liang, Ziqi

2018-01-01

Conventional 3D organic-inorganic halide perovskites have recently undergone unprecedented rapid development. Yet, their inherent instabilities over moisture, light, and heat remain a crucial challenge prior to the realization of commercialization. By contrast, the emerging 2D Ruddlesden-Popper-type perovskites have recently attracted increasing attention owing to their great environmental stability. However, the research of 2D perovskites is just in their infancy. In comparison to 3D analogues, they are natural quantum wells with a much larger exciton binding energy. Moreover, their inner structural, dielectric, optical, and excitonic properties remain to be largely explored, limiting further applications. This review begins with an introduction to 2D perovskites, along with a detailed comparison to 3D counterparts. Then, a discussion of the organic spacer cation engineering of 2D perovskites is presented. Next, quasi-2D perovskites that fall between 3D and 2D perovskites are reviewed and compared. The unique excitonic properties, electron-phonon coupling, and polarons of 2D perovskites are then be revealed. A range of their (opto)electronic applications is highlighted in each section. Finally, a summary is given, and the strategies toward structural design, growth control, and photophysics studies of 2D perovskites for high-performance electronic devices are rationalized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct measurement of the absolute absorption spectrum of individual semiconducting single-wall carbon nanotubes

NASA Astrophysics Data System (ADS)

Blancon, Jean-Christophe; Paillet, Matthieu; Tran, Huy Nam; Than, Xuan Tinh; Guebrou, Samuel Aberra; Ayari, Anthony; Miguel, Alfonso San; Phan, Ngoc-Minh; Zahab, Ahmed-Azmi; Sauvajol, Jean-Louis; Fatti, Natalia Del; Vallée, Fabrice

2013-09-01

The optical properties of single-wall carbon nanotubes are very promising for developing novel opto-electronic components and sensors with applications in many fields. Despite numerous studies performed using photoluminescence or Raman and Rayleigh scattering, knowledge of their optical response is still partial. Here we determine using spatial modulation spectroscopy, over a broad optical spectral range, the spectrum and amplitude of the absorption cross-section of individual semiconducting single-wall carbon nanotubes. These quantitative measurements permit determination of the oscillator strength of the different excitonic resonances and their dependencies on the excitonic transition and type of semiconducting nanotube. A non-resonant background is also identified and its cross-section comparable to the ideal graphene optical absorbance. Furthermore, investigation of the same single-wall nanotube either free standing or lying on a substrate shows large broadening of the excitonic resonances with increase of oscillator strength, as well as stark weakening of polarization-dependent antenna effects, due to nanotube-substrate interaction.

Optical and Excitonic Properties of Atomically Thin Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Berkelbach, Timothy C.; Reichman, David R.

2018-03-01

Starting with the isolation of a single sheet of graphene, the study of layered materials has been one of the most active areas of condensed matter physics, chemistry, and materials science. Single-layer transition-metal dichalcogenides are direct-gap semiconducting analogs of graphene that exhibit novel electronic and optical properties. These features provide exciting opportunities for the discovery of both new fundamental physical phenomena as well as innovative device platforms. Here, we review the progress associated with the creation and use of a simple microscopic framework for describing the optical and excitonic behavior of few-layer transition-metal dichalcogenides, which is based on symmetry, band structure, and the effective interactions between charge carriers in these materials. This approach provides an often quantitative account of experiments that probe the physics associated with strong electron–hole interactions in these quasi two-dimensional systems and has been successfully employed by many groups to both describe and predict emergent excitonic behavior in these layered semiconducting systems.

Coherent wavepackets in the Fenna-Matthews-Olson complex are robust to excitonic-structure perturbations caused by mutagenesis

NASA Astrophysics Data System (ADS)

Maiuri, Margherita; Ostroumov, Evgeny E.; Saer, Rafael G.; Blankenship, Robert E.; Scholes, Gregory D.

2018-02-01

Femtosecond pulsed excitation of light-harvesting complexes creates oscillatory features in their response. This phenomenon has inspired a large body of work aimed at uncovering the origin of the coherent beatings and possible implications for function. Here we exploit site-directed mutagenesis to change the excitonic level structure in Fenna-Matthews-Olson (FMO) complexes and compare the coherences using broadband pump-probe spectroscopy. Our experiments detect two oscillation frequencies with dephasing on a picosecond timescale—both at 77 K and at room temperature. By studying these coherences with selective excitation pump-probe experiments, where pump excitation is in resonance only with the lowest excitonic state, we show that the key contributions to these oscillations stem from ground-state vibrational wavepackets. These experiments explicitly show that the coherences—although in the ground electronic state—can be probed at the absorption resonances of other bacteriochlorophyll molecules because of delocalization of the electronic excitation over several chromophores.

Giant magnetic splitting inducing near-unity valley polarization in van der Waals heterostructures.

PubMed

Nagler, Philipp; Ballottin, Mariana V; Mitioglu, Anatolie A; Mooshammer, Fabian; Paradiso, Nicola; Strunk, Christoph; Huber, Rupert; Chernikov, Alexey; Christianen, Peter C M; Schüller, Christian; Korn, Tobias

2017-11-16

Monolayers of semiconducting transition metal dichalcogenides exhibit intriguing fundamental physics of strongly coupled spin and valley degrees of freedom for charge carriers. While the possibility of exploiting these properties for information processing stimulated concerted research activities towards the concept of valleytronics, maintaining control over spin-valley polarization proved challenging in individual monolayers. A promising alternative route explores type II band alignment in artificial van der Waals heterostructures. The resulting formation of interlayer excitons combines the advantages of long carrier lifetimes and spin-valley locking. Here, we demonstrate artificial design of a two-dimensional heterostructure enabling intervalley transitions that are not accessible in monolayer systems. The resulting giant effective g factor of -15 for interlayer excitons induces near-unity valley polarization via valley-selective energetic splitting in high magnetic fields, even after nonselective excitation. Our results highlight the potential to deterministically engineer novel valley properties in van der Waals heterostructures using crystallographic alignment.

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.

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.

Bistable Topological Insulator with Exciton-Polaritons

NASA Astrophysics Data System (ADS)

Kartashov, Yaroslav V.; Skryabin, Dmitry V.

2017-12-01

The functionality of many nonlinear and quantum optical devices relies on the effect of optical bistability. Using microcavity exciton-polaritons in a honeycomb arrangement of microcavity pillars, we report the resonance response and bistability of topological edge states. A balance between the pump, loss, and nonlinearity ensures a broad range of dynamical stability and controls the distribution of power between counterpropagating states on the opposite edges of the honeycomb lattice stripe. Tuning energy and polarization of the pump photons, while keeping their momentum constant, we demonstrate control of the propagation direction of the dominant edge state. Our results facilitate the development of practical applications of topological photonics.

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

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.

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.

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.

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.

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.

Radiation creation of cation defects in alkali halide crystals: Review and today's concept (Review Article)

NASA Astrophysics Data System (ADS)

Lushchik, A.; Lushchik, Ch.; Vasil'chenko, E.; Popov, A. I.

2018-04-01

Irradiation of alkali halide crystals creates pairs of Frenkel defects both in anion and cation sublattices. However, the particular nonimpact creation mechanisms (related to the decay of different electronic excitations) of cation Frenkel pairs are still unclear. At helium temperatures, there is yet no direct evidences of the creation of stable (long-lived) elemental cation defects. On the other hand, a number of complex structural defects containing cation vacancies and/or interstitials, were detected after irradiation of alkali halides at higher temperatures. Besides already proved mechanism related to the association of H and VK centers into trihalide molecules, the following possibilities of cation interstitial-vacancy pair creation are analyzed as well: (i) a direct decay of cation or anion excitons, (ii) the transformation of anion Frenkel pairs, formed at the decay of anion excitons or e-h recombination, into cation ones.

Band gap of corundumlike α -Ga2O3 determined by absorption and ellipsometry

NASA Astrophysics Data System (ADS)

Segura, A.; Artús, L.; Cuscó, R.; Goldhahn, R.; Feneberg, M.

2017-07-01

The electronic structure near the band gap of the corundumlike α phase of Ga2O3 has been investigated by means of optical absorption and spectroscopic ellipsometry measurements in the ultraviolet (UV) range (400-190 nm). The absorption coefficient in the UV region and the imaginary part of the dielectric function exhibit two prominent absorption thresholds with wide but well-defined structures at 5.6 and 6.3 eV which have been ascribed to allowed direct transitions from crystal-field split valence bands to the conduction band. Excitonic effects with large Gaussian broadening are taken into account through the Elliott-Toyozawa model, which yields an exciton binding energy of 110 meV and direct band gaps of 5.61 and 6.44 eV. The large broadening of the absorption onset is related to the slightly indirect character of the material.

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.

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.

Wrapping cytochrome c around single-wall carbon nanotube: engineered nanohybrid building blocks for infrared detection at high quantum efficiency

PubMed Central

Gong, Youpin; Liu, Qingfeng; Wilt, Jamie Samantha; Gong, Maogang; Ren, Shenqiang; Wu, Judy

2015-01-01

Biomolecule cytochrome c (Cty c), a small molecule of a chain of amino acids with extraordinary electron transport, was helically wrapped around a semiconductive single-wall carbon nanotube (s-SWCNT) to form a molecular building block for uncooled infrared detection with two uniquely designed functionalities: exciton dissociation to free charge carriers at the heterojunction formed on the s-SWCNT/Cty c interface and charge transport along the electron conducting chain of Cty c (acceptor) and hole conducting channel through s-SWCNT (donor). Such a design aims at addressing the long-standing challenges in exciton dissociation and charge transport in an SWCNT network, which have bottlenecked development of photonic SWCNT-based infrared detectors. Using these building blocks, uncooled s-SWCNT/Cyt c thin film infrared detectors were synthesized and shown to have extraordinary photoresponsivity up to 0.77 A W−1 due to a high external quantum efficiency (EQE) in exceeding 90%, which represents a more than two orders of magnitude enhancement than the best previously reported on CNT-based infrared detectors with EQE of only 1.72%. From a broad perspective, this work on novel s-SWCNT/Cyt c nanohybrid infrared detectors has developed a successful platform of engineered carbon nanotube/biomolecule building blocks with superior properties for optoelectronic applications. PMID:26066737

Wrapping cytochrome c around single-wall carbon nanotube: engineered nanohybrid building blocks for infrared detection at high quantum efficiency.

PubMed

Gong, Youpin; Liu, Qingfeng; Wilt, Jamie Samantha; Gong, Maogang; Ren, Shenqiang; Wu, Judy

2015-06-11

Biomolecule cytochrome c (Cty c), a small molecule of a chain of amino acids with extraordinary electron transport, was helically wrapped around a semiconductive single-wall carbon nanotube (s-SWCNT) to form a molecular building block for uncooled infrared detection with two uniquely designed functionalities: exciton dissociation to free charge carriers at the heterojunction formed on the s-SWCNT/Cty c interface and charge transport along the electron conducting chain of Cty c (acceptor) and hole conducting channel through s-SWCNT (donor). Such a design aims at addressing the long-standing challenges in exciton dissociation and charge transport in an SWCNT network, which have bottlenecked development of photonic SWCNT-based infrared detectors. Using these building blocks, uncooled s-SWCNT/Cyt c thin film infrared detectors were synthesized and shown to have extraordinary photoresponsivity up to 0.77 A W(-1) due to a high external quantum efficiency (EQE) in exceeding 90%, which represents a more than two orders of magnitude enhancement than the best previously reported on CNT-based infrared detectors with EQE of only 1.72%. From a broad perspective, this work on novel s-SWCNT/Cyt c nanohybrid infrared detectors has developed a successful platform of engineered carbon nanotube/biomolecule building blocks with superior properties for optoelectronic applications.

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.

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.

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

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.

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

Picosecond Dynamics of Excitonic Magnetic Polarons in Colloidal Diffusion-Doped Cd(1-x)Mn(x)Se Quantum Dots.

PubMed

Nelson, Heidi D; Bradshaw, Liam R; Barrows, Charles J; Vlaskin, Vladimir A; Gamelin, Daniel R

2015-11-24

Spontaneous magnetization is observed at zero magnetic field in photoexcited colloidal Cd(1-x)Mn(x)Se (x = 0.13) quantum dots (QDs) prepared by diffusion doping, reflecting strong Mn(2+)-exciton exchange coupling. The picosecond dynamics of this phenomenon, known as an excitonic magnetic polaron (EMP), are examined using a combination of time-resolved photoluminescence, magneto-photoluminescence, and Faraday rotation (TRFR) spectroscopies, in conjunction with continuous-wave absorption, magnetic circular dichroism (MCD), and magnetic circularly polarized photoluminescence (MCPL) spectroscopies. The data indicate that EMPs form with random magnetization orientations at zero external field, but their formation can be directed by an external magnetic field. After formation, however, external magnetic fields are unable to reorient the EMPs within the luminescence lifetime, implicating anisotropy in the EMP potential-energy surfaces. TRFR measurements in a transverse magnetic field reveal rapid (<5 ps) spin transfer from excitons to Mn(2+) followed by coherent EMP precession at the Mn(2+) Larmor frequency for over a nanosecond. A dynamical TRFR phase inversion is observed during EMP formation attributed to the large shifts in excitonic absorption energies during spontaneous magnetization. Partial optical orientation of the EMPs by resonant circularly polarized photoexcitation is also demonstrated. Collectively, these results highlight the extraordinary physical properties of colloidal diffusion-doped Cd(1-x)Mn(x)Se QDs that result from their unique combination of strong quantum confinement, large Mn(2+) concentrations, and relatively narrow size distributions. The insights gained from these measurements advance our understanding of spin dynamics and magnetic exchange in colloidal doped semiconductor nanostructures, with potential ramifications for future spin-based information technologies.

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.

Optical and electronic properties of 2 H -Mo S2 under pressure: Revealing the spin-polarized nature of bulk electronic bands

NASA Astrophysics Data System (ADS)

Brotons-Gisbert, Mauro; Segura, Alfredo; Robles, Roberto; Canadell, Enric; Ordejón, Pablo; Sánchez-Royo, Juan F.

2018-05-01

Monolayers of transition-metal dichalcogenide semiconductors present spin-valley locked electronic bands, a property with applications in valleytronics and spintronics that is usually believed to be absent in their centrosymmetric (as the bilayer or bulk) counterparts. Here we show that bulk 2 H -Mo S2 hides a spin-polarized nature of states determining its direct band gap, with the spin sequence of valence and conduction bands expected for its single layer. This relevant finding is attained by investigating the behavior of the binding energy of A and B excitons under high pressure, by means of absorption measurements and density-functional-theory calculations. These results raise an unusual situation in which bright and dark exciton degeneracy is naturally broken in a centrosymmetric material. Additionally, the phonon-assisted scattering process of excitons has been studied by analyzing the pressure dependence of the linewidth of discrete excitons observed at the absorption coefficient edge of 2 H -Mo S2 . Also, the pressure dependence of the indirect optical transitions of bulk 2 H -Mo S2 has been analyzed by absorption measurements and density-functional-theory calculations. These results reflect a progressive closure of the indirect band gap as pressure increases, indicating that metallization of bulk Mo S2 may occur at pressures higher than 26 GPa.

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.

Multiple exciton generation and recombination in carbon nanotubes and nanocrystals.

PubMed

Kanemitsu, Yoshihiko

2013-06-18

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

Self Assembly and Interface Engineering of Organic Functional Materials for High Performance Polymer Solar Cells

NASA Astrophysics Data System (ADS)

Jen, Alex

2010-03-01

The performance of polymer solar cells are strongly dependent on the efficiency of light harvesting, exciton dissociation, charge transport, and charge collection at the metal/organic, metal/metal oxide, and organic/metal oxide interfaces. To improve the device performance, two parallel approaches were used: 1) developing novel low band gap conjugated polymers with good charge-transporting properties and 2) modifying the interfaces between the organic/metal oxide and organic/metal layers with functional self-assembling monolayers to tune their energy barriers. Moreover, the molecule engineering approach was also used to tune the energy level, charge mobility, and morphology of organic semiconductors.

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.

Electrostatics of electron-hole interactions in van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Cavalcante, L. S. R.; Chaves, A.; Van Duppen, B.; Peeters, F. M.; Reichman, D. R.

2018-03-01

The role of dielectric screening of electron-hole interaction in van der Waals heterostructures is theoretically investigated. A comparison between models available in the literature for describing these interactions is made and the limitations of these approaches are discussed. A simple numerical solution of Poisson's equation for a stack of dielectric slabs based on a transfer matrix method is developed, enabling the calculation of the electron-hole interaction potential at very low computational cost and with reasonable accuracy. Using different potential models, direct and indirect exciton binding energies in these systems are calculated within Wannier-Mott theory, and a comparison of theoretical results with recent experiments on excitons in two-dimensional materials is discussed.

Quasi-particle energies and optical excitations of hydrogenated and fluorinated germanene.

PubMed

Shu, Huabing; Li, Yunhai; Wang, Shudong; Wang, Jinlan

2015-02-14

Using density functional theory, the G0W0 method and Bethe-Salpeter equation calculations, we systematically explore the structural, electronic and optical properties of hydrogenated and fluorinated germanene. The hydrogenated/fluorinated germanene tends to form chair and zigzag-line configurations and its electronic and optical properties show close geometry dependence. The chair hydrogenated/fluorinated and zigzag-line fluorinated germanene are direct band-gap semiconductors, while the zigzag-line hydrogenated germanene owns an indirect band-gap. Moreover, the quasi-particle corrections are significant and strong excitonic effects with large exciton binding energies are observed. Moreover, the zigzag-line hydrogenated/fluorinated germanene shows highly anisotropic optical responses, which may be used as a good optical linear polarizer.

Solution Phase Exciton Diffusion Dynamics of a Charge-Transfer Copolymer PTB7 and a Homopolymer P3HT

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

Cho, Sung; Rolczynski, Brian S.; Xu, Tao

2015-06-18

Using ultrafast polarization-controlled transient absorption (TA) measurements, dynamics of the initial exciton states were investigated on the time scale of tens of femtoseconds to about 80 ps in two different types of conjugated polymers extensively used in active layers of organic photovoltaic devices. These polymers are poly(3-fluorothienothiophenebenzodithiophene) (PTB7) and poly-3-hexylthiophene (P3HT), which are charge-transfer polymers and homopolymers, respectively. In PTB7, the initial excitons with excess vibrational energy display two observable ultrafast time constants, corresponding to coherent exciton diffusion before the vibrational relaxation, and followed by incoherent exciton diffusion processes to a neighboring local state after the vibrational relaxation. In contrast,more » P3HT shows only one exciton diffusion or conformational motion time constant of 34 ps, even though its exciton decay kinetics are multiexponential. Based on the experimental results, an exciton dynamics mechanism is conceived taking into account the excitation energy and structural dependence in coherent and incoherent exciton diffusion processes, as well as other possible deactivation processes including the formation of the pseudo-charge-transfer and charge separate states, as well as interchain exciton hopping or coherent diffusion.« less

Solution Phase Exciton Diffusion Dynamics of a Charge-Transfer Copolymer PTB7 and a Homopolymer P3HT.

PubMed

Cho, Sung; Rolczynski, Brian S; Xu, Tao; Yu, Luping; Chen, Lin X

2015-06-18

Using ultrafast polarization-controlled transient absorption (TA) measurements, dynamics of the initial exciton states were investigated on the time scale of tens of femtoseconds to about 80 ps in two different types of conjugated polymers extensively used in active layers of organic photovoltaic devices. These polymers are poly(3-fluorothienothiophenebenzodithiophene) (PTB7) and poly-3-hexylthiophene (P3HT), which are charge-transfer polymers and homopolymers, respectively. In PTB7, the initial excitons with excess vibrational energy display two observable ultrafast time constants, corresponding to coherent exciton diffusion before the vibrational relaxation, and followed by incoherent exciton diffusion processes to a neighboring local state after the vibrational relaxation. In contrast, P3HT shows only one exciton diffusion or conformational motion time constant of 34 ps, even though its exciton decay kinetics are multiexponential. Based on the experimental results, an exciton dynamics mechanism is conceived taking into account the excitation energy and structural dependence in coherent and incoherent exciton diffusion processes, as well as other possible deactivation processes including the formation of the pseudo-charge-transfer and charge separate states, as well as interchain exciton hopping or coherent diffusion.

The growth, characterization, and application of highly ordered small molecule semiconducting thin films

NASA Astrophysics Data System (ADS)

Lunt, Richard Royal, III

Organic semiconductors have gained tremendous attention recently as their use in field effect transistors, sensors, solar cells, lasers, and organic light emitting diodes have been demonstrated, offering the potential for low-cost alternatives. Since renewable energy remains one the greatest challenges of the 21st century, the possibility for low-cost and flexible organic photovoltaics is particularly exciting. In the first part of this thesis, we demonstrate a route to the controlled growth of oriented crystalline films through organic vapor-phase deposition (OVPD), in conjunction with organic-inorganic, and organic-organic quasi-epitaxy. This method for producing highly ordered crystalline thin-film heterostructures combines the control of film growth with the electronic properties expected to approach that of organic single crystals, making them potentially useful for high efficiency organic thin-film devices and solar cells. We further demonstrate OVPD as a method for the deposition of large-scale organic electronics with low material waste, a key ability in fulfilling the promise of low-cost organic devices. The second part of this thesis is focused on understanding factors that govern energy (i.e. exciton) transport. The two single most important and fundamental properties of organic semiconductors are the transport of charge and energy. While charge mobility has been extensively studied and convincingly linked to the degree of crystalline order and orientation, the principles governing energy transport, i.e. exciton migration, in this class of materials and the subsequent connection to crystalline properties still remain ambiguous. Therefore, we aim to understand key aspects governing exciton motion in organic materials to better engineer materials, film morphologies, and film architectures for organic electronics with improved performance. To this end, we have developed a new method for measuring exciton diffusion and characterize a range of archetypal organic compounds. We then derive a simple theoretical model that provides insight into the control of exciton migration in organic systems through changes in both crystal orientation (anisotropy) and degree of crystalline order, which is crucial for the management of energy transport in a wide range of important organic electronic devices.

Frenkel versus charge-transfer exciton dispersion in molecular crystals

NASA Astrophysics Data System (ADS)

Cudazzo, Pierluigi; Gatti, Matteo; Rubio, Angel; Sottile, Francesco

2013-11-01

By solving the many-body Bethe-Salpeter equation at finite momentum transfer, we characterize the exciton dispersion in two prototypical molecular crystals, picene and pentacene, in which localized Frenkel excitons compete with delocalized charge-transfer excitons. We explain the exciton dispersion on the basis of the interplay between electron and hole hopping and electron-hole exchange interaction, unraveling a simple microscopic description to distinguish Frenkel and charge-transfer excitons. This analysis is general and can be applied to other systems in which the electron wave functions are strongly localized, as in strongly correlated insulators.

Exciton center-of-mass localization and dielectric environment effect in monolayer WS2

NASA Astrophysics Data System (ADS)

Hichri, Aïda; Ben Amara, Imen; Ayari, Sabrine; Jaziri, Sihem

2017-06-01

The ultrathin transition metal dichalcogenides (TMDs) have emerged as promising materials for various applications using two dimensional semiconductors. They have attracted increasing attention due to their unique optical properties originate from neutral and charged excitons. In this paper, we study the strong localization of exciton center-of-mass motion within random potential fluctuations caused by the monolayer defects. Here, we report negatively charged exciton formation in monolayer TMDs, notably tungsten disulfide WS2. Our theory is based on an effective mass model of neutral and charged excitons, parameterized by ab-initio calculations. Taking into the account the strong correlation between the monolayer WS2 and the surrounding dielectric environment, our theoretical results are in good agreement with one-photon photoluminescence (PL) and reflectivity measurements. We also show that the exciton state with p-symmetry, experimentally observed by two-photon PL emission, is energetically below the 2s-state. We use the equilibrium mass action law, to quantify the relative weight of exciton and trion PL. We show that exciton and trion emission can be tuned and controlled by external parameters like temperature, pumping, and injection electrons. Finally, in comparison with experimental measurements, we show that exciton emission in monolayer tungsten dichalcogenides is substantially reduced. This feature suggests that free exciton can be trapped in disordered potential wells to form a localized exciton and therefore offers a route toward novel optical properties.

Subdiffusive exciton transport in quantum dot solids.

PubMed

Akselrod, Gleb M; Prins, Ferry; Poulikakos, Lisa V; Lee, Elizabeth M Y; Weidman, Mark C; Mork, A Jolene; Willard, Adam P; Bulović, Vladimir; Tisdale, William A

2014-06-11

Colloidal quantum dots (QDs) are promising materials for use in solar cells, light-emitting diodes, lasers, and photodetectors, but the mechanism and length of exciton transport in QD materials is not well understood. We use time-resolved optical microscopy to spatially visualize exciton transport in CdSe/ZnCdS core/shell QD assemblies. We find that the exciton diffusion length, which exceeds 30 nm in some cases, can be tuned by adjusting the inorganic shell thickness and organic ligand length, offering a powerful strategy for controlling exciton movement. Moreover, we show experimentally and through kinetic Monte Carlo simulations that exciton diffusion in QD solids does not occur by a random-walk process; instead, energetic disorder within the inhomogeneously broadened ensemble causes the exciton diffusivity to decrease over time. These findings reveal new insights into exciton dynamics in disordered systems and demonstrate the flexibility of QD materials for photonic and optoelectronic applications.

One-Dimensional Singlet Exciton Diffusion in Poly(3-hexylthiophene) Crystalline Domains.

PubMed

Tamai, Yasunari; Matsuura, Yuu; Ohkita, Hideo; Benten, Hiroaki; Ito, Shinzaburo

2014-01-16

Singlet exciton dynamics in crystalline domains of regioregular poly(3-hexylthiophene) (P3HT) films was studied by transient absorption spectroscopy. Upon the selective excitation of crystalline P3HT at the absorption edge, no red shift of the singlet exciton band was observed with an elapse of time, suggesting singlet exciton dynamics in relatively homogeneous P3HT crystalline domains without downhill relaxation in the energetic disorder. Even under such selective excitation conditions, the annihilation rate coefficient γ(t) was still dependent on time, γ(t) ∝ t(-1/2), which is attributed to anisotropic exciton diffusion in P3HT crystalline domains. From the annihilation rate coefficient, the singlet exciton diffusion coefficient D and exciton diffusion length LD in the crystalline domains were evaluated to be 7.9 × 10(-3) cm(2) s(-1) and 20 nm, respectively. The origin of the time-dependent exciton dynamics is discussed in terms of dimensionality.

Chromophore-Dependent Intramolecular Exciton-Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics.

PubMed

Padula, Daniele; Lee, Myeong H; Claridge, Kirsten; Troisi, Alessandro

2017-11-02

In this paper, we adopt an approach suitable for monitoring the time evolution of the intramolecular contribution to the spectral density of a set of identical chromophores embedded in their respective environments. We apply the proposed method to the Fenna-Matthews-Olson (FMO) complex, with the objective to quantify the differences among site-dependent spectral densities and the impact of such differences on the exciton dynamics of the system. Our approach takes advantage of the vertical gradient approximation to reduce the computational demands of the normal modes analysis. We show that the region of the spectral density that is believed to strongly influence the exciton dynamics changes significantly in the timescale of tens of nanoseconds. We then studied the impact of the intramolecular vibrations on the exciton dynamics by considering a model of FMO in a vibronic basis and neglecting the interaction with the environment to isolate the role of the intramolecular exciton-vibration coupling. In agreement with the assumptions in the literature, we demonstrate that high frequency modes at energy much larger than the excitonic energy splitting have negligible influence on exciton dynamics despite the large exciton-vibration coupling. We also find that the impact of including the site-dependent spectral densities on exciton dynamics is not very significant, indicating that it may be acceptable to apply the same spectral density on all sites. However, care needs to be taken for the description of the exciton-vibrational coupling in the low frequency part of intramolecular modes because exciton dynamics is more susceptible to low frequency modes despite their small Huang-Rhys factors.

Exciton Seebeck effect in molecular systems

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

Yan, Yun-An, E-mail: yunan@nano.gznc.edu.cn; Cai, Shaohong

2014-08-07

We investigate the exciton dynamics under temperature difference with the hierarchical equations of motion. Through a nonperturbative simulation of the transient absorption of a heterogeneous trimer model, we show that the temperature difference causes exciton population redistribution and affects the exciton transfer time. It is found that one can reproduce not only the exciton population redistribution but also the change of the exciton transfer time induced by the temperature difference with a proper tuning of the site energies of the aggregate. In this sense, there exists a site energy shift equivalence for any temperature difference in a broad range. Thismore » phenomenon is similar to the Seebeck effect as well as spin Seebeck effect and can be named as exciton Seebeck effect.« less

Robust valley polarization of helium ion modified atomically thin MoS2

NASA Astrophysics Data System (ADS)

Klein, J.; Kuc, A.; Nolinder, A.; Altzschner, M.; Wierzbowski, J.; Sigger, F.; Kreupl, F.; Finley, J. J.; Wurstbauer, U.; Holleitner, A. W.; Kaniber, M.

2018-01-01

Atomically thin semiconductors have dimensions that are commensurate with critical feature sizes of future optoelectronic devices defined using electron/ion beam lithography. Robustness of their emergent optical and valleytronic properties is essential for typical exposure doses used during fabrication. Here, we explore how focused helium ion bombardement affects the intrinsic vibrational, luminescence and valleytronic properties of atomically thin MoS2 . By probing the disorder dependent vibrational response we deduce the interdefect distance by applying a phonon confinement model. We show that the increasing interdefect distance correlates with disorder-related luminscence arising 180 meV below the neutral exciton emission. We perform ab initio density functional theory of a variety of defect related morphologies, which yield first indications on the origin of the observed additional luminescence. Remarkably, no significant reduction of free exciton valley polarization is observed until the interdefect distance approaches a few nanometers, namely the size of the free exciton Bohr radius. Our findings pave the way for direct writing of sub-10 nm nanoscale valleytronic devices and circuits using focused helium ions.

Spectral broadening of optical transitions in InAs/GaAs coupled quantum dot pairs

NASA Astrophysics Data System (ADS)

Kumar, P.; Czarnocki, C.; Jennings, C.; Casara, J.; Monteros, A. L.; Zahbihi, N.; Scheibner, M.; Economou, S. E.; Bracker, A. S.; Pursley, B. C.; Gammon, D.; Carter, S. G.

The optical transitions in InAs/GaAs coupled quantum dot (CQD) pairs are investigated experimentally. These coupled dot systems provide new means to study the interaction of quantum states with the mechanical modes of the crystal environment. Here, the line width and line shape of CQD optical transitions are analyzed in detail as a function of temperature, excitation power, excitation energy, and tunnel coupling strength. A significant line broadening, up to 25 times the typical lifetime-limited linewidth of single-dot excitons, is being observed at level anti-crossings where the coherent tunnel coupling between spatially direct and indirect exciton states is considerable. The experimental observations are compared with theoretical predictions where linewidth broadening at anti-crossings is attributed to the phonon assisted transitions, and found to be strongly dependent on the energy splitting of the two exciton branches. This work focuses on understanding the linewidth broadening due to the pure dephasing, and fundamental aspects of the interaction of these systems with the local environment. This work was supported by the Defense Threat Reduction Agency, Basic Research Award HDTRA1-15-1-0011.

Ab initio modeling of excitonic and charge-transfer states in organic semiconductors: the PTB1/PCBM low band gap system.

PubMed

Borges, Itamar; Aquino, Adélia J A; Köhn, Andreas; Nieman, Reed; Hase, William L; Chen, Lin X; Lischka, Hans

2013-12-11

A detailed quantum chemical simulation of the excitonic and charge-transfer (CT) states of a bulk heterojunction model containing poly(thieno[3,4-b]thiophene benzodithiophene) (PTB1)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is reported. The largest molecular model contains two stacked PTB1 trimer chains interacting with C60 positioned on top of and lateral to the (PTB1)3 stack. The calculations were performed using the algebraic diagrammatic construction method to second order (ADC(2)). One main result of the calculations is that the CT states are located below the bright inter-chain excitonic state, directly accessible via internal conversion processes. The other important aspects of the calculations are the formation of discrete bands of CT states originating from the lateral C60's and the importance of inter-chain charge delocalization for the stability of the CT states. A simple model for the charge separation step is also given, revealing the energetic feasibility of the overall photovoltaic process.

3D Localized Trions in Monolayer WSe2 in a Charge Tunable van der Waals Heterostructure.

PubMed

Chakraborty, Chitraleema; Qiu, Liangyu; Konthasinghe, Kumarasiri; Mukherjee, Arunabh; Dhara, Sajal; Vamivakas, Nick

2018-05-09

Monolayer transition metal dichalcogenides (TMDCs) have recently emerged as a host material for localized optically active quantum emitters that generate single photons. (1-5) Here, we investigate fully localized excitons and trions from such TMDC quantum emitters embedded in a van der Waals heterostructure. We use direct electrostatic doping through the vertical heterostructure device assembly to generate quantum confined trions. Distinct spectral jumps as a function of applied voltage bias, and excitation power-dependent charging, demonstrate the observation of the two different excitonic complexes. We also observe a reduction of the intervalley electron-hole exchange interaction in the confined trion due to the addition of an extra electron, which is manifested by a decrease in its fine structure splitting. We further confirm this decrease of exchange interaction for the case of the charged states by a comparative study of the circular polarization resolved photoluminescence from individual excitonic states. The valley polarization selection rules inherited by the localized trions will provide a pathway toward realizing a localized spin-valley-photon interface.

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

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.

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.

Distinct exciton dissociation behavior of organolead trihalide perovskite and excitonic semiconductors studied in a same device

DOE PAGES

Hu, Miao; Bi, Cheng; Yuan, Yongbo; ...

2015-01-15

The nonexcitonic character for organometal trihalide perovskites is demonstrated by examining the field-dependent exciton dissociation behavior. Moreover, it is found that photogenerated excitons can be effectively dissociated into free charges inside perovskite without the assistance of charge extraction layer or external field, which is a stark contrast to the charge-separation behavior in excitonic materials in the same photovoltaic operation system.

Trion formation dynamics in monolayer transition metal dichalcogenides

DOE PAGES

Singh, Akashay; Moody, Galan; Schaibley, John R.; ...

2016-01-05

Here, we report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides, specifically molybdenum diselenide (MoSe 2), using resonant two-color pump-probe spectroscopy. When resonantly pumping the exciton transition, trions are generated on a picosecond time scale through exciton-electron interaction. As the pump energy is tuned from the high energy to low energy side of the inhomogeneously broadened exciton resonance, the trion formation time increases by ~50%. This feature can be explained by the existence of both localized and delocalized excitons in a disordered potential and suggests the existence of an exciton mobility edge in transition metal dichalcogenides.

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.

Exciton transport in π-conjugated polymers with conjugation defects.

PubMed

Meng, Ruixuan; Li, Yuan; Li, Chong; Gao, Kun; Yin, Sun; Wang, Luxia

2017-09-20

In π-conjugated polymers for photovoltaic applications, intrinsic conjugation defects are known to play crucial roles in impacting exciton transport after photoexcitation. However, the understanding of the associated microscopic processes still remains limited. Here, we present a theoretical investigation of the effects of different conjugation defects on the dynamics of exciton transport in two linearly coupled poly(p-phenylene vinylene) (PPV) molecules. The model system is constructed by employing an extended version of the Su-Schrieffer-Heeger model and the exciton behaviors are simulated by means of a quantum nonadiabatic dynamics. We identify two types of conjugation defects, i.e., weakening conjugation and strengthening conjugation, which are demonstrated to play different roles in impacting the dynamics of exciton transport in the system. The weakening conjugation acts as an energy well inclined to trap a moving exciton, while the strengthening conjugation acts as an energy barrier inclined to block the exciton. We also systematically simulate both intrachain and interchain dynamics of exciton transport, and find that an exciton could experience a "short-time delaying", "trapping", "blocking", or "hopping" process, which is determined by the defect type, strength, and position. These findings provide a microscopic understanding of how the exciton transport dynamics can be impacted by conjugation defects in an actual polymer system.

Observation of two distinct negative trions in tungsten disulfide monolayers

DOE PAGES

Boulesbaa, Abdelaziz; Huang, Bing; Wang, Kai; ...

2015-09-25

We report on the observation of two distinct photogenerated negative trion states T A and T B in two-dimensional tungsten disulfide (2D-WS 2) monolayers. These trions are postulated to emerge from their parent excitons X A and X B, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between T A and T B photoformation, following dissociation of X A and X B through hole trapping at internal or substrate defect sites. While T A arises directly from its parent X A, Tmore » B emerges through a different transition accessible only after X B dissociates through a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS 2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T 1) and ~1.98 eV (T 2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics of the excitons X A and X B’s characteristic absorption bands, at ~2.03 and ~2.40 eV, respectively, were separately monitored and compared with the photoinduced absorption features. Selective excitation of the lowest exciton level X A using λ pump < 2.4 eV forms only trion T 1, which implies that the electron that remains from the dissociation of exciton X A is involved in the creation of this trion with a binding energy ~ 10 meV with respect to X A. The absorption peak that corresponds to trion T 2 appears when λ pump > 2.4 eV, which is just sufficient to excite exciton X B. The dynamics of trion T 2 formation are found to correlate with the disappearance of the bleach of X B exciton, which indicates the involvement of holes participating in the bleach dynamics of exciton X B. Static electrical-doping photoabsorption measurements confirm the presence of an induced absorption peak similar to that of T 2. Since the proposed trion formation process here involves exciton dissociation through hole-trapping by defects in the 2D crystal or substrate, this discovery highlights the strong role that defects have in defining the optical and electrical properties of 2D metal chalcogenides, which is relevant to a broad spectrum of basic science and technology applications.« less

Quantum states and optical responses of low-dimensional electron hole systems

NASA Astrophysics Data System (ADS)

Ogawa, Tetsuo

2004-09-01

Quantum states and their optical responses of low-dimensional electron-hole systems in photoexcited semiconductors and/or metals are reviewed from a theoretical viewpoint, stressing the electron-hole Coulomb interaction, the excitonic effects, the Fermi-surface effects and the dimensionality. Recent progress of theoretical studies is stressed and important problems to be solved are introduced. We cover not only single-exciton problems but also few-exciton and many-exciton problems, including electron-hole plasma situations. Dimensionality of the Wannier exciton is clarified in terms of its linear and nonlinear responses. We also discuss a biexciton system, exciton bosonization technique, high-density degenerate electron-hole systems, gas-liquid phase separation in an excited state and the Fermi-edge singularity due to a Mahan exciton in a low-dimensional metal.

Nonlinear optical spectra having characteristics of Fano interferences in coherently coupled lowest exciton biexciton states in semiconductor quantum dots

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

Gotoh, Hideki, E-mail: gotoh.hideki@lab.ntt.co.jp; Sanada, Haruki; Yamaguchi, Hiroshi

2014-10-15

Optical nonlinear effects are examined using a two-color micro-photoluminescence (micro-PL) method in a coherently coupled exciton-biexciton system in a single quantum dot (QD). PL and photoluminescence excitation spectroscopy (PLE) are employed to measure the absorption spectra of the exciton and biexciton states. PLE for Stokes and anti-Stokes PL enables us to clarify the nonlinear optical absorption properties in the lowest exciton and biexciton states. The nonlinear absorption spectra for excitons exhibit asymmetric shapes with peak and dip structures, and provide a distinct contrast to the symmetric dip structures of conventional nonlinear spectra. Theoretical analyses with a density matrix method indicatemore » that the nonlinear spectra are caused not by a simple coherent interaction between the exciton and biexciton states but by coupling effects among exciton, biexciton and continuum states. These results indicate that Fano quantum interference effects appear in exciton-biexciton systems at QDs and offer important insights into their physics.« less

Bright and dark singlet excitons via linear and two-photon spectroscopy in monolayer transition metal dichalcogenides

DOE PAGES

Berkelbach, Timothy C.; Hybertsen, Mark S.; Reichmann, David R.

2015-08-10

We discuss the linear and two-photon spectroscopic selection rules for spin-singlet excitons in monolayer transition-metal dichalcogenides. Our microscopic formalism combines a fully k-dependent few-orbital band structure with a many-body Bethe-Salpeter equation treatment of the electron-hole interaction, using a model dielectric function. We show analytically and numerically that the single-particle, valley-dependent selection rules are preserved in the presence of excitonic effects. Furthermore, we definitively demonstrate that the bright (one-photon allowed) excitons have s-type azimuthal symmetry and that dark p-type excitons can be probed via two-photon spectroscopy. Thus, the screened Coulomb interaction in these materials substantially deviates from the 1/ε₀r form; thismore » breaks the “accidental” angular momentum degeneracy in the exciton spectrum, such that the 2p exciton has a lower energy than the 2s exciton by at least 50 meV. We compare our calculated two-photon absorption spectra to recent experimental measurements.« less

Theory of optical absorption by interlayer excitons in transition metal dichalcogenide heterobilayers

NASA Astrophysics Data System (ADS)

Wu, Fengcheng; Lovorn, Timothy; MacDonald, A. H.

2018-01-01

We present a theory of optical absorption by interlayer excitons in a heterobilayer formed from transition metal dichalcogenides. The theory accounts for the presence of small relative rotations that produce a momentum shift between electron and hole bands located in different layers, and a moiré pattern in real space. Because of the momentum shift, the optically active interlayer excitons are located at the moiré Brillouin zone's corners, instead of at its center, and would have elliptical optical selection rules if the individual layers were translationally invariant. We show that the exciton moiré potential energy restores circular optical selection rules by coupling excitons with different center of mass momenta. A variety of interlayer excitons with both senses of circular optical activity, and energies that are tunable by twist angle, are present at each valley. The lowest energy exciton states are generally localized near the exciton potential energy minima. We discuss the possibility of using the moiré pattern to achieve scalable two-dimensional arrays of nearly identical quantum dots.

Excitonic Effects in Methylammonium Lead Halide Perovskites.

PubMed

Chen, Xihan; Lu, Haipeng; Yang, Ye; Beard, Matthew C

2018-05-17

The exciton binding energy in methylammonium lead iodide (MAPbI 3 ) is about 10 meV, around 1/3 of the available thermal energy ( k B T ∼ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination, and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.

Signatures of four-particle correlations associated with exciton-carrier interactions in coherent spectroscopy on bulk GaAs

NASA Astrophysics Data System (ADS)

Webber, D.; Wilmer, B. L.; Liu, X.; Dobrowolska, M.; Furdyna, J. K.; Bristow, A. D.; Hall, K. C.

2016-10-01

Transient four-wave mixing studies of bulk GaAs under conditions of broad bandwidth excitation of primarily interband transitions have enabled four-particle correlations tied to degenerate (exciton-exciton) and nondegenerate (exciton-carrier) interactions to be studied. Real two-dimensional Fourier-transform spectroscopy (2DFTS) spectra reveal a complex response at the heavy-hole exciton emission energy that varies with the absorption energy, ranging from dispersive on the diagonal through absorptive for low-energy interband transitions to dispersive with the opposite sign for interband transitions high above band gap. Simulations using a multilevel model augmented by many-body effects provide excellent agreement with the 2DFTS experiments and indicate that excitation-induced dephasing (EID) and excitation-induced shift (EIS) affect degenerate and nondegenerate interactions equivalently, with stronger exciton-carrier coupling relative to exciton-exciton coupling by approximately an order of magnitude. These simulations also indicate that EID effects are three times stronger than EIS in contributing to the coherent response of the semiconductor.

Fine structure and lifetime of dark excitons in transition metal dichalcogenide monolayers

NASA Astrophysics Data System (ADS)

Robert, C.; Amand, T.; Cadiz, F.; Lagarde, D.; Courtade, E.; Manca, M.; Taniguchi, T.; Watanabe, K.; Urbaszek, B.; Marie, X.

2017-10-01

The intricate interplay between optically dark and bright excitons governs the light-matter interaction in transition metal dichalcogenide monolayers. We have performed a detailed investigation of the "spin-forbidden" dark excitons in WSe2 monolayers by optical spectroscopy in an out-of-plane magnetic field Bz. In agreement with the theoretical predictions deduced from group theory analysis, magnetophotoluminescence experiments reveal a zero-field splitting δ =0.6 ±0.1 meV between two dark exciton states. The low-energy state is strictly dipole forbidden (perfectly dark) at Bz=0 , while the upper state is partially coupled to light with z polarization ("gray" exciton). The first determination of the dark neutral exciton lifetime τD in a transition metal dichalcogenide monolayer is obtained by time-resolved photoluminescence. We measure τD˜110 ±10 ps for the gray exciton state, i.e., two orders of magnitude longer than the radiative lifetime of the bright neutral exciton at T =12 K .

Intrinsic homogeneous linewidth and broadening mechanisms of excitons in monolayer transition metal dichalcogenides

DOE PAGES

Moody, Galan; Dass, Chandriker Kavir; Hao, Kai; ...

2015-09-18

In this paper, the band-edge optical response of transition metal dichalcogenides, an emerging class of atomically thin semiconductors, is dominated by tightly bound excitons localized at the corners of the Brillouin zone (valley excitons). A fundamental yet unknown property of valley excitons in these materials is the intrinsic homogeneous linewidth, which reflects irreversible quantum dissipation arising from system (exciton) and bath (vacuum and other quasiparticles) interactions and determines the timescale during which excitons can be coherently manipulated. Here we use optical two-dimensional Fourier transform spectroscopy to measure the exciton homogeneous linewidth in monolayer tungsten diselenide (WSe 2). The homogeneous linewidthmore » is found to be nearly two orders of magnitude narrower than the inhomogeneous width at low temperatures. We evaluate quantitatively the role of exciton–exciton and exciton–phonon interactions and population relaxation as linewidth broadening mechanisms. The key insights reported here—strong many-body effects and intrinsically rapid radiative recombination—are expected to be ubiquitous in atomically thin semiconductors.« less

Large-k exciton dynamics in GaN epilayers: Nonthermal and thermal regimes

NASA Astrophysics Data System (ADS)

Vinattieri, Anna; Bogani, Franco; Cavigli, Lucia; Manzi, Donatella; Gurioli, Massimo; Feltin, Eric; Carlin, Jean-François; Martin, Denis; Butté, Raphaël; Grandjean, Nicolas

2013-02-01

We present a detailed investigation performed at low temperature (T<50 K) concerning the exciton dynamics in GaN epilayers grown on c-plane sapphire substrates, focusing on the exciton formation and the transition from the nonthermal to the thermal regime. The time-resolved kinetics of longitudinal-optical-phonon replicas is used to address the energy relaxation in the excitonic band. From picosecond time-resolved spectra, we bring evidence for a long lasting nonthermal excitonic distribution, which accounts for the first 50 ps. Such a behavior is confirmed in different experimental conditions when both nonresonant and resonant excitations are used. At low excitation power density, the exciton formation and their subsequent thermalization are dominated by impurity scattering rather than by acoustic phonon scattering. The estimate of the average energy of the excitons as a function of delay after the excitation pulse provides information on the relaxation time, which describes the evolution of the exciton population to the thermal regime.

Chain-Length-Dependent Exciton Dynamics in Linear Oligothiophenes Probed Using Ensemble and Single-Molecule Spectroscopy.

PubMed

Kim, Tae-Woo; Kim, Woojae; Park, Kyu Hyung; Kim, Pyosang; Cho, Jae-Won; Shimizu, Hideyuki; Iyoda, Masahiko; Kim, Dongho

2016-02-04

Exciton dynamics in π-conjugated molecular systems is highly susceptible to conformational disorder. Using time-resolved and single-molecule spectroscopic techniques, the effect of chain length on the exciton dynamics in a series of linear oligothiophenes, for which the conformational disorder increased with increasing chain length, was investigated. As a result, extraordinary features of the exciton dynamics in longer-chain oligothiophene were revealed. Ultrafast fluorescence depolarization processes were observed due to exciton self-trapping in longer and bent chains. Increase in exciton delocalization during dynamic planarization processes was also observed in the linear oligothiophenes via time-resolved fluorescence spectra but was restricted in L-10T because of its considerable conformational disorder. Exciton delocalization was also unexpectedly observed in a bent chain using single-molecule fluorescence spectroscopy. Such delocalization modulates the fluorescence spectral shape by attenuating the 0-0 peak intensity. Collectively, these results provide significant insights into the exciton dynamics in conjugated polymers.

Organic photovoltaics: elucidating the ultra-fast exciton dissociation mechanism in disordered materials.

PubMed

Heitzer, Henry M; Savoie, Brett M; Marks, Tobin J; Ratner, Mark A

2014-07-14

Organic photovoltaics (OPVs) offer the opportunity for cheap, lightweight and mass-producible devices. However, an incomplete understanding of the charge generation process, in particular the timescale of dynamics and role of exciton diffusion, has slowed further progress in the field. We report a new Kinetic Monte Carlo model for the exciton dissociation mechanism in OPVs that addresses the origin of ultra-fast (<1 ps) dissociation by incorporating exciton delocalization. The model reproduces experimental results, such as the diminished rapid dissociation with increasing domain size, and also lends insight into the interplay between mixed domains, domain geometry, and exciton delocalization. Additionally, the model addresses the recent dispute on the origin of ultra-fast exciton dissociation by comparing the effects of exciton delocalization and impure domains on the photo-dynamics.This model provides insight into exciton dynamics that can advance our understanding of OPV structure-function relationships. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intrinsic homogeneous linewidth and broadening mechanisms of excitons in monolayer transition metal dichalcogenides

PubMed Central

Moody, Galan; Kavir Dass, Chandriker; Hao, Kai; Chen, Chang-Hsiao; Li, Lain-Jong; Singh, Akshay; Tran, Kha; Clark, Genevieve; Xu, Xiaodong; Berghäuser, Gunnar; Malic, Ermin; Knorr, Andreas; Li, Xiaoqin

2015-01-01

The band-edge optical response of transition metal dichalcogenides, an emerging class of atomically thin semiconductors, is dominated by tightly bound excitons localized at the corners of the Brillouin zone (valley excitons). A fundamental yet unknown property of valley excitons in these materials is the intrinsic homogeneous linewidth, which reflects irreversible quantum dissipation arising from system (exciton) and bath (vacuum and other quasiparticles) interactions and determines the timescale during which excitons can be coherently manipulated. Here we use optical two-dimensional Fourier transform spectroscopy to measure the exciton homogeneous linewidth in monolayer tungsten diselenide (WSe2). The homogeneous linewidth is found to be nearly two orders of magnitude narrower than the inhomogeneous width at low temperatures. We evaluate quantitatively the role of exciton–exciton and exciton–phonon interactions and population relaxation as linewidth broadening mechanisms. The key insights reported here—strong many-body effects and intrinsically rapid radiative recombination—are expected to be ubiquitous in atomically thin semiconductors. PMID:26382305

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

Core molecule dependence of energy migration in phenylacetylene nanostar dendrimers: Ab initio molecular orbital-configuration interaction based quantum master equation study

NASA Astrophysics Data System (ADS)

Kishi, Ryohei; Minami, Takuya; Fukui, Hitoshi; Takahashi, Hideaki; Nakano, Masayoshi

2008-06-01

The core molecule dependence of energy (exciton) migration in phenylacetylene nanostar dendrimers is investigated using the ab initio molecular orbital (MO)-configuration interaction based quantum master equation approach. We examine three kinds of core molecular species, i.e., benzene, anthracene, and pentacene, with different highest occupied MO-lowest unoccupied MO (HOMO-LUMO) gaps, which lead to different orbital interactions between the dendron parts and the core molecule. The nanostars bearing anthracene and pentacene cores are characterized by multistep exciton states with spatially well-segmented distributions: The exciton distributions of high-lying exciton states are spatially localized well in the periphery region, whereas those of low-lying exciton states are done in the core region. On the other hand, for the nanostar bearing benzene core, which also has multistep exciton states, the spatial exciton distributions of low-lying exciton states are delocalized over the dendron and the core regions. It is found that the former nanostars exhibit nearly complete exciton migration from the periphery to the core molecule in contrast to the latter one, in which significant exciton distribution remains in the dendron parts attached to the core after the exciton relaxation, although all these dendrimers exhibit fast exciton relaxation from the initially populated states. It is predicted from the analysis based on the MO correlation diagrams and the relative relaxation factor that the complete exciton migration to the core occurs not only when the HOMO-LUMO gap of the core molecule is nearly equal to that of the dendron parts attached to the core (anthracene case) but also when fairly smaller than that (pentacene case), whereas the complete migration is not achieved when the HOMO-LUMO gap of the core is larger than that of the dendron parts (benzene case). These results suggest that the fast and complete exciton migration of real dendrimers could be realized by adjusting the HOMO-LUMO gap of the core molecule to be smaller than that of dendron parts, although there exist more complicated relaxation processes as compared to simple dendritic aggregate models studied so far.

Correction of the exciton Bohr radius in monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Li, Run-Ze; Dong, Xi-Ying; Li, Zhi-Qing; Wang, Zi-Wu

2018-07-01

We theoretically investigate the correction of exciton Bohr radius in monolayer transition metal dichalcogenides (TMDCs) on different polar substrates arising from the exciton-optical phonon coupling, in which both the intrinsic longitudinal optical phonon and surface optical phonon modes couple with the exciton are taken into account. We find that the exciton Bohr radius is enlarged markedly due to these coupling. Moreover, it can be changed on a large scale by modulating the polarizability of polar substrate and the internal distance between the monolayer TMDCs and polar substrate. Theoretical result provides a potential explanation for the variation of the exciton Bohr radius in experimental measurement.

Crossovers from excitons to plasmons in narrow-gap carbon nanotubes

NASA Astrophysics Data System (ADS)

Uryu, Seiji

2018-06-01

Plasmons and excitons, bound states of electrons and holes, are collective charge excitations in solids. In this study, we numerically show that in most metallic carbon nanotubes, which are called narrow-gap carbon nanotubes, excitons cross over to plasmons as the wave vector increases. This indicates that resonance with the excitons changes to that with the plasmons by changing the nanotube length, which can explain the origin of observed peaks in the terahertz or far-infrared region in the optical absorption spectra of metallic carbon nanotubes. In the crossovers from excitons to plasmons, a depolarization effect on the many-body wave functions of the plasmons and excitons is clarified.

Low temperature exciton dynamics and structural changes in perylene bisimide aggregates

NASA Astrophysics Data System (ADS)

Wolter, Steffen; Magnus Westphal, Karl; Hempel, Magdalena; Würthner, Frank; Kühn, Oliver; Lochbrunner, Stefan

2017-09-01

The temperature dependent exciton dynamics of J-aggregates formed by a perylene bisimide dye is investigated down to liquid nitrogen temperature (77 K) by femtosecond pump-probe spectroscopy. The analysis of the transient absorption data using a diffusion model for the excitons does not only reveal an overall decrease of the exciton mobility, but also a change in the dimensionality of the exciton transport at low temperatures. This change in dimensionality is further investigated by kinetic Monte Carlo simulations, identifying weakly interlinked one-dimensional aggregate chains as the most likely structure at low temperatures. This causes the exciton transport to be highly anisotropic.

Local Matrix-Cluster Interactions In La1-x SrxCoO3.

NASA Astrophysics Data System (ADS)

Giblin, Sean; Terry, Ian; Boothroyd, Andrew; Prabhakaran, Dharmalingiam; Wu, Jing; Leighton, Chris

2006-03-01

Magneto-electronic phase separation plays an integral part in many recent advances in the understanding of correlated electron systems. We have studied the magnetically phase separated material La1-x SrxCoO3 and the parent compound LaCoO3, using muon spectroscopy and magnetic susceptibility measurements. The muon as a local magnetic probe is sensitive to the magnetic field distribution in LaCoO3 in the LS state, which is a direct consequence of magnetic excitons. We believe that these excitons are interacting with the Co ions undergoing the known thermally induced spin transition. By directly comparing the results of the parent compound with La1-x SrxCoO3 we can observe the hole-rich ferromagnetic clusters interacting with the neighboring hole poor matrix for low x. This mechanism, detected here for the first time, may play an important role in the rich electrical and magnetic properties of La1-x SrxCoO3.

A sub-femtojoule electrical spin-switch based on optically trapped polariton condensates.

PubMed

Dreismann, Alexander; Ohadi, Hamid; Del Valle-Inclan Redondo, Yago; Balili, Ryan; Rubo, Yuri G; Tsintzos, Simeon I; Deligeorgis, George; Hatzopoulos, Zacharias; Savvidis, Pavlos G; Baumberg, Jeremy J

2016-10-01

Practical challenges to extrapolating Moore's law favour alternatives to electrons as information carriers. Two promising candidates are spin-based and all-optical architectures, the former offering lower energy consumption, the latter superior signal transfer down to the level of chip-interconnects. Polaritons-spinor quasi-particles composed of semiconductor excitons and microcavity photons-directly couple exciton spins and photon polarizations, combining the advantages of both approaches. However, their implementation for spintronics has been hindered because polariton spins can be manipulated only optically or by strong magnetic fields. Here we use an external electric field to directly control the spin of a polariton condensate, bias-tuning the emission polarization. The nonlinear spin dynamics offers an alternative route to switching, allowing us to realize an electrical spin-switch exhibiting ultralow switching energies below 0.5 fJ. Our results lay the foundation for development of devices based on the electro-optical control of coherent spin ensembles on a chip.

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

Electronic and optical properties of exciton, trions and biexciton in II-VI parabolic quantum dot

NASA Astrophysics Data System (ADS)

Sujanah, P.; John Peter, A.; Woo Lee, Chang

2015-08-01

Binding energies of exciton, trions and biexciton and their interband optical transition energies are studied in a CdTe/ZnTe quantum dot nanostructure taking into consideration the geometrical confinement effect. The radial spread of the wavefunctions, binding energies, optical transition energies, oscillator strength, radiative life time and the absorption coefficients of exciton, positively and negatively charged excitons and biexciton are carried out. It is found that the ratio of the radiative life time of exciton with the trions and biexciton enhances with the reduction of geometrical confinement. The results show that (i) the binding energies of exciton, positive and negative trions and the biexciton have strong influence on the reduction of geometrical confinement effect, (ii) the binding energy is found to decrease from the binding energies of exciton to positive trion through biexciton and negative trion binding energies, (iii) the oscillator strength of trions is found to be lesser than exciton and the biexciton and (iv) the electronic and optical properties of exciton, trions and the biexciton are considerably dependent on the spatial confinement, incident photon energy and the radiative life time. The obtained results are in good agreement with the other existing literature.

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

Magneto-optical quantum interferences in a system of spinor excitons

NASA Astrophysics Data System (ADS)

Kuan, Wen-Hsuan; Gudmundsson, Vidar

2018-04-01

In this work we investigate magneto-optical properties of two-dimensional semiconductor quantum-ring excitons with Rashba and Dresselhaus spin-orbit interactions threaded by a magnetic flux perpendicular to the plane of the ring. By calculating the excitonic Aharonov-Bohm spectrum, we study the Coulomb and spin-orbit effects on the Aharonov-Bohm features. From the light-matter interactions of the excitons, we find that for scalar excitons, there are open channels for spontaneous recombination resulting in a bright photoluminescence spectrum, whereas the forbidden recombination of dipolar excitons results in a dark photoluminescence spectrum. We investigate the generation of persistent charge and spin currents. The exploration of spin orientations manifests that by adjusting the strength of the spin-orbit interactions, the exciton can be constructed as a squeezed complex with specific spin polarization. Moreover, a coherently moving dipolar exciton acquires a nontrivial dual Aharonov-Casher phase, creating the possibility to generate persistent dipole currents and spin dipole currents. Our study reveals that in the presence of certain spin-orbit generated fields, the manipulation of the magnetic field provides a potential application for quantum-ring spinor excitons to be utilized in nano-scaled magneto-optical switches.

Mapping the exciton diffusion in semiconductor nanocrystal solids.

PubMed

Kholmicheva, Natalia; Moroz, Pavel; Bastola, Ebin; Razgoniaeva, Natalia; Bocanegra, Jesus; Shaughnessy, Martin; Porach, Zack; Khon, Dmitriy; Zamkov, Mikhail

2015-03-24

Colloidal nanocrystal solids represent an emerging class of functional materials that hold strong promise for device applications. The macroscopic properties of these disordered assemblies are determined by complex trajectories of exciton diffusion processes, which are still poorly understood. Owing to the lack of theoretical insight, experimental strategies for probing the exciton dynamics in quantum dot solids are in great demand. Here, we develop an experimental technique for mapping the motion of excitons in semiconductor nanocrystal films with a subdiffraction spatial sensitivity and a picosecond temporal resolution. This was accomplished by doping PbS nanocrystal solids with metal nanoparticles that force the exciton dissociation at known distances from their birth. The optical signature of the exciton motion was then inferred from the changes in the emission lifetime, which was mapped to the location of exciton quenching sites. By correlating the metal-metal interparticle distance in the film with corresponding changes in the emission lifetime, we could obtain important transport characteristics, including the exciton diffusion length, the number of predissociation hops, the rate of interparticle energy transfer, and the exciton diffusivity. The benefits of this approach to device applications were demonstrated through the use of two representative film morphologies featuring weak and strong interparticle coupling.

Exciton diamagnetic shift and optical properties in CdSe nanocrystal quantum dots in magnetic fields

NASA Astrophysics Data System (ADS)

Wu, Shudong; Cheng, Liwen

2018-04-01

The magnetic field dependence of the optical properties of CdSe nanocrystal quantum dots (NQDs) is investigated theoretically using a perturbation method within the effective-mass approximation. The results show that the magnetic field lifts the degeneracy of the electron (hole) states. A blue-shift in the absorption spectra of m ≥ 0 exciton states is observed while the absorption peak of m < 0 exciton states is first red-shifted and then blue-shifted with increasing the magnetic field strength B. This is attributed to the interplay of the orbital Zeeman effect and the additive confinement induced by the magnetic field. The excitonic absorption coefficient is almost independent of B in the strong confinement regime. The applied magnetic field causes the splitting of degenerated exciton states, resulting in the new absorption peaks. Based on the first-order perturbation theory, we propose the analytical expressions for the exciton binding energy, exciton transition energy and exciton diamagnetic shift of 1s, 1p-1, 1p0, 1p1, 1d-2, 1d-1, 1d0, 1d1, 1d2 and 2s exciton states on the applied magnetic field in the strong confinement regime.

Ultrafast exciton relaxation in monolayer transition metal dichalcogenides

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

Thilagam, A., E-mail: thilaphys@gmail.com

2016-04-28

We examine a mechanism by which excitons undergo ultrafast relaxation in common monolayer transition metal dichalcogenides. It is shown that at densities ≈1 × 10{sup 11 }cm{sup −2} and temperatures ≤60 K, excitons in well known monolayers (MoS{sub 2}, MoSe{sub 2}, WS{sub 2}, and WSe{sub 2}) exist as point-like structureless electron-hole quasi-particles. We evaluate the average rate of exciton energy relaxation due to acoustic phonons via the deformation potential and the piezoelectric coupling mechanisms and examine the effect of spreading of the excitonic wavefunction into the region perpendicular to the monolayer plane. Our results show that the exciton relaxation rate is enhanced with increasemore » in the exciton temperature, while it is decreased with increase in the lattice temperature. Good agreements with available experimental data are obtained when the calculations are extrapolated to room temperatures. A unified approach taking into account the deformation potential and piezoelectric coupling mechanisms shows that exciton relaxation induced by phonons is as significant as defect assisted scattering and trapping of excitons by surface states in monolayer transition metal dichalcogenides.« less

Charge-transfer excitons at organic semiconductor surfaces and interfaces.

PubMed

Zhu, X-Y; Yang, Q; Muntwiler, M

2009-11-17

When a material of low dielectric constant is excited electronically from the absorption of a photon, the Coulomb attraction between the excited electron and the hole gives rise to an atomic H-like quasi-particle called an exciton. The bound electron-hole pair also forms across a material interface, such as the donor/acceptor interface in an organic heterojunction solar cell; the result is a charge-transfer (CT) exciton. On the basis of typical dielectric constants of organic semiconductors and the sizes of conjugated molecules, one can estimate that the binding energy of a CT exciton across a donor/acceptor interface is 1 order of magnitude greater than k(B)T at room temperature (k(B) is the Boltzmann constant and T is the temperature). How can the electron-hole pair escape this Coulomb trap in a successful photovoltaic device? To answer this question, we use a crystalline pentacene thin film as a model system and the ubiquitous image band on the surface as the electron acceptor. We observe, in time-resolved two-photon photoemission, a series of CT excitons with binding energies < or = 0.5 eV below the image band minimum. These CT excitons are essential solutions to the atomic H-like Schrodinger equation with cylindrical symmetry. They are characterized by principal and angular momentum quantum numbers. The binding energy of the lowest lying CT exciton with 1s character is more than 1 order of magnitude higher than k(B)T at room temperature. The CT(1s) exciton is essentially the so-called exciplex and has a very low probability of dissociation. We conclude that hot CT exciton states must be involved in charge separation in organic heterojunction solar cells because (1) in comparison to CT(1s), hot CT excitons are more weakly bound by the Coulomb potential and more easily dissociated, (2) density-of-states of these hot excitons increase with energy in the Coulomb potential, and (3) electronic coupling from a donor exciton to a hot CT exciton across the D/A interface can be higher than that to CT(1s) as expected from energy resonance arguments. We suggest a design principle in organic heterojunction solar cells: there must be strong electronic coupling between molecular excitons in the donor and hot CT excitons across the D/A interface.

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.

Generic picture of the emission properties of III-nitride polariton laser diodes: Steady state and current modulation response

NASA Astrophysics Data System (ADS)

Iorsh, Ivan; Glauser, Marlene; Rossbach, Georg; Levrat, Jacques; Cobet, Munise; Butté, Raphaël; Grandjean, Nicolas; Kaliteevski, Mikhail A.; Abram, Richard A.; Kavokin, Alexey V.

2012-09-01

The main emission characteristics of electrically driven polariton lasers based on planar GaN microcavities with embedded InGaN quantum wells are studied theoretically. The polariton emission dependence on pump current density is first modeled using a set of semiclassical Boltzmann equations for the exciton polaritons that are coupled to the rate equation describing the electron-hole plasma population. Two experimentally relevant pumping geometries are considered, namely the direct injection of electrons and holes into the strongly coupled microcavity region and intracavity optical pumping via an embedded light-emitting diode. The theoretical framework allows the determination of the minimum threshold current density Jthr,min as a function of lattice temperature and exciton-cavity photon detuning for the two pumping schemes. A Jthr,min value of 5 and 6 A cm-2 is derived for the direct injection scheme and for the intracavity optical pumping one, respectively, at room temperature at the optimum detuning. Then an approximate quasianalytical model is introduced to derive solutions for both the steady-state and high-speed current modulation. This analysis makes it possible to show that the exciton population, which acts as a reservoir for the stimulated relaxation process, gets clamped once the condensation threshold is crossed, a behavior analogous to what happens in conventional laser diodes with the carrier density above threshold. Finally, the modulation transfer function is calculated for both pumping geometries and the corresponding cutoff frequency is determined.

Room-Temperature Micron-Scale Exciton Migration in a Stabilized Emissive Molecular Aggregate.

PubMed

Caram, Justin R; Doria, Sandra; Eisele, Dörthe M; Freyria, Francesca S; Sinclair, Timothy S; Rebentrost, Patrick; Lloyd, Seth; Bawendi, Moungi G

2016-11-09

We report 1.6 ± 1 μm exciton transport in self-assembled supramolecular light-harvesting nanotubes (LHNs) assembled from amphiphillic cyanine dyes. We stabilize LHNs in a sucrose glass matrix, greatly reducing light and oxidative damage and allowing the observation of exciton-exciton annihilation signatures under weak excitation flux. Fitting to a one-dimensional diffusion model, we find an average exciton diffusion constant of 55 ± 20 cm 2 /s, among the highest measured for an organic system. We develop a simple model that uses cryogenic measurements of static and dynamic energetic disorder to estimate a diffusion constant of 32 cm 2 /s, in agreement with experiment. We ascribe large exciton diffusion lengths to low static and dynamic energetic disorder in LHNs. We argue that matrix-stabilized LHNS represent an excellent model system to study coherent excitonic transport.

Excitons in atomically thin 2D semiconductors and their applications

NASA Astrophysics Data System (ADS)

Xiao, Jun; Zhao, Mervin; Wang, Yuan; Zhang, Xiang

2017-06-01

The research on emerging layered two-dimensional (2D) semiconductors, such as molybdenum disulfide (MoS2), reveals unique optical properties generating significant interest. Experimentally, these materials were observed to host extremely strong light-matter interactions as a result of the enhanced excitonic effect in two dimensions. Thus, understanding and manipulating the excitons are crucial to unlocking the potential of 2D materials for future photonic and optoelectronic devices. In this review, we unravel the physical origin of the strong excitonic effect and unique optical selection rules in 2D semiconductors. In addition, control of these excitons by optical, electrical, as well as mechanical means is examined. Finally, the resultant devices such as excitonic light emitting diodes, lasers, optical modulators, and coupling in an optical cavity are overviewed, demonstrating how excitons can shape future 2D optoelectronics.

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.

Strain Control of Exciton-Phonon Coupling in Atomically Thin Semiconductors.

PubMed

Niehues, Iris; Schmidt, Robert; Drüppel, Matthias; Marauhn, Philipp; Christiansen, Dominik; Selig, Malte; Berghäuser, Gunnar; Wigger, Daniel; Schneider, Robert; Braasch, Lisa; Koch, Rouven; Castellanos-Gomez, Andres; Kuhn, Tilmann; Knorr, Andreas; Malic, Ermin; Rohlfing, Michael; Michaelis de Vasconcellos, Steffen; Bratschitsch, Rudolf

2018-03-14

Semiconducting transition metal dichalcogenide (TMDC) monolayers have exceptional physical properties. They show bright photoluminescence due to their unique band structure and absorb more than 10% of the light at their excitonic resonances despite their atomic thickness. At room temperature, the width of the exciton transitions is governed by the exciton-phonon interaction leading to strongly asymmetric line shapes. TMDC monolayers are also extremely flexible, sustaining mechanical strain of about 10% without breaking. The excitonic properties strongly depend on strain. For example, exciton energies of TMDC monolayers significantly redshift under uniaxial tensile strain. Here, we demonstrate that the width and the asymmetric line shape of excitonic resonances in TMDC monolayers can be controlled with applied strain. We measure photoluminescence and absorption spectra of the A exciton in monolayer MoSe 2 , WSe 2 , WS 2 , and MoS 2 under uniaxial tensile strain. We find that the A exciton substantially narrows and becomes more symmetric for the selenium-based monolayer materials, while no change is observed for atomically thin WS 2 . For MoS 2 monolayers, the line width increases. These effects are due to a modified exciton-phonon coupling at increasing strain levels because of changes in the electronic band structure of the respective monolayer materials. This interpretation based on steady-state experiments is corroborated by time-resolved photoluminescence measurements. Our results demonstrate that moderate strain values on the order of only 1% are already sufficient to globally tune the exciton-phonon interaction in TMDC monolayers and hold the promise for controlling the coupling on the nanoscale.

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.

Accelerating FRET between Near-Infrared Emitting Quantum Dots Using a Molecular J-Aggregate as an Exciton Bridge.

PubMed

Wang, Chen; Weiss, Emily A

2017-09-13

Fast energy transfer (EnT) among quantum dots (QDs) with near-infrared (NIR) emission is essential for fully exploiting their light harvesting and photon downconversion (multiexciton generation) abilities. This paper demonstrates a relayed EnT mechanism that accelerates the migration of NIR excitons between PbS QDs by a factor of 20 from that of one-step EnT through a polyelectrolyte and even a factor of ∼2 from that of one-step EnT between QDs in direct contact, by employing a J-aggregate (J-agg) of a cyanine dye as an exciton bridge. The donor QDs, acceptor QDs, and J-agg are electrostatically assembled into a sandwich structure with layer-by-layer deposition. Estimates of EnT rate and yield from transient and steady-state absorption and photoluminescence spectroscopies show that the rate-limiting step in the relay is EnT from the donor QD to the J-agg, while EnT from the J-agg to the acceptor QD occurs in <10 ps. A comparison of this system to the analogous solution-phase system suggests that the overall donor-to-acceptor EnT yield in the relay (18%) can be improved by depositing the J-agg with more intermolecular order. This work demonstrates the viability of relayed EnT through a molecular bridge as a strategy for accelerating long-distance exciton migration in assemblies of QDs, in particular in the near-infrared.

Synthesis, structural, thermal and optical studies of inorganic-organic hybrid semiconductors, R-PbI4

NASA Astrophysics Data System (ADS)

Pradeesh, K.; Nageswara Rao, K.; Vijaya Prakash, G.

2013-02-01

Wide varieties of naturally self-assembled two-dimensional inorganic-organic (IO) hybrid semiconductors, (4-ClC6H4NH3)2PbI4, (C6H9C2H4NH3)2PbI4, (CnH2n+1NH3)2PbI4 (where n = 12, 16, 18), (CnH2n-1NH3)2PbI4 (where n = 3, 4, 5), (C6H5C2H4NH3)2PbI4, NH3(CH2)12NH3PbI4, and (C4H3SC2H4NH3)2PbI4, were fabricated by intercalating structurally diverse organic guest moieties into lead iodide perovskite structure. The crystal packing of all these fabricated IO-hybrids comprises of well-ordered organic and inorganic layers, stacked-up alternately along c-axis. Almost all these hybrids are thermally stable upto 200 °C and show strong room-temperature exciton absorption and photoluminescence features. These strongly confined optical excitons are highly influenced by structural deformation of PbI matrix due to the conformation of organic moiety. A systematic correlation of optical exciton behavior of IO-hybrids with the organic/inorganic layer thicknesses, intercalating organic moieties, and various structural disorders were discussed. This systematic study clearly suggests that the PbI layer crumpling is directly responsible for the tunability of optical exciton energy.

Order of magnitude enhancement of monolayer MoS 2 photoluminescence due to near-field energy influx from nanocrystal films

DOE PAGES

Guo, Tianle; Sampat, Siddharth; Zhang, Kehao; ...

2017-02-03

Two-dimensional transition metal dichalcogenides (TMDCs) like MoS 2 are promising candidates for various optoelectronic applications. The typical photoluminescence (PL) of monolayer MoS 2 is however known to suffer very low quantum yields. We demonstrate a 10-fold increase of MoS 2 excitonic PL enabled by nonradiative energy transfer (NRET) from adjacent nanocrystal quantum dot (NQD) films. The understanding of this effect is facilitated by our application of transient absorption (TA) spectroscopy to monitor the energy influx into the monolayer MoS 2 in the process of ET from photoexcited CdSe/ZnS nanocrystals. In contrast to PL spectroscopy, TA can detect even non-emissive excitons,more » and we register an order of magnitude enhancement of the MoS 2 excitonic TA signatures in hybrids with NQDs. The appearance of ET-induced nanosecond-scale kinetics in TA features is consistent with PL dynamics of energy-accepting MoS 2 and PL quenching data of the energy-donating NQDs. The observed enhancement is attributed to the reduction of recombination losses for excitons gradually transferred into MoS 2 under quasi-resonant conditions as compared with their direct photoproduction. Furthermore, the TA and PL data clearly illustrate the efficacy of MoS 2 and likely other TMDC materials as energy acceptors and the possibility of their practical utilization in NRET-coupled hybrid nanostructures.« less

Rational Design of Charge-Transfer Interactions in Halogen-Bonded Co-crystals toward Versatile Solid-State Optoelectronics.

PubMed

Zhu, Weigang; Zheng, Renhui; Zhen, Yonggang; Yu, Zhenyi; Dong, Huanli; Fu, Hongbing; Shi, Qiang; Hu, Wenping

2015-09-02

Charge-transfer (CT) interactions between donor (D) and acceptor (A) groups, as well as CT exciton dynamics, play important roles in optoelectronic devices, such as organic solar cells, photodetectors, and light-emitting sources, which are not yet well understood. In this contribution, the self-assembly behavior, molecular stacking structure, CT interactions, density functional theory (DFT) calculations, and corresponding physicochemical properties of two similar halogen-bonded co-crystals are comprehensively investigated and compared, to construct an "assembly-structure-CT-property" relationship. Bpe-IFB wire-like crystals (where Bpe = 1,2-bis(4-pyridyl)ethylene and IFB = 1,3,5-trifluoro-2,4,6-triiodobenzene), packed in a segregated stacking form with CT ground and excited states, are measured to be quasi-one-dimensional (1D) semiconductors and show strong violet-blue photoluminescence (PL) from the lowest CT1 excitons (ΦPL = 26.1%), which can be confined and propagate oppositely along the 1D axial direction. In comparison, Bpe-F4DIB block-like crystals (F4DIB = 1,4-diiodotetrafluorobenzene), packed in a mixed stacking form without CT interactions, are determined to be insulators and exhibit unique white light emission and two-dimensional optical waveguide property. Surprisingly, it seems that the intrinsic spectroscopic states of Bpe and F4DIB do not change after co-crystallization, which is also confirmed by theoretical calculations, thus offering a new design principle for white light emitting materials. More importantly, we show that the CT interactions in co-crystals are related to their molecular packing and can be triggered or suppressed by crystal engineering, which eventually leads to distinct optoelectronic properties. These results help us to rationally control the CT interactions in organic D-A systems by tuning the molecular stacking, toward the development of a fantastic "optoelectronic world".

Coherent detection of THz-induced sideband emission from excitons in the nonperturbative regime

NASA Astrophysics Data System (ADS)

Uchida, K.; Otobe, T.; Mochizuki, T.; Kim, C.; Yoshita, M.; Tanaka, K.; Akiyama, H.; Pfeiffer, L. N.; West, K. W.; Hirori, H.

2018-04-01

Strong interaction of a terahertz (THz) wave with excitons induces nonperturbative optical effects such as Rabi splitting and high-order sideband generation. Here, we investigated coherent properties of THz-induced sideband emissions from GaAs/AlGaAs multiquantum wells. With increasing THz electric field, optical susceptibility of the THz-dressed exciton shows a redshift with spectral broadening and extraordinary phase shift. This implies that the field ionization of the 1 s exciton modifies the THz-dressed exciton in the nonperturbative regime.

Exciton Dynamics and Many Body Interactions in Layered Semiconducting Materials Revealed with Non-linear Coherent Spectroscopy

NASA Astrophysics Data System (ADS)

Dey, Prasenjit

Atomically thin, semiconducting transition metal dichalogenides (TMDs), a special class of layered semiconductors, that can be shaped as a perfect two dimensional material, have garnered a lot of attention owing to their fascinating electronic properties which are achievable at the extreme nanoscale. In contrast to graphene, the most celebrated two-dimensional (2D) material thus far; TMDs exhibit a direct band gap in the monolayer regime. The presence of a non-zero bandgap along with the broken inversion symmetry in the monolayer limit brands semiconducting TMDs as the perfect candidate for future optoelectronic and valleytronics-based device application. These remarkable discoveries demand exploration of different materials that possess similar properties alike TMDs. Recently, III-VI layered semiconducting materials (example: InSe, GaSe etc.) have also emerged as potential materials for optical device based applications as, similar to TMDs, they can be shaped into a perfect two-dimensional form as well as possess a sizable band gap in their nano-regime. The perfect 2D character in layered materials cause enhancement of strong Coulomb interaction. As a result, excitons, a coulomb bound quasiparticle made of electron-hole pair, dominate the optical properties near the bandgap. The basis of development for future optoelectronic-based devices requires accurate characterization of the essential properties of excitons. Two fundamental parameters that characterize the quantum dynamics of excitons are: a) the dephasing rate, gamma, which represents the coherence loss due to the interaction of the excitons with their environment (for example- phonons, impurities, other excitons, etc.) and b) excited state population decay rate arising from radiative and non-radiative relaxation processes. The dephasing rate is representative of the time scale over which excitons can be coherently manipulated, therefore accurately probing the source of exciton decoherence is crucial for understanding the basic unexplored science as well as creating technological developments. The dephasing dynamics in semiconductors typically occur in the picosecond to femtosecond timescale, thus the use of ultrafast laser spectroscopy is a potential route to probe such excitonic responses. The focus of this dissertation is two-fold: firstly, to develop the necessary instrumentation to accurately probe the aforementioned parameters and secondly, to explore the quantum dynamics and the underlying many-body interactions in different layered semiconducting materials. A custom-built multidimensional optical non-linear spectrometer was developed in order to perform two-dimensional spectroscopic (2DFT) measurements. The advantages of this technique are multifaceted compared to regular one-dimensional and non-linear incoherent techniques. 2DFT technique is based on an enhanced version of Four wave mixing experiments. This powerful tool is capable of identifying the resonant coupling, probing the coherent pathways, unambiguously extracting the homogeneous linewidth in the presence of inhomogeneity and decomposing a complex spectra into real and imaginary parts. It is not possible to uncover such crucial features by employing one dimensional non-linear technique. Monolayers as well as bulk TMDs and group III-VI bulk layered materials are explored in this dissertation. The exciton quantum dynamics is explored with three pulse four-wave mixing whereas the phase sensitive measurements are obtained by employing two-dimensional Fourier transform spectroscopy. Temperature and excitation density dependent 2DFT experiments unfold the information associated with the many-body interactions in the layered semiconducting samples.

Resolving ultrafast exciton migration in organic solids at the nanoscale

NASA Astrophysics Data System (ADS)

Penwell, Samuel B.; Ginsberg, Lucas D. S.; Noriega, Rodrigo; Ginsberg, Naomi S.

2017-11-01

Effectiveness of molecular-based light harvesting relies on transport of excitons to charge-transfer sites. Measuring exciton migration, however, has been challenging because of the mismatch between nanoscale migration lengths and the diffraction limit. Instead of using bulk substrate quenching methods, here we define quenching boundaries all-optically with sub-diffraction resolution, thus characterizing spatiotemporal exciton migration on its native nanometre and picosecond scales. By transforming stimulated emission depletion microscopy into a time-resolved ultrafast approach, we measure a 16-nm migration length in poly(2,5-di(hexyloxy)cyanoterephthalylidene) conjugated polymer films. Combined with Monte Carlo exciton hopping simulations, we show that migration in these films is essentially diffusive because intrinsic chromophore energetic disorder is comparable to chromophore inhomogeneous broadening. Our approach will enable previously unattainable correlation of local material structure to exciton migration character, applicable not only to photovoltaic or display-destined organic semiconductors but also to explaining the quintessential exciton migration exhibited in photosynthesis.

Multiple exciton generation in chiral carbon nanotubes: Density functional theory based computation

NASA Astrophysics Data System (ADS)

Kryjevski, Andrei; Mihaylov, Deyan; Kilina, Svetlana; Kilin, Dmitri

2017-10-01

We use a Boltzmann transport equation (BE) to study time evolution of a photo-excited state in a nanoparticle including phonon-mediated exciton relaxation and the multiple exciton generation (MEG) processes, such as exciton-to-biexciton multiplication and biexciton-to-exciton recombination. BE collision integrals are computed using Kadanoff-Baym-Keldysh many-body perturbation theory based on density functional theory simulations, including exciton effects. We compute internal quantum efficiency (QE), which is the number of excitons generated from an absorbed photon in the course of the relaxation. We apply this approach to chiral single-wall carbon nanotubes (SWCNTs), such as (6,2) and (6,5). We predict efficient MEG in the (6,2) and (6,5) SWCNTs within the solar spectrum range starting at the 2Eg energy threshold and with QE reaching ˜1.6 at about 3Eg, where Eg is the electronic gap.

Electrically tunable organic–inorganic hybrid polaritons with monolayer WS2

PubMed Central

Flatten, Lucas C.; Coles, David M.; He, Zhengyu; Lidzey, David G.; Taylor, Robert A.; Warner, Jamie H.; Smith, Jason M.

2017-01-01

Exciton-polaritons are quasiparticles consisting of a linear superposition of photonic and excitonic states, offering potential for nonlinear optical devices. The excitonic component of the polariton provides a finite Coulomb scattering cross section, such that the different types of exciton found in organic materials (Frenkel) and inorganic materials (Wannier-Mott) produce polaritons with different interparticle interaction strength. A hybrid polariton state with distinct excitons provides a potential technological route towards in situ control of nonlinear behaviour. Here we demonstrate a device in which hybrid polaritons are displayed at ambient temperatures, the excitonic component of which is part Frenkel and part Wannier-Mott, and in which the dominant exciton type can be switched with an applied voltage. The device consists of an open microcavity containing both organic dye and a monolayer of the transition metal dichalcogenide WS2. Our findings offer a perspective for electrically controlled nonlinear polariton devices at room temperature. PMID:28094281

Excitons in atomically thin 2D semiconductors and their applications

DOE PAGES

Xiao, Jun; Zhao, Mervin; Wang, Yuan; ...

2017-01-01

The research on emerging layered two-dimensional (2D) semiconductors, such as molybdenum disulfide (MoS 2), reveals unique optical properties generating significant interest. Experimentally, these materials were observed to host extremely strong light-matter interactions as a result of the enhanced excitonic effect in two dimensions. Thus, understanding and manipulating the excitons are crucial to unlocking the potential of 2D materials for future photonic and optoelectronic devices. Here in this review, we unravel the physical origin of the strong excitonic effect and unique optical selection rules in 2D semiconductors. In addition, control of these excitons by optical, electrical, as well as mechanical meansmore » is examined. Finally, the resultant devices such as excitonic light emitting diodes, lasers, optical modulators, and coupling in an optical cavity are overviewed, demonstrating how excitons can shape future 2D optoelectronics.« less

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

Beard, Matthew C; Chen, Xihan; Lu, Haipeng

The exciton binding energy in methylammonium lead iodide (MAPbI3) is about 10 meV, around 1/3 of the available thermal energy (kBT ~ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination,more » and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.« less

Understanding molecular structure dependence of exciton diffusion in conjugated small molecules

NASA Astrophysics Data System (ADS)

Li, Zi; Zhang, Xu; Woellner, Cristiano F.; Lu, Gang

2014-04-01

First-principles simulations are carried out to understand molecular structure dependence of exciton diffusion in a series of small conjugated molecules arranged in a disordered, crystalline, and blend structure. Exciton diffusion length (LD), lifetime, and diffusivity in four diketopyrrolopyrrole derivatives are calculated and the results compare very well with experimental values. The correlation between exciton diffusion and molecular structure is examined in detail. In the disordered molecule structure, a longer backbone length leads to a shorter exciton lifetime and a higher exciton diffusivity, but it does not change LD substantially. Removal of the end alkyl chains or the extra branch on the side alkyl chains reduces LD. In the crystalline structure, exciton diffusion exhibits a strong anisotropy whose origin can be elucidated from the intermolecular transition density interaction point of view. In the blend structure, LD increases with the crystalline ratios, which are estimated and consistent with the experimental results.

Superfluidity of dipolar excitons in a transition metal dichalcogenide double layer

NASA Astrophysics Data System (ADS)

Berman, Oleg L.; Kezerashvili, Roman Ya.

2017-09-01

We study formation and superfluidity of dipolar excitons in double layer heterostructures formed by two transition metal dichalcogenide (TMDC) atomically thin layers. Considering screening effects for an electron-hole interaction via the harmonic oscillator approximation for the Keldysh potential, the analytical expressions for the exciton energy spectrum and the mean field critical temperature Tc for the superfluidity are obtained. It is shown that binding energies of A excitons are larger than for B excitons. The mean field critical temperature for a two-component dilute exciton system in a TMDC double layer is analyzed and shown that the latter is an increasing function of the factor Q , determined by the effective masses of A and B excitons and their reduced mass. Comparison of the calculations for Tc performed by employing the Coulomb and Keldysh interactions demonstrates the importance of screening effects in TMDC.

Selective Amplification of the Primary Exciton in a MoS_{2} Monolayer.

PubMed

Lee, Hyun Seok; Kim, Min Su; Jin, Youngjo; Han, Gang Hee; Lee, Young Hee; Kim, Jeongyong

2015-11-27

Optoelectronics applications for transition-metal dichalcogenides are still limited by weak light absorption and their complex exciton modes are easily perturbed by varying excitation conditions because they are inherent in atomically thin layers. Here, we propose a method of selectively amplifying the primary exciton (A^{0}) among the exciton complexes in monolayer MoS_{2} via cyclic reexcitation of cavity-free exciton-coupled plasmon propagation. This was implemented by partially overlapping a Ag nanowire on a MoS_{2} monolayer separated by a thin SiO_{2} spacer. Exciton-coupled plasmons in the nanowire enhance the A^{0} radiation in MoS_{2}. The cumulative amplification of emission enhancement by cyclic plasmon traveling reaches approximately twentyfold selectively for the A^{0}, while excluding other B exciton and multiexciton by significantly reduced band filling, without oscillatory spectra implying plasmonic cavity effects.

Exciton diffusion coefficient measurement in ZnO nanowires under electron beam irradiation.

PubMed

Donatini, Fabrice; Pernot, Julien

2018-03-09

In semiconductor nanowires (NWs) the exciton diffusion coefficient can be determined using a scanning electron microscope fitted with a cathodoluminescence system. High spatial and temporal resolution cathodoluminescence experiments are needed to measure independently the exciton diffusion length and lifetime in single NWs. However, both diffusion length and lifetime can be affected by the electron beam bombardment during observation and measurement. Thus, in this work the exciton lifetime in a ZnO NW is measured versus the electron beam dose (EBD) via a time-resolved cathodoluminescence experiment with a temporal resolution of 50 ps. The behavior of the measured exciton lifetime is consistent with our recent work on the EBD dependence of the exciton diffusion length in similar NWs investigated under comparable SEM conditions. Combining the two results, the exciton diffusion coefficient in ZnO is determined at room temperature and is found constant over the full span of EBD.

Crossover from polariton lasing to exciton lasing in a strongly coupled ZnO microcavity.

PubMed

Lai, Ying-Yu; Chou, Yu-Hsun; Lan, Yu-Pin; Lu, Tien-Chang; Wang, Shing-Chung; Yamamoto, Yoshihisa

2016-02-03

Unlike conventional photon lasing, in which the threshold is limited by the population inversion of the electron-hole plasma, the exciton lasing generated by exciton-exciton scattering and the polariton lasing generated by dynamical condensates have received considerable attention in recent years because of the sub-Mott density and low-threshold operation. This paper presents a novel approach to generate both exciton and polariton lasing in a strongly coupled microcavity (MC) and determine the critical driving requirements for simultaneously triggering these two lasing operation in temperature <140 K and large negative polariton-exciton offset (<-133 meV) conditions. In addition, the corresponding lasing behaviors, such as threshold energy, linewidth, phase diagram, and angular dispersion are verified. The results afford a basis from which to understand the complicated lasing mechanisms in strongly coupled MCs and verify a new method with which to trigger dual laser emission based on exciton and polariton.

Exciton interference revealed by energy dependent exciton transfer rate for ring-structured molecular systems.

PubMed

Yan, Yun-An

2016-01-14

The quantum interference is an intrinsic phenomenon in quantum physics for photon and massive quantum particles. In principle, the quantum interference may also occur with quasi-particles, such as the exciton. In this study, we show how the exciton quantum interference can be significant in aggregates through theoretical simulations with hierarchical equations of motion. The systems under investigation are generalized donor-bridge-acceptor model aggregates with the donor consisting of six homogeneous sites assuming the nearest neighbor coupling. For the models with single-path bridge, the exciton transfer time only shows a weak excitation energy dependence. But models with double-path bridge have a new short transfer time scale and the excitation energy dependence of the exciton transfer time assumes clear peak structure which is detectable with today's nonlinear spectroscopy. This abnormality is attributed to the exciton quantum interference and the condition for a clear observation in experiment is also explored.

Multiple exciton generation in chiral carbon nanotubes: Density functional theory based computation.

PubMed

Kryjevski, Andrei; Mihaylov, Deyan; Kilina, Svetlana; Kilin, Dmitri

2017-10-21

We use a Boltzmann transport equation (BE) to study time evolution of a photo-excited state in a nanoparticle including phonon-mediated exciton relaxation and the multiple exciton generation (MEG) processes, such as exciton-to-biexciton multiplication and biexciton-to-exciton recombination. BE collision integrals are computed using Kadanoff-Baym-Keldysh many-body perturbation theory based on density functional theory simulations, including exciton effects. We compute internal quantum efficiency (QE), which is the number of excitons generated from an absorbed photon in the course of the relaxation. We apply this approach to chiral single-wall carbon nanotubes (SWCNTs), such as (6,2) and (6,5). We predict efficient MEG in the (6,2) and (6,5) SWCNTs within the solar spectrum range starting at the 2E g energy threshold and with QE reaching ∼1.6 at about 3E g , where E g is the electronic gap.

Ultrafast dynamics of multi-exciton state coupled to coherent vibration in zinc chlorin aggregates for artificial photosynthesis.

PubMed

Shi, Tongchao; Liu, Zhengzheng; Miyatake, Tomohiro; Tamiaki, Hitoshi; Kobayashi, Takayoshi; Zhang, Zeyu; Du, Juan; Leng, Yuxin

2017-11-27

Ultrafast vibronic dynamics induced by the interaction of the Frenkel exciton with the coherent molecular vibrations in a layer-structured zinc chlorin aggregates prepared for artificial photosynthesis have been studied by 7.1 fs real-time vibrational spectroscopy with multi-spectrum detection. The fast decay of 100 ± 5fs is ascribed to the relaxation from the higher multi-exciton state (MES) to the one-exciton state, and the slow one of 863 ± 70fs is assigned to the relaxation from Q-exciton state to the dark nonfluorescent charge-transfer (CT) state, respectively. In addition, the wavelength dependences of the exciton-vibration coupling strength are found to follow the zeroth derivative of the transient absorption spectra of the exciton. It could be explained in term of the transition dipole moment modulated by dynamic intensity borrowing between the B transition and the Q transition through the vibronic interactions.

The Zeeman splitting of bulk 2H-MoTe2 single crystal in high magnetic field

NASA Astrophysics Data System (ADS)

Sun, Yan; Zhang, Junpei; Ma, Zongwei; Chen, Cheng; Han, Junbo; Chen, Fangchu; Luo, Xuan; Sun, Yuping; Sheng, Zhigao

2017-03-01

A high magnetic field magneto-optical spectrum is utilized to study the A exciton of bulk 2H-MoTe2 single crystal. A clear Zeeman splitting of the A exciton is observed under high magnetic fields up to 41.68 T, and the g-factor (-2.09 ± 0.08) is deduced. Moreover, a high magnetic field enables us to obtain the quadratic diamagnetic shifts of the A exciton (0.486 μeV T-2). Accordingly, the binding energy, reduced mass, and radius of the A exciton were obtained by using both two and three dimensional models. Compared with other transition metal dichalcogenides (TMDs), the A exciton of bulk 2H-MoTe2 has a relatively small binding energy and larger exciton radius, which provide fundamental parameters for comprehensive understanding of excitons in TMDs as well as their future applications.

Many-body effects and excitonic features in 2D biphenylene carbon

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

Lüder, Johann, E-mail: johann.luder@physics.uu.se; Puglia, Carla; Eriksson, Olle

2016-01-14

The remarkable excitonic effects in low dimensional materials in connection to large binding energies of excitons are of great importance for research and technological applications such as in solar energy and quantum information processing as well as for fundamental investigations. In this study, the unique electronic and excitonic properties of the two dimensional carbon network biphenylene carbon were investigated with GW approach and the Bethe-Salpeter equation accounting for electron correlation effects and electron-hole interactions, respectively. Biphenylene carbon exhibits characteristic features including bright and dark excitons populating the optical gap of 0.52 eV and exciton binding energies of 530 meV asmore » well as a technologically relevant intrinsic band gap of 1.05 eV. Biphenylene carbon’s excitonic features, possibly tuned, suggest possible applications in the field of solar energy and quantum information technology in the future.« less

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.

Interlayer excitons in a bulk van der Waals semiconductor.

PubMed

Arora, Ashish; Drüppel, Matthias; Schmidt, Robert; Deilmann, Thorsten; Schneider, Robert; Molas, Maciej R; Marauhn, Philipp; Michaelis de Vasconcellos, Steffen; Potemski, Marek; Rohlfing, Michael; Bratschitsch, Rudolf

2017-09-21

Bound electron-hole pairs called excitons govern the electronic and optical response of many organic and inorganic semiconductors. Excitons with spatially displaced wave functions of electrons and holes (interlayer excitons) are important for Bose-Einstein condensation, superfluidity, dissipationless current flow, and the light-induced exciton spin Hall effect. Here we report on the discovery of interlayer excitons in a bulk van der Waals semiconductor. They form due to strong localization and spin-valley coupling of charge carriers. By combining high-field magneto-reflectance experiments and ab initio calculations for 2H-MoTe 2 , we explain their salient features: the positive sign of the g-factor and the large diamagnetic shift. Our investigations solve the long-standing puzzle of positive g-factors in transition metal dichalcogenides, and pave the way for studying collective phenomena in these materials at elevated temperatures.Excitons, quasi-particles of bound electron-hole pairs, are at the core of the optoelectronic properties of layered transition metal dichalcogenides. Here, the authors unveil the presence of interlayer excitons in bulk van der Waals semiconductors, arising from strong localization and spin-valley coupling of charge carriers.

An Ab Initio Exciton Model Including Charge-Transfer Excited States

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

Li, Xin; Parrish, Robert M.; Liu, Fang

Here, the Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited statesmore » and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.« less

Multi-excitonic (N=1,2 and 3) quantum dots in magnetic field: Analytical mapping of correlations (exchange) by multipole expansion

NASA Astrophysics Data System (ADS)

Singh, Sunny; Kaur, Harsimran; Sharma, Shivalika; Aggarwal, Priyanka; Hazra, Ram Kuntal

2017-04-01

The understanding of the physics of exciton, bi-exciton, tri-exciton and the subsequent insight into controlling the properties of mesoscopic systems holds the key to various exotic optical, electrical and magnetic phenomena like superconductivity, Mott insulation, Quantum Hall effect etc. Many of exciton properties are similar to atomic hydrogen that attracts researchers to explore electronic structure of exciton in quantum dots, but nontriviality arises due to coulombic interactions among electrons and holes. We propose an exact integral of coulomb (exchange) correlation in terms of finitely summed Lauricella functions to examine 3-D exciton of harmonic dots confined in zero and non-zero arbitrary magnetic field. The highlight of our work is the use of exact variational solution for coloumbic interaction between the hole and the electron and evaluation of the cross terms arising out of the coupling among centre-of-mass and relative coordinates. We also have extended the size of the system to generalized N-body problem with N=3,4 for tri-exciton (e-e-h/e-h-h)

Theory of optical absorption by interlayer excitons in transition metal dichalcogenide heterobilayers

DOE PAGES

Wu, Fengcheng; Lovorn, Timothy; MacDonald, A. H.

2018-01-22

In this paper, we present a theory of optical absorption by interlayer excitons in a heterobilayer formed from transition metal dichalcogenides. The theory accounts for the presence of small relative rotations that produce a momentum shift between electron and hole bands located in different layers, and a moire pattern in real space. Because of the momentum shift, the optically active interlayer excitons are located at the moire Brillouin zone's corners, instead of at its center, and would have elliptical optical selection rules if the individual layers were translationally invariant. We show that the exciton moire potential energy restores circular opticalmore » selection rules by coupling excitons with different center of mass momenta. A variety of interlayer excitons with both senses of circular optical activity, and energies that are tunable by twist angle, are present at each valley. The lowest energy exciton states are generally localized near the exciton potential energy minima. Finally, we discuss the possibility of using the moire pattern to achieve scalable two-dimensional arrays of nearly identical quantum dots.« less

An Ab Initio Exciton Model Including Charge-Transfer Excited States

DOE PAGES

Li, Xin; Parrish, Robert M.; Liu, Fang; ...

2017-06-15

Here, the Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited statesmore » and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.« less

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.

Polaronic exciton behavior in gas-phase water

NASA Astrophysics Data System (ADS)

Udal'tsov, Alexander V.

2018-03-01

Features of the absorption spectrum of gas-phase water in the energy range 7-10 eV have been considered applying polaronic exciton theory. The interaction of the incident photon generating polaronic exciton in water is described taking into account angular momentum of the electron so that polaronic exciton radii have been estimated in dependence on spin-orbit coupling under proton sharing. The suggested approach admits an estimate of kinetic and rotation energies of the polaronic exciton. As a result sixteen steps of half Compton wavelength, λC/2 = h/(2mec) changing polaronic exciton radius were found consistent with local maxima and shoulders in the spectrum. Thus, the absorption of gas-phase water in the energy range 8.5-10 eV has been interpreted in terms of polaronic exciton rotation mainly coupled with the proton sharing. The incident photon interaction with water is also considered in terms of Compton interaction, when the rotation energy plays a role like the energy loss of the incident photon under Compton scattering. The found symmetry and the other evidence allowed to conclude about polaronic exciton migration under the interaction angle 90°.

An Ab Initio Exciton Model Including Charge-Transfer Excited States.

PubMed

Li, Xin; Parrish, Robert M; Liu, Fang; Kokkila Schumacher, Sara I L; Martínez, Todd J

2017-08-08

The Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states [ Acc. Chem. Res. 2014 , 47 , 2857 - 2866 ]. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited states and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.

Theory of optical absorption by interlayer excitons in transition metal dichalcogenide heterobilayers

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

Wu, Fengcheng; Lovorn, Timothy; MacDonald, A. H.

In this paper, we present a theory of optical absorption by interlayer excitons in a heterobilayer formed from transition metal dichalcogenides. The theory accounts for the presence of small relative rotations that produce a momentum shift between electron and hole bands located in different layers, and a moire pattern in real space. Because of the momentum shift, the optically active interlayer excitons are located at the moire Brillouin zone's corners, instead of at its center, and would have elliptical optical selection rules if the individual layers were translationally invariant. We show that the exciton moire potential energy restores circular opticalmore » selection rules by coupling excitons with different center of mass momenta. A variety of interlayer excitons with both senses of circular optical activity, and energies that are tunable by twist angle, are present at each valley. The lowest energy exciton states are generally localized near the exciton potential energy minima. Finally, we discuss the possibility of using the moire pattern to achieve scalable two-dimensional arrays of nearly identical quantum dots.« less

Exciton exciton annihilation dynamics in chromophore complexes. II. Intensity dependent transient absorption of the LH2 antenna system.

PubMed

Bruggemann, B; May, V

2004-02-01

Using the multiexciton density matrix theory of excitation energy transfer in chromophore complexes developed in a foregoing paper [J. Chem. Phys. 118, 746 (2003)], the computation of ultrafast transient absorption spectra is presented. Beside static disorder and standard mechanisms of excitation energy dissipation the theory incorporates exciton exciton annihilation (EEA) processes. To elucidate signatures of EEA in intensity dependent transient absorption data the approach is applied to the B850 ring of the LH2 found in rhodobacter sphaeroides. As main indications for two-exciton population and resulting EEA we found (i) a weakening of the dominant single-exciton bleaching structure in the transient absorption, and (ii) an intermediate suppression of long-wavelength and short-wavelength shoulders around the bleaching structure. The suppression is caused by stimulated emission from the two-exciton to the one-exciton state and the return of the shoulders follows from a depletion of two-exciton population according to EEA. The EEA-signature survives as a short-wavelength shoulder in the transient absorption if orientational and energetic disorder are taken into account. Therefore, the observation of the EEA-signatures should be possible when doing frequency resolved transient absorption experiments with a sufficiently strongly varying pump-pulse intensity. Copyright 2004 American Institute of Physics

Magnetic field effect on the energy levels of an exciton in a GaAs quantum dot: Application for excitonic lasers.

PubMed

Jahan, K Luhluh; Boda, A; Shankar, I V; Raju, Ch Narasimha; Chatterjee, Ashok

2018-03-22

The problem of an exciton trapped in a Gaussian quantum dot (QD) of GaAs is studied in both two and three dimensions in the presence of an external magnetic field using the Ritz variational method, the 1/N expansion method and the shifted 1/N expansion method. The ground state energy and the binding energy of the exciton are obtained as a function of the quantum dot size, confinement strength and the magnetic field and compared with those available in the literature. While the variational method gives the upper bound to the ground state energy, the 1/N expansion method gives the lower bound. The results obtained from the shifted 1/N expansion method are shown to match very well with those obtained from the exact diagonalization technique. The variation of the exciton size and the oscillator strength of the exciton are also studied as a function of the size of the quantum dot. The excited states of the exciton are computed using the shifted 1/N expansion method and it is suggested that a given number of stable excitonic bound states can be realized in a quantum dot by tuning the quantum dot parameters. This can open up the possibility of having quantum dot lasers using excitonic states.

Optical identification of sulfur vacancies: Bound excitons at the edges of monolayer tungsten disulfide

PubMed Central

Carozo, Victor; Wang, Yuanxi; Fujisawa, Kazunori; Carvalho, Bruno R.; McCreary, Amber; Feng, Simin; Lin, Zhong; Zhou, Chanjing; Perea-López, Néstor; Elías, Ana Laura; Kabius, Bernd; Crespi, Vincent H.; Terrones, Mauricio

2017-01-01

Defects play a significant role in tailoring the optical properties of two-dimensional materials. Optical signatures of defect-bound excitons are important tools to probe defective regions and thus interrogate the optical quality of as-grown semiconducting monolayer materials. We have performed a systematic study of defect-bound excitons using photoluminescence (PL) spectroscopy combined with atomically resolved scanning electron microscopy and first-principles calculations. Spatially resolved PL spectroscopy at low temperatures revealed bound excitons that were present only on the edges of monolayer tungsten disulfide and not in the interior. Optical pumping of the bound excitons was sublinear, confirming their bound nature. Atomic-resolution images reveal that the areal density of monosulfur vacancies is much larger near the edges (0.92 ± 0.45 nm−2) than in the interior (0.33 ± 0.11 nm−2). Temperature-dependent PL measurements found a thermal activation energy of ~36 meV; surprisingly, this is much smaller than the bound-exciton binding energy of ~300 meV. We show that this apparent inconsistency is related to a thermal dissociation of the bound exciton that liberates the neutral excitons from negatively charged point defects. First-principles calculations confirm that sulfur monovacancies introduce midgap states that host optical transitions with finite matrix elements, with emission energies ranging from 200 to 400 meV below the neutral-exciton emission line. These results demonstrate that bound-exciton emission induced by monosulfur vacancies is concentrated near the edges of as-grown monolayer tungsten disulfide. PMID:28508048

Excitonic instability in optically pumped three-dimensional Dirac materials

NASA Astrophysics Data System (ADS)

Pertsova, Anna; Balatsky, Alexander V.

2018-02-01

Recently it was suggested that transient excitonic instability can be realized in optically pumped two-dimensional (2D) Dirac materials (DMs), such as graphene and topological insulator surface states. Here we discuss the possibility of achieving a transient excitonic condensate in optically pumped three-dimensional (3D) DMs, such as Dirac and Weyl semimetals, described by nonequilibrium chemical potentials for photoexcited electrons and holes. Similar to the equilibrium case with long-range interactions, we find that for pumped 3D DMs with screened Coulomb potential two possible excitonic phases exist, an excitonic insulator phase and the charge density wave phase originating from intranodal and internodal interactions, respectively. In the pumped case, the critical coupling for excitonic instability vanishes; therefore the two phases coexist for arbitrarily weak coupling strengths. The excitonic gap in the charge density wave phase is always the largest one. The competition between screening effects and the increase of the density of states with optical pumping results in a rich phase diagram for the transient excitonic condensate. Based on the static theory of screening, we find that under certain conditions the value of the dimensionless coupling constant screening in 3D DMs can be weaker than in 2D DMs. Furthermore, we identify the signatures of the transient excitonic condensate that could be probed by scanning tunneling spectroscopy, photoemission, and optical conductivity measurements. Finally, we provide estimates of critical temperatures and excitonic gaps for existing and hypothetical 3D DMs.

Effect of localized surface-plasmon mode on exciton transport and radiation emission in carbon nanotubes.

PubMed

Roslyak, Oleksiy; Cherqui, Charles; Dunlap, David H; Piryatinski, Andrei

2014-07-17

We report on a general theoretical approach to study exciton transport and emission in a single-walled carbon nanotube (SWNT) in the presence of a localized surface-plasmon (SP) mode within a metal nanoparticle interacting via near-field coupling. We derive a set of quantum mechanical equations of motion and approximate rate equations that account for the exciton, SP, and the environmental degrees of freedom. The material equations are complemented by an expression for the radiated power that depends on the exciton and SP populations and coherences, allowing for an examination of the angular distribution of the emitted radiation that would be measured in experiment. Numerical simulations for a (6,5) SWNT and cone-shaped Ag metal tip (MT) have been performed using this methodology. Comparison with physical parameters shows that the near-field interaction between the exciton-SP occurs in a weak coupling regime, with the diffusion processes being much faster than the exciton-SP population exchange. In such a case, the effect of the exciton population transfer to the MT with its subsequent dissipation (i.e., the Förster energy transfer) is to modify the exciton steady state distribution while reducing the equilibration time for excitons to reach a steady sate distribution. We find that the radiation distribution is dominated by SP emission for a SWNT-MT separation of a few tens of nanometers due to the fast SP emission rate, whereas the exciton-SP coherences can cause its rotation.

Suppression of exciton dephasing in sidewall-functionalized carbon nanotubes embedded into metallo-dielectric antennas.

PubMed

Shayan, Kamran; He, Xiaowei; Luo, Yue; Rabut, Claire; Li, Xiangzhi; Hartmann, Nicolai F; Blackburn, Jeffrey L; Doorn, Stephen K; Htoon, Han; Strauf, Stefan

2018-06-26

Covalent functionalization of single-walled carbon nanotubes (SWCNTs) is a promising route to enhance the quantum yield of exciton emission and can lead to single-photon emission at room temperature. However, the spectral linewidth of the defect-related E11* emission remains rather broad. Here, we systematically investigate the low-temperature exciton emission of individual SWCNTs that have been dispersed with sodium-deoxycholate (DOC) and polyfluorene (PFO-BPy), are grown by laser vaporization (LV) or by CoMoCat techniques and are functionalized with oxygen as well as 3,5-dichlorobenzene groups. The E11 excitons in oxygen-functionalized SWCNTs remain rather broad with up to 10 meV linewidth while exciton emission from 3,5-dichlorobenzene functionalized SWCNTs is found to be about one order of magnitude narrower. In all cases, wrapping with PFO-BPy provides significantly better protection against pump induced dephasing compared to DOC. To further study the influence of exciton localization on pump-induced dephasing, we have embedded the functionalized SWCNTs into metallo-dielectric antenna cavities to maximize light collection. We show that 0D excitons attributed to the E11* emission of 3,5-dichlorobenzene quantum defects of LV-grown SWCNTs can display near resolution-limited linewidths down to 35 μeV. Interestingly, these 0D excitons give rise to a 3-fold suppressed pump-induced exciton dephasing compared to the E11 excitons in the same SWCNT. These findings provide a foundation to build a unified description of the emergence of novel optical behavior from the interplay of covalently introduced defects, dispersants, and exciton confinement in SWCNTs and might further lead to the realization of indistinguishable photons from carbon nanotubes.

Theoretical and computational studies of excitons in conjugated polymers

NASA Astrophysics Data System (ADS)

Barford, William; Bursill, Robert J.; Smith, Richard W.

2002-09-01

We present a theoretical and computational analysis of excitons in conjugated polymers. We use a tight-binding model of π-conjugated electrons, with 1/r interactions for large r. In both the weak-coupling limit (defined by W>>U) and the strong-coupling limit (defined by W<

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.

Electronic structure calculation of single and coupled self-assembled quantum dots

NASA Astrophysics Data System (ADS)

Mlinar, Vladan

There are two main contributions of this thesis. First, from the theoretical point of view, we find that different treatments of the nanostructure-barrier interface in the framework of multiband effective-mass theory, result in the existence of non-physical solutions for the hole energy levels of a nanostructure. Our proposed improvement is an approach based on the envelope-function theory for nanostructures developed by Burt and Foreman. In structures with a large difference of the structural parameters between the constituent materials, such as InAs/GaAs quantum nanostructures, the conventional multiband models lead to non-physical solutions. Second, we investigate underlying physics of the theoretically less investigated QD systems. Variation of electronic and optical properties of InAs/GaAs QDs and QDM grown on [11k] substrates, where k=1,2,3 were analyzed and we found that: (i) The QD size in the growth direction determines the degree of influence of the substrate orientation: the flatter the dots, the larger the difference from the reference [001] case. (ii) The small variation of inter-dot distance in eight QD molecule qualitatively changes the transition energy dependence on the substrate orientation. (iii) Size of the QD in the growth direction determines the influence of the (In,Ga)As capping layer on the optical properties of [11k] grown InAs QDs, where k=1,2,3. Next, two cases of type II QDs where hole is localized outside the dot, were discussed: InP/InGaP QDs and QDMs in an external magnetic field, and InAs QDs capped with Ga(As,Sb). Competition between confinement, quantum mechanical coupling, and strain influence the exciton diamagnetic shift in single QD and double and triple QDM is investigated in details. Available experimental data were successfully described by one of the optically active exciton states of the lowest lying exciton quartet. Finally, the electronic and optical properties of unstrained GaAs self-assembled QDs with precisely known sizes and shape, placed in an external magnetic field are investigated. For magnetic fields applied both, in growth direction and perpendicular to it (B≤50T), we found good agreement between our predicted exciton diamagnetic shift and recent experimental magneto-photoluminescence data.

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.

Rayleigh surface wave interaction with the 2D exciton Bose-Einstein condensate

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

Boev, M. V.; Kovalev, V. M., E-mail: vadimkovalev@isp.nsc.ru

We describe the interaction of a Rayleigh surface acoustic wave (SAW) traveling on the semiconductor substrate with the excitonic gas in a double quantum well located on the substrate surface. We study the SAW attenuation and its velocity renormalization due to the coupling to excitons. Both the deformation potential and piezoelectric mechanisms of the SAW-exciton interaction are considered. We focus on the frequency and excitonic density dependences of the SAW absorption coefficient and velocity renormalization at temperatures both above and well below the critical temperature of Bose-Einstein condensation of the excitonic gas. We demonstrate that the SAW attenuation and velocitymore » renormalization are strongly different below and above the critical temperature.« less

Radiative energy transfer from MoS2 excitons to surface plasmons

NASA Astrophysics Data System (ADS)

Kang, Yimin; Li, Bowen; Fang, Zheyu

2017-12-01

In this work, we demonstrated the energy transfer process from few-layer MoS2 to gold dimer arrays via ultrafast pump-probe spectroscopy. With the overlap between the MoS2 exciton and the designed plasmon dipolar modes in the frequency domain, the exciton energy can be radiatively transferred to plasmonic structures, excited the localized surface plasmon resonance, and then enhanced the oscillation of coherent acoustic phonons. Power-dependent differential reflection signals and an analytical model based on the rate equation of exciton density were carried out to quantitatively study the energy transfer process. Our finding explores the energy flow between MoS2 excitons and surface plasmons, and can be contributed to the design of exciton-plasmon structures utilizing ultrathin materials.

Two Birds with One Stone: Tailoring Singlet Fission for Both Triplet Yield and Exciton Diffusion Length

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

Zhu, Tong; Wan, Yan; Guo, Zhi

2016-06-27

By direct imaging of singlet and triplet populations with ultrafast microscopy, it is shown that the triplet diffusion length and singlet fission yield can be simultaneously optimized for tetracene and its derivatives, making them ideal structures for application in bilayer solar cells.

Efficient charge-carrier extraction from Ag₂S quantum dots prepared by the SILAR method for utilization of multiple exciton generation.

PubMed

Zhang, Xiaoliang; Liu, Jianhua; Johansson, Erik M J

2015-01-28

The utilization of electron-hole pairs (EHPs) generated from multiple excitons in quantum dots (QDs) is of great interest toward efficient photovoltaic devices and other optoelectronic devices; however, extraction of charge carriers remains difficult. Herein, we extract photocharges from Ag2S QDs and investigate the dependence of the electric field on the extraction of charges from multiple exciton generation (MEG). Low toxic Ag2S QDs are directly grown on TiO2 mesoporous substrates by employing the successive ionic layer adsorption and reaction (SILAR) method. The contact between QDs is important for the initial charge separation after MEG and for the carrier transport, and the space between neighbor QDs decreases with more SILAR cycles, resulting in better charge extraction. At the optimal electric field for extraction of photocharges, the results suggest that the threshold energy (hνth) for MEG is 2.41Eg. The results reveal that Ag2S QD is a promising material for efficient extraction of charges from MEG and that QDs prepared by SILAR have an advantageous electrical contact facilitating charge separation and extraction.

Near Infrared Emission from Defects in Few-Layer Phosphorene

NASA Astrophysics Data System (ADS)

Aghaeimeibodi, Shahriar; Kim, Je-Hyung; Waks, Edo

Atomically thin films of black phosphorus have recently received significant attention as low dimensional optical materials with a direct exciton emission whose wavelength is tunable by controlling the number of layers. In addition to this excitonic emission, recent work has revealed emission from defect states and reported new methods to manipulate them. Monolayer phosphorene exhibits emission from localized defect states at wavelengths near 920 nm. Increasing the number of layers should shift defect emission to longer wavelengths, enabling the material to span a broader spectral range. But defect emission from few-layer phosphorene has not yet been reported. Here, we demonstrate a new class of near infrared defects in few layer phosphorene. Photoluminescence measurement shows a bright emission around 1240 nm with a sublinear growth of emission intensity with linear increase of excitation intensity, confirming the defect nature of this emission. From time-resolved lifetime measurements we determine an emission lifetime of 1.2 ns, in contrast to exciton and trion lifetimes from few layer phosphorene previously reported to be in the range of a few hundred picoseconds. This work highlights the potential of bright defects of phosphorene for near infrared optoelectronic applications.

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.

Optoelectronics of supported and suspended 2D semiconductors

NASA Astrophysics Data System (ADS)

Bolotin, Kirill

2014-03-01

Two-dimensional semiconductors, materials such monolayer molybdenum disulfide (MoS2) are characterized by strong spin-orbit and electron-electron interactions. However, both electronic and optoelectronic properties of these materials are dominated by disorder-related scattering. In this talk, we investigate approaches to reduce scattering and explore physical phenomena arising in intrinsic 2D semiconductors. First, we discuss fabrication of pristine suspended monolayer MoS2 and use photocurrent spectroscopy measurements to study excitons in this material. We observe band-edge and van Hove singularity excitons and estimate their binding energies. Furthermore, we study dissociation of these excitons and uncover the mechanism of their contribution to photoresponse of MoS2. Second, we study strain-induced modification of bandstructures of 2D semiconductors. With increasing strain, we find large and controllable band gap reduction of both single- and bi-layer MoS2. We also detect experimental signatures consistent with strain-induced transition from direct to indirect band gap in monolayer MoS2. Finally, we fabricate heterostructures of dissimilar 2D semiconductors and study their photoresponse. For closely spaced 2D semiconductors we detect charge transfer, while for separation larger than 10nm we observe Forster-like energy transfer between excitations in different layers.

Excitonic Properties of Chemically Synthesized 2D Organic-Inorganic Hybrid Perovskite Nanosheets.

PubMed

Zhang, Qi; Chu, Leiqiang; Zhou, Feng; Ji, Wei; Eda, Goki

2018-05-01

2D organic-inorganic hybrid perovskites (OIHPs) represent a unique class of materials with a natural quantum-well structure and quasi-2D electronic properties. Here, a versatile direct solution-based synthesis of mono- and few-layer OIHP nanosheets and a systematic study of their electronic structure as a function of the number of monolayers by photoluminescence and absorption spectroscopy are reported. The monolayers of various OIHPs are found to exhibit high electronic quality as evidenced by high quantum yield and negligible Stokes shift. It is shown that the ground exciton peak blueshifts by ≈40 meV when the layer thickness reduces from bulk to monolayer. It is also shown that the exciton binding energy remains effectively unchanged for (C 6 H 5 (CH 2 ) 2 NH 3 ) 2 PbI 4 with the number of layers. Similar trends are observed for (C 4 H 9 NH 3 ) 2 PbI 4 in contrast to the previous report. Further, the photoluminescence lifetime is found to decrease with the number of monolayers, indicating the dominant role of surface trap states in nonradiative recombination of the electron-hole pairs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low temperature excitonic spectroscopy and dynamics as a probe of quality in hybrid perovskite thin films.

PubMed

Sarang, Som; Ishihara, Hidetaka; Chen, Yen-Chang; Lin, Oliver; Gopinathan, Ajay; Tung, Vincent C; Ghosh, Sayantani

2016-10-19

We have developed a framework for using temperature dependent static and dynamic photoluminescence (PL) of hybrid organic-inorganic perovskites (PVSKs) to characterize lattice defects in thin films, based on the presence of nanodomains at low temperature. Our high-stability PVSK films are fabricated using a novel continuous liquid interface propagation technique, and in the tetragonal phase (T > 120 K), they exhibit bi-exponential recombination from free charge carriers with an average PL lifetime of ∼200 ns. Below 120 K, the emergence of the orthorhombic phase is accompanied by a reduction in lifetimes by an order of magnitude, which we establish to be the result of a crossover from free carrier to exciton-dominated radiative recombination. Analysis of the PL as a function of excitation power at different temperatures provides direct evidence that the exciton binding energy is different in the two phases, and using these results, we present a theoretical approach to estimate this variable binding energy. Our findings explain this anomalous low temperature behavior for the first time, attributing it to an inherent fundamental property of the hybrid PVSKs that can be used as an effective probe of thin film quality.

Optical manipulation of valley pseudospin

DOE PAGES

Ye, Ziliang; Sun, Dezheng; Heinz, Tony F.

2016-09-19

The coherent manipulation of spin and pseudospin underlies existing and emerging quantum technologies, including quantum communication and quantum computation. Valley polarization, associated with the occupancy of degenerate, but quantum mechanically distinct valleys in momentum space, closely resembles spin polarization and has been proposed as a pseudospin carrier for the future quantum electronics. Valley exciton polarization has been created in the transition metal dichalcogenide monolayers using excitation by circularly polarized light and has been detected both optically and electrically. In addition, the existence of coherence in the valley pseudospin has been identified experimentally. The manipulation of such valley coherence has, however,more » remained out of reach. In this paper, we demonstrate all-optical control of the valley coherence by means of the pseudomagnetic field associated with the optical Stark effect. Using below-bandgap circularly polarized light, we rotate the valley exciton pseudospin in monolayer WSe 2 on the femtosecond timescale. Both the direction and speed of the rotation can be manipulated optically by tuning the dynamic phase of excitons in opposite valleys. Finally, this study unveils the possibility of generation, manipulation, and detection of the valley pseudospin by coupling to photons.« less

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

Grosso, G.; Nardin, G.; Morier-Genoud, F.

Exciton polaritons have been shown to be an optimal system in order to investigate the properties of bosonic quantum fluids. We report here on the observation of dark solitons in the wake of engineered circular obstacles and their decay into streets of quantized vortices. Our experiments provide a time-resolved access to the polariton phase and density, which allows for a quantitative study of instabilities of freely evolving polaritons. The decay of solitons is quantified and identified as an effect of disorder-induced transverse perturbations in the dissipative polariton gas.

Twenty-Fifth Annual Conference on the Physics and Chemistry of Semiconductor Interfaces. Volume 16, Number 4

DTIC Science & Technology

1998-08-01

Shigefusa Chichibu, Takayuki Sofa, Kazumi Wada, and Shuji Nakamura Dynamics of localized excitons in InGaN/GaN quantum wells ,. 0 _ _ . w 7onn...Electron. Electron Phys. 11, 413 (1959). 2E. G. Bylander, J. Appl. Phys. 49, 1188 (1978). 3M. Hiraki et al., J. Lumin. 12/13, 941 (1976). 4A. O...University of Tokyo, Noda, Chiba 278-8510, Japan Takayuki Sotab) TT . . . Department of Electrical, Electronics, and Computer Engineering, Waseda

External quantum efficiency exceeding 100% in a singlet-exciton-fission-based solar cell

NASA Astrophysics Data System (ADS)

Baldo, Marc

2013-03-01

Singlet exciton fission can be used to split a molecular excited state in two. In solar cells, it promises to double the photocurrent from high energy photons, thereby breaking the single junction efficiency limit. We demonstrate organic solar cells that exploit singlet exciton fission in pentacene to generate more than one electron per incident photon in the visible spectrum. Using a fullerene acceptor, a poly(3-hexylthiophene) exciton confinement layer, and a conventional optical trapping scheme, the peak external quantum efficiency is (109 +/-1)% at λ = 670 nm for a 15-nm-thick pentacene film. The corresponding internal quantum efficiency is (160 +/-10)%. Independent confirmation of the high internal efficiency is obtained by analysis of the magnetic field effect on photocurrent, which determines that the triplet yield approaches 200% for pentacene films thicker than 5 nm. To our knowledge, this is the first solar cell to generate quantum efficiencies above 100% in the visible spectrum. Alternative multiple exciton generation approaches have been demonstrated previously in the ultraviolet, where there is relatively little sunlight. Singlet exciton fission differs from these other mechanisms because spin conservation disallows the usual dominant loss process: a thermal relaxation of the high-energy exciton into a single low-energy exciton. Consequently, pentacene is efficient in the visible spectrum at λ = 670 nm because only the collapse of the singlet exciton into twotriplets is spin-allowed. Supported as part of the Center for Excitonics, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001088.

Ultra-fast relaxation, decoherence, and localization of photoexcited states in π-conjugated polymers

NASA Astrophysics Data System (ADS)

Mannouch, Jonathan R.; Barford, William; Al-Assam, Sarah

2018-01-01

The exciton relaxation dynamics of photoexcited electronic states in poly(p-phenylenevinylene) are theoretically investigated within a coarse-grained model, in which both the exciton and nuclear degrees of freedom are treated quantum mechanically. The Frenkel-Holstein Hamiltonian is used to describe the strong exciton-phonon coupling present in the system, while external damping of the internal nuclear degrees of freedom is accounted for by a Lindblad master equation. Numerically, the dynamics are computed using the time evolving block decimation and quantum jump trajectory techniques. The values of the model parameters physically relevant to polymer systems naturally lead to a separation of time scales, with the ultra-fast dynamics corresponding to energy transfer from the exciton to the internal phonon modes (i.e., the C-C bond oscillations), while the longer time dynamics correspond to damping of these phonon modes by the external dissipation. Associated with these time scales, we investigate the following processes that are indicative of the system relaxing onto the emissive chromophores of the polymer: (1) Exciton-polaron formation occurs on an ultra-fast time scale, with the associated exciton-phonon correlations present within half a vibrational time period of the C-C bond oscillations. (2) Exciton decoherence is driven by the decay in the vibrational overlaps associated with exciton-polaron formation, occurring on the same time scale. (3) Exciton density localization is driven by the external dissipation, arising from "wavefunction collapse" occurring as a result of the system-environment interactions. Finally, we show how fluorescence anisotropy measurements can be used to investigate the exciton decoherence process during the relaxation dynamics.

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.

Exciton binding energy in a pyramidal quantum dot

NASA Astrophysics Data System (ADS)

Anitha, A.; Arulmozhi, M.

2018-05-01

The effects of spatially dependent effective mass, non-parabolicity of the conduction band and dielectric screening function on exciton binding energy in a pyramid-shaped quantum dot of GaAs have been investigated by variational method as a function of base width of the pyramid. We have assumed that the pyramid has a square base with area a× a and height of the pyramid H=a/2. The trial wave function of the exciton has been chosen according to the even mirror boundary condition, i.e. the wave function of the exciton at the boundary could be non-zero. The results show that (i) the non-parabolicity of the conduction band affects the light hole (lh) and heavy hole (hh) excitons to be more bound than that with parabolicity of the conduction band, (ii) the dielectric screening function (DSF) affects the lh and hh excitons to be more bound than that without the DSF and (iii) the spatially dependent effective mass (SDEM) affects the lh and hh excitons to be less bound than that without the SDEM. The combined effects of DSF and SDEM on exciton binding energy have also been calculated. The results are compared with those available in the literature.

Electrical Tuning of Interlayer Exciton Gases in WSe2 Bilayers.

PubMed

Wang, Zefang; Chiu, Yi-Hsin; Honz, Kevin; Mak, Kin Fai; Shan, Jie

2018-01-10

van der Waals heterostructures formed by stacking two-dimensional atomic crystals are a unique platform for exploring new phenomena and functionalities. Interlayer excitons, bound states of spatially separated electron-hole pairs in van der Waals heterostructures, have demonstrated potential for rich valley physics and optoelectronics applications and been proposed to facilitate high-temperature superfluidity. Here, we demonstrate highly tunable interlayer excitons by an out-of-plane electric field in homobilayers of transition metal dichalcogenides. Continuous tuning of the exciton dipole from negative to positive orientation has been achieved, which is not possible in heterobilayers due to the presence of large built-in interfacial electric fields. A large linear field-induced redshift up to ∼100 meV has been observed in the exciton resonance energy. The Stark effect is accompanied by an enhancement of the exciton recombination lifetime by more than two orders of magnitude to >20 ns. The long recombination lifetime has allowed the creation of an interlayer exciton gas with density as large as 1.2 × 10 11 cm -2 by moderate continuous-wave optical pumping. Our results have paved the way for the realization of degenerate exciton gases in atomically thin semiconductors.

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.

Terahertz field-induced ionization and perturbed free induction decay of excitons in bulk GaAs

NASA Astrophysics Data System (ADS)

Murotani, Yuta; Takayama, Masayuki; Sekiguchi, Fumiya; Kim, Changsu; Akiyama, Hidefumi; Shimano, Ryo

2018-03-01

We investigated the interaction between an intense terahertz (THz) pulse and excitons in bulk GaAs by using THz pump near-infrared (NIR) optical probe spectroscopy. We observed a clear spectral oscillation in the NIR transient absorption spectra at low temperature, which is interpreted as the THz pump-induced perturbed free induction decay (PFID) of the excitonic interband polarization. We performed a numerical simulation based on a microscopic theory and identified that the observed PFID signal originates from the THz field-induced ionization of excitons. Using a real-space representation of the excitonic wave function, we visualized how the ionization of an exciton proceeds under the intense single-cycle THz electric field. We also calculated the nonlinear susceptibility with the lowest-order perturbation theory assuming a weak THz pump, which showed a similar spectral feature with that obtained by the full treatment to field-induced ionization process. This coincidence is attributed to the fact that 1s-excitonic interband polarization is modified predominantly through interactions with the p-wave component of the excitonic wave function. A simple phenomenological expression of the PFID signal is presented to discuss effects of the THz pump pulse duration on the spectral oscillation.

Exciton and intracenter radiative recombination in ZnMnTe and CdMnTe quantum wells with optically active manganese ions

NASA Astrophysics Data System (ADS)

Agekyan, V. F.; Akai, I.; Vasil'Ev, N. N.; Karasawa, T.; Karczewski, G.; Serov, A. Yu.; Filosofov, N. G.

2007-06-01

The emission spectra of Zn1-x Mn x Te/Zn0.6Mg0.4Te and Cd1-x Mn x Te/Cd0.5Mg0.5Te quantum-well structures with different manganese concentrations and quantum-well widths are studied at excitation power densities ranging from 105 to 107 W cm-2. Under strong optical pumping, intracenter luminescence of Mn2+ ions degrades as a result of the interaction of excited managanese ions with high-density excitons. This process is accompanied by a strong broadening of the emission band of quantum-well excitons due to the exciton-exciton interaction and saturation of the exciton ground state. Under pumping at a power density of 105 W cm-2, stimulated emission of quantum-well excitons arises in CdTe/Cd0.5Mg0.5Te. The luminescence kinetics of the quantum-well and barrier excitons is investigated with a high temporal resolution. The effect of the quantum-well width and the managanese concentration on the kinetics and band shape of the Mn2+ intracenter luminescence characterized by the contribution of the manganese interface ions is determined.

Resonance Raman signature of intertube excitons in compositionally-defined carbon nanotube bundles

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

Simpson, Jeffrey R.; Roslyak, Oleksiy; Duque, Juan G.

Electronic interactions in low-dimensional nanomaterial heterostructures can lead to novel optical responses arising from exciton delocalization over the constituent materials. Similar phenomena have been suggested to arise between closely interacting semiconducting carbon nanotubes of identical structure. Such behavior in carbon nanotubes has potential to generate new exciton physics, impact exciton transport mechanisms in nanotube networks, and place nanotubes as one-dimensional models for such behaviors in systems of higher dimensionality. Here we use resonance Raman spectroscopy to probe intertube interactions in (6,5) chirality-enriched bundles. Raman excitation profiles for the radial breathing mode and G-mode display a previously unobserved sharp resonance feature.more » We show the feature is evidence for creation of intertube excitons and is identified as a Fano resonance arising from the interaction between intratube and intertube excitons. The universality of the model suggests that similar Raman excitation profile features may be observed for interlayer exciton resonances in 2D multilayered systems.« less

Crossover from polariton lasing to exciton lasing in a strongly coupled ZnO microcavity

PubMed Central

Lai, Ying-Yu; Chou, Yu-Hsun; Lan, Yu-Pin; Lu, Tien-Chang; Wang, Shing-Chung; Yamamoto, Yoshihisa

2016-01-01

Unlike conventional photon lasing, in which the threshold is limited by the population inversion of the electron-hole plasma, the exciton lasing generated by exciton-exciton scattering and the polariton lasing generated by dynamical condensates have received considerable attention in recent years because of the sub-Mott density and low-threshold operation. This paper presents a novel approach to generate both exciton and polariton lasing in a strongly coupled microcavity (MC) and determine the critical driving requirements for simultaneously triggering these two lasing operation in temperature <140 K and large negative polariton-exciton offset (<−133 meV) conditions. In addition, the corresponding lasing behaviors, such as threshold energy, linewidth, phase diagram, and angular dispersion are verified. The results afford a basis from which to understand the complicated lasing mechanisms in strongly coupled MCs and verify a new method with which to trigger dual laser emission based on exciton and polariton. PMID:26838665

Experimental evidences of quantum confined 2D indirect excitons in single barrier GaAs/AlAs/GaAs heterostructure using photocapacitance at room temperature

NASA Astrophysics Data System (ADS)

Bhunia, Amit; Singh, Mohit Kumar; Galvão Gobato, Y.; Henini, Mohamed; Datta, Shouvik

2018-01-01

We investigated excitonic absorptions in a GaAs/AlAs/GaAs single barrier heterostructure using both photocapacitance and photocurrent spectroscopies at room temperature. Photocapacitance spectra show well defined resonance peaks of indirect excitons formed around the Γ-AlAs barrier. Unlike DC-photocurrent spectra, frequency dependent photocapacitance spectra interestingly red shift, sharpen up, and then decrease with increasing tunneling at higher biases. Such dissimilarities clearly point out that different exciton dynamics govern these two spectral measurements. We also argue why such quantum confined dipoles of indirect excitons can have thermodynamically finite probabilities to survive even at room temperature. Finally, our observations demonstrate that the photocapacitance technique, which was seldom used to detect excitons in the past, is useful for selective detection and experimental tuning of relatively small numbers (˜1011/cm2) of photo-generated indirect excitons having large effective dipole moments in this type of quasi-two dimensional heterostructures.

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.

Linear Scaling of the Exciton Binding Energy versus the Band Gap of Two-Dimensional Materials

NASA Astrophysics Data System (ADS)

Choi, Jin-Ho; Cui, Ping; Lan, Haiping; Zhang, Zhenyu

2015-08-01

The exciton is one of the most crucial physical entities in the performance of optoelectronic and photonic devices, and widely varying exciton binding energies have been reported in different classes of materials. Using first-principles calculations within the G W -Bethe-Salpeter equation approach, here we investigate the excitonic properties of two recently discovered layered materials: phosphorene and graphene fluoride. We first confirm large exciton binding energies of, respectively, 0.85 and 2.03 eV in these systems. Next, by comparing these systems with several other representative two-dimensional materials, we discover a striking linear relationship between the exciton binding energy and the band gap and interpret the existence of the linear scaling law within a simple hydrogenic picture. The broad applicability of this novel scaling law is further demonstrated by using strained graphene fluoride. These findings are expected to stimulate related studies in higher and lower dimensions, potentially resulting in a deeper understanding of excitonic effects in materials of all dimensionalities.

Resonance Raman signature of intertube excitons in compositionally-defined carbon nanotube bundles

DOE PAGES

Simpson, Jeffrey R.; Roslyak, Oleksiy; Duque, Juan G.; ...

2018-02-12

Electronic interactions in low-dimensional nanomaterial heterostructures can lead to novel optical responses arising from exciton delocalization over the constituent materials. Similar phenomena have been suggested to arise between closely interacting semiconducting carbon nanotubes of identical structure. Such behavior in carbon nanotubes has potential to generate new exciton physics, impact exciton transport mechanisms in nanotube networks, and place nanotubes as one-dimensional models for such behaviors in systems of higher dimensionality. Here we use resonance Raman spectroscopy to probe intertube interactions in (6,5) chirality-enriched bundles. Raman excitation profiles for the radial breathing mode and G-mode display a previously unobserved sharp resonance feature.more » We show the feature is evidence for creation of intertube excitons and is identified as a Fano resonance arising from the interaction between intratube and intertube excitons. The universality of the model suggests that similar Raman excitation profile features may be observed for interlayer exciton resonances in 2D multilayered systems.« less

Resonance Raman signature of intertube excitons in compositionally-defined carbon nanotube bundles.

PubMed

Simpson, Jeffrey R; Roslyak, Oleksiy; Duque, Juan G; Hároz, Erik H; Crochet, Jared J; Telg, Hagen; Piryatinski, Andrei; Walker, Angela R Hight; Doorn, Stephen K

2018-02-12

Electronic interactions in low-dimensional nanomaterial heterostructures can lead to novel optical responses arising from exciton delocalization over the constituent materials. Similar phenomena have been suggested to arise between closely interacting semiconducting carbon nanotubes of identical structure. Such behavior in carbon nanotubes has potential to generate new exciton physics, impact exciton transport mechanisms in nanotube networks, and place nanotubes as one-dimensional models for such behaviors in systems of higher dimensionality. Here we use resonance Raman spectroscopy to probe intertube interactions in (6,5) chirality-enriched bundles. Raman excitation profiles for the radial breathing mode and G-mode display a previously unobserved sharp resonance feature. We show the feature is evidence for creation of intertube excitons and is identified as a Fano resonance arising from the interaction between intratube and intertube excitons. The universality of the model suggests that similar Raman excitation profile features may be observed for interlayer exciton resonances in 2D multilayered systems.

Exciton interference revealed by energy dependent exciton transfer rate for ring-structured molecular systems

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

Yan, Yun-An, E-mail: yunan@gznc.edu.cn

2016-01-14

The quantum interference is an intrinsic phenomenon in quantum physics for photon and massive quantum particles. In principle, the quantum interference may also occur with quasi-particles, such as the exciton. In this study, we show how the exciton quantum interference can be significant in aggregates through theoretical simulations with hierarchical equations of motion. The systems under investigation are generalized donor-bridge-acceptor model aggregates with the donor consisting of six homogeneous sites assuming the nearest neighbor coupling. For the models with single-path bridge, the exciton transfer time only shows a weak excitation energy dependence. But models with double-path bridge have a newmore » short transfer time scale and the excitation energy dependence of the exciton transfer time assumes clear peak structure which is detectable with today’s nonlinear spectroscopy. This abnormality is attributed to the exciton quantum interference and the condition for a clear observation in experiment is also explored.« less

Resolving ultrafast exciton migration in organic solids at the nanoscale.

PubMed

Penwell, Samuel B; Ginsberg, Lucas D S; Noriega, Rodrigo; Ginsberg, Naomi S

2017-11-01

Effectiveness of molecular-based light harvesting relies on transport of excitons to charge-transfer sites. Measuring exciton migration, however, has been challenging because of the mismatch between nanoscale migration lengths and the diffraction limit. Instead of using bulk substrate quenching methods, here we define quenching boundaries all-optically with sub-diffraction resolution, thus characterizing spatiotemporal exciton migration on its native nanometre and picosecond scales. By transforming stimulated emission depletion microscopy into a time-resolved ultrafast approach, we measure a 16-nm migration length in poly(2,5-di(hexyloxy)cyanoterephthalylidene) conjugated polymer films. Combined with Monte Carlo exciton hopping simulations, we show that migration in these films is essentially diffusive because intrinsic chromophore energetic disorder is comparable to chromophore inhomogeneous broadening. Our approach will enable previously unattainable correlation of local material structure to exciton migration character, applicable not only to photovoltaic or display-destined organic semiconductors but also to explaining the quintessential exciton migration exhibited in photosynthesis.

Exciton Dynamics in Monolayer Transition Metal Dichalcogenides.

PubMed

Moody, Galan; Schaibley, John; Xu, Xiaodong

2016-07-01

Since the discovery of semiconducting monolayer transition metal dichalcogenides, a variety of experimental and theoretical studies have been carried out seeking to understand the intrinsic exciton population recombination and valley relaxation dynamics. Reports of the exciton decay time range from hundreds of femtoseconds to ten nanoseconds, while the valley depolarization time can exceed one nanosecond. At present, however, a consensus on the microscopic mechanisms governing exciton radiative and non-radiative recombination is lacking. The strong exciton oscillator strength resulting in up to ~ 20% absorption for a single monolayer points to ultrafast radiative recombination. However, the low quantum yield and large variance in the reported lifetimes suggest that non-radiative Auger-type processes obscure the intrinsic exciton radiative lifetime. In either case, the electron-hole exchange interaction plays an important role in the exciton spin and valley dynamics. In this article, we review the experiments and theory that have led to these conclusions and comment on future experiments that could complement our current understanding.

Exciton Dynamics in Monolayer Transition Metal Dichalcogenides

PubMed Central

Moody, Galan; Schaibley, John; Xu, Xiaodong

2017-01-01

Since the discovery of semiconducting monolayer transition metal dichalcogenides, a variety of experimental and theoretical studies have been carried out seeking to understand the intrinsic exciton population recombination and valley relaxation dynamics. Reports of the exciton decay time range from hundreds of femtoseconds to ten nanoseconds, while the valley depolarization time can exceed one nanosecond. At present, however, a consensus on the microscopic mechanisms governing exciton radiative and non-radiative recombination is lacking. The strong exciton oscillator strength resulting in up to ~ 20% absorption for a single monolayer points to ultrafast radiative recombination. However, the low quantum yield and large variance in the reported lifetimes suggest that non-radiative Auger-type processes obscure the intrinsic exciton radiative lifetime. In either case, the electron-hole exchange interaction plays an important role in the exciton spin and valley dynamics. In this article, we review the experiments and theory that have led to these conclusions and comment on future experiments that could complement our current understanding. PMID:28890600

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.

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.

Charge Separation and Recombination at Polymer-Fullerene Heterojunctions: Delocalization and Hybridization Effects.

PubMed

D'Avino, Gabriele; Muccioli, Luca; Olivier, Yoann; Beljonne, David

2016-02-04

We address charge separation and recombination in polymer/fullerene solar cells with a multiscale modeling built from accurate atomistic inputs and accounting for disorder, interface electrostatics and genuine quantum effects on equal footings. Our results show that bound localized charge transfer states at the interface coexist with a large majority of thermally accessible delocalized space-separated states that can be also reached by direct photoexcitation, thanks to their strong hybridization with singlet polymer excitons. These findings reconcile the recent experimental reports of ultrafast exciton separation ("hot" process) with the evidence that high quantum yields do not require excess electronic or vibrational energy ("cold" process), and show that delocalization, by shifting the density of charge transfer states toward larger effective electron-hole radii, may reduce energy losses through charge recombination.

Reflection and extinction of light by self-assembled monolayers of a quinque-thiophene derivative: A coherent scattering approach

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

Gholamrezaie, Fatemeh; Meskers, Stefan C. J., E-mail: s.c.j.meskers@tue.nl; Leeuw, Dago M. de

Scattering matrix theory is used to describe resonant optical properties of molecular monolayers. Three types of coupling are included: exciton-exciton, exciton-photon, and exciton-phonon coupling. We use the K-matrix formalism, developed originally to describe neutron scattering spectra in nuclear physics to compute the scattering of polaritons by phonons. This perturbation approach takes into account the three couplings and allows one to go beyond molecular exciton theory without the need of introducing additional boundary conditions for the polariton. We demonstrate that reflection, absorption, and extinction of light by 2D self-assembled monolayers of molecules containing quinque-thiophene chromophoric groups can be calculated. The extractedmore » coherence length of the Frenkel exciton is discussed.« less

Theoretical investigation of excitonic magnetism in LaSrCoO4

NASA Astrophysics Data System (ADS)

Fernández Afonso, J.; Sotnikov, A.; Kuneš, J.

2018-04-01

We use the LDA+U approach to search for possible ordered ground states of LaSrCoO4. We find a staggered arrangement of magnetic multipoles to be stable over a broad range of Co 3d interaction parameters. This ordered state can be described as a spin-density-wave-type condensate of dxy \\otimes dx^2-y^2 excitons carrying spin S  =  1. Further, we construct an effective strong-coupling model, calculate the exciton dispersion and investigate closing of the exciton gap, which marks the exciton condensation instability. Comparing the layered LaSrCoO4 with its pseudo cubic analog LaCoO3, we find that for the same interaction parameters the excitonic gap is smaller (possibly vanishing) in the layered cobaltite.

Polarization-dependent exciton dynamics in tetracene single crystals

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

Zhang, Bo; Zhang, Chunfeng, E-mail: cfzhang@nju.edu.cn; Xu, Yanqing

2014-12-28

We conduct polarization-dependent ultrafast spectroscopy to study the dynamics of singlet fission (SF) in tetracene single crystals. The spectrotemporal species for singlet and triplet excitons in transient absorption spectra are found to be strongly dependent on probe polarization. By carefully analyzing the polarization dependence, the signals contributed by different transitions related to singlet excitons have been disentangled, which is further applied to construct the correlation between dynamics of singlet and triplet excitons. The anisotropy of exciton dynamics provides an alternative approach to tackle the long-standing challenge in understanding the mechanism of singlet fission in organic semiconductors.

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.

Exciton binding energy in GaAsBiN spherical quantum dot heterostructures

NASA Astrophysics Data System (ADS)

Das, Subhasis; Dhar, S.

2017-03-01

The ground state exciton binding energies (EBE) of heavy hole excitons in GaAs1-x-yBixNy - GaAs spherical quantum dots (QD) are calculated using a variational approach under 1s hydrogenic wavefunctions within the framework of effective mass approximation. Both the nitrogen and the bismuth content in the material are found to affect the binding energy, in particular for larger nitrogen content and lower dot radii. Calculations also show that the ground state exciton binding energies of heavy holes increase more at smaller dot sizes as compared to that for the light hole excitons.

Plasmon-Exciton Coupling Interaction for Surface Catalytic Reactions.

PubMed

Wang, Jingang; Lin, Weihua; Xu, Xuefeng; Ma, Fengcai; Sun, Mengtao

2018-05-01

In this review, we firstly reveal the physical principle of plasmon-exciton coupling interaction with steady absorption spectroscopy, and ultrafast transition absorption spectroscopy, based on the pump-prop technology. Secondly, we introduce the fabrication of electro-optical device of two-dimensional semiconductor-nanostructure noble metals hybrid, based on the plasmon-exciton coupling interactions. Thirdly, we introduce the applications of plasmon-exciton coupling interaction in the field of surface catalytic reactions. Lastly, the perspective of plasmon-exciton coupling interaction and applications closed this review. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasmonic Structure Enhanced Exciton Generation at the Interface between the Perovskite Absorber and Copper Nanoparticles

PubMed Central

Lin, Kuen-Feng; Chiang, Chien-Hung; Wu, Chun-Guey

2014-01-01

The refractive index and extinction coefficient of a triiodide perovskite absorber (TPA) were obtained by fitting the transmittance spectra of TPA/PEDOT:PSS/ITO/glass using the transfer matrix method. Cu nanoplasmonic structures were designed to enhance the exciton generation in the TPA and to simultaneously reduce the film thickness of the TPA. Excitons were effectively generated at the interface between TPA and Cu nanoparticles, as observed through the 3D finite-difference time-domain method. The exciton distribution is advantageous for the exciton dissociation and carrier transport. PMID:25295290

Multicomponent exciton gas in cuprous oxide: cooling behaviour and the role of Auger decay

NASA Astrophysics Data System (ADS)

Semkat, D.; Sobkowiak, S.; Schöne, F.; Stolz, H.; Koch, Th; Fehske, H.

2017-10-01

In this paper we present a hydrodynamic model to describe the dynamics of para- and orthoexcitons in cuprous oxide at ultralow temperatures inside a stress induced potential trap. We take into account the finite lifetime of the excitons, the excitation process and exciton-phonon as well as exciton-exciton interaction. Furthermore, we model the two-body loss mechanism assuming an Auger-like effect and compare it to an alternative explanation which relies on the formation of biexcitons. We discuss in detail the influence on the numerical results and compare the predictions to experimental data.

Theory of exciton transfer and diffusion in conjugated polymers

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

Barford, William, E-mail: william.barford@chem.ox.ac.uk; Tozer, Oliver Robert; University College, University of Oxford, Oxford OX1 4BH

We describe a theory of Förster-type exciton transfer between conjugated polymers. The theory is built on three assumptions. First, we assume that the low-lying excited states of conjugated polymers are Frenkel excitons coupled to local normal modes, and described by the Frenkel-Holstein model. Second, we assume that the relevant parameter regime is ℏω < J, i.e., the adiabatic regime, and thus the Born-Oppenheimer factorization of the electronic and nuclear degrees of freedom is generally applicable. Finally, we assume that the Condon approximation is valid, i.e., the exciton-polaron wavefunction is essentially independent of the normal modes. The resulting expression for themore » exciton transfer rate has a familiar form, being a function of the exciton transfer integral and the effective Franck-Condon factors. The effective Franck-Condon factors are functions of the effective Huang-Rhys parameters, which are inversely proportional to the chromophore size. The Born-Oppenheimer expressions were checked against DMRG calculations, and are found to be within 10% of the exact value for a tiny fraction of the computational cost. This theory of exciton transfer is then applied to model exciton migration in conformationally disordered poly(p-phenylene vinylene). Key to this modeling is the assumption that the donor and acceptor chromophores are defined by local exciton ground states (LEGSs). Since LEGSs are readily determined by the exciton center-of-mass wavefunction, this theory provides a quantitative link between polymer conformation and exciton migration. Our Monte Carlo simulations indicate that the exciton diffusion length depends weakly on the conformation of the polymer, with the diffusion length increasing slightly as the chromophores became straighter and longer. This is largely a geometrical effect: longer and straighter chromophores extend over larger distances. The calculated diffusion lengths of ∼10 nm are in good agreement with experiment. The spectral properties of the migrating excitons are also investigated. The emission intensity ratio of the 0-0 and 0-1 vibronic peaks is related to the effective Huang-Rhys parameter of the emitting state, which in turn is related to the chromophore size. The intensity ratios calculated from the effective Huang-Rhys parameters are in agreement with experimental spectra, and the time-resolved trend for the intensity ratio to decrease with time was also reproduced as the excitation migrates to shorter, lower energy chromophores as a function of time. In addition, the energy of the exciton state shows a logarithmic decrease with time, in agreement with experimental observations.« less

Theory of exciton transfer and diffusion in conjugated polymers.

PubMed

Barford, William; Tozer, Oliver Robert

2014-10-28

We describe a theory of Förster-type exciton transfer between conjugated polymers. The theory is built on three assumptions. First, we assume that the low-lying excited states of conjugated polymers are Frenkel excitons coupled to local normal modes, and described by the Frenkel-Holstein model. Second, we assume that the relevant parameter regime is ℏω < J, i.e., the adiabatic regime, and thus the Born-Oppenheimer factorization of the electronic and nuclear degrees of freedom is generally applicable. Finally, we assume that the Condon approximation is valid, i.e., the exciton-polaron wavefunction is essentially independent of the normal modes. The resulting expression for the exciton transfer rate has a familiar form, being a function of the exciton transfer integral and the effective Franck-Condon factors. The effective Franck-Condon factors are functions of the effective Huang-Rhys parameters, which are inversely proportional to the chromophore size. The Born-Oppenheimer expressions were checked against DMRG calculations, and are found to be within 10% of the exact value for a tiny fraction of the computational cost. This theory of exciton transfer is then applied to model exciton migration in conformationally disordered poly(p-phenylene vinylene). Key to this modeling is the assumption that the donor and acceptor chromophores are defined by local exciton ground states (LEGSs). Since LEGSs are readily determined by the exciton center-of-mass wavefunction, this theory provides a quantitative link between polymer conformation and exciton migration. Our Monte Carlo simulations indicate that the exciton diffusion length depends weakly on the conformation of the polymer, with the diffusion length increasing slightly as the chromophores became straighter and longer. This is largely a geometrical effect: longer and straighter chromophores extend over larger distances. The calculated diffusion lengths of ~10 nm are in good agreement with experiment. The spectral properties of the migrating excitons are also investigated. The emission intensity ratio of the 0-0 and 0-1 vibronic peaks is related to the effective Huang-Rhys parameter of the emitting state, which in turn is related to the chromophore size. The intensity ratios calculated from the effective Huang-Rhys parameters are in agreement with experimental spectra, and the time-resolved trend for the intensity ratio to decrease with time was also reproduced as the excitation migrates to shorter, lower energy chromophores as a function of time. In addition, the energy of the exciton state shows a logarithmic decrease with time, in agreement with experimental observations.

Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer.

PubMed

Duan, Hong-Guang; Prokhorenko, Valentyn I; Cogdell, Richard J; Ashraf, Khuram; Stevens, Amy L; Thorwart, Michael; Miller, R J Dwayne

2017-08-08

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales [Formula: see text]100 fs. Today's understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds. This orthodox picture of incoherent energy transfer between clusters of a few pigments sharing delocalized excitons has been challenged by ultrafast optical spectroscopy experiments with the Fenna-Matthews-Olson protein, in which interference oscillatory signals up to 1.5 ps were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidence of any long-lived electronic quantum coherence, but confirm the orthodox view of rapidly decaying electronic quantum coherence on a timescale of 60 fs. Our results can be considered as generic and give no hint that electronic quantum coherence plays any biofunctional role in real photoactive biomolecular complexes. Because in this structurally well-defined protein the distances between bacteriochlorophylls are comparable to those of other light-harvesting complexes, we anticipate that this finding is general and directly applies to even larger photoactive biomolecular complexes.

Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer

NASA Astrophysics Data System (ADS)

Duan, Hong-Guang; Prokhorenko, Valentyn I.; Cogdell, Richard J.; Ashraf, Khuram; Stevens, Amy L.; Thorwart, Michael; Miller, R. J. Dwayne

2017-08-01

During the first steps of photosynthesis, the energy of impinging solar photons is transformed into electronic excitation energy of the light-harvesting biomolecular complexes. The subsequent energy transfer to the reaction center is commonly rationalized in terms of excitons moving on a grid of biomolecular chromophores on typical timescales <<100 fs. Today’s understanding of the energy transfer includes the fact that the excitons are delocalized over a few neighboring sites, but the role of quantum coherence is considered as irrelevant for the transfer dynamics because it typically decays within a few tens of femtoseconds. This orthodox picture of incoherent energy transfer between clusters of a few pigments sharing delocalized excitons has been challenged by ultrafast optical spectroscopy experiments with the Fenna-Matthews-Olson protein, in which interference oscillatory signals up to 1.5 ps were reported and interpreted as direct evidence of exceptionally long-lived electronic quantum coherence. Here, we show that the optical 2D photon echo spectra of this complex at ambient temperature in aqueous solution do not provide evidence of any long-lived electronic quantum coherence, but confirm the orthodox view of rapidly decaying electronic quantum coherence on a timescale of 60 fs. Our results can be considered as generic and give no hint that electronic quantum coherence plays any biofunctional role in real photoactive biomolecular complexes. Because in this structurally well-defined protein the distances between bacteriochlorophylls are comparable to those of other light-harvesting complexes, we anticipate that this finding is general and directly applies to even larger photoactive biomolecular complexes.

Exciton Binding Energy of Monolayer WS2

PubMed Central

Zhu, Bairen; Chen, Xi; Cui, Xiaodong

2015-01-01

The optical properties of monolayer transition metal dichalcogenides (TMDC) feature prominent excitonic natures. Here we report an experimental approach to measuring the exciton binding energy of monolayer WS2 with linear differential transmission spectroscopy and two-photon photoluminescence excitation spectroscopy (TP-PLE). TP-PLE measurements show the exciton binding energy of 0.71 ± 0.01 eV around K valley in the Brillouin zone. PMID:25783023

On the condensation of exciton polaritons in microcavities induced by a magnetic field

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

Kochereshko, V. P., E-mail: Vladimir.Kochereshko@mail.ioffe.ru; Avdoshina, D. V.; Savvidis, P.

2016-11-15

The photoluminescence spectra of exciton polaritons in microcavities under conditions of three-dimensional quantization are studied as a factor of the density of the optical excitation and magnetic field. The behavior of the degree of circular polarization of the exciton luminescence in a magnetic field shows that, when the concentration of excitons increases, they condense at the lowest Zeeman sublevel.

Bright triplet excitons in caesium lead halide perovskites

NASA Astrophysics Data System (ADS)

Becker, Michael A.; Vaxenburg, Roman; Nedelcu, Georgian; Sercel, Peter C.; Shabaev, Andrew; Mehl, Michael J.; Michopoulos, John G.; Lambrakos, Samuel G.; Bernstein, Noam; Lyons, John L.; Stöferle, Thilo; Mahrt, Rainer F.; Kovalenko, Maksym V.; Norris, David J.; Rainò, Gabriele; Efros, Alexander L.

2018-01-01

Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund’s rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the ‘dark exciton’. Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX3, with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin-orbit coupling in the conduction band of a perovskite is combined with the Rashba effect. We then apply our model to CsPbX3 nanocrystals, and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster than any other semiconductor nanocrystal at room and cryogenic temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting, lasers and displays, these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.

Exciton-Delocalizing Ligands Can Speed Up Energy Migration in Nanocrystal Solids.

PubMed

Azzaro, Michael S; Dodin, Amro; Zhang, Diana Y; Willard, Adam P; Roberts, Sean T

2018-05-09

Researchers have long sought to use surface ligands to enhance energy migration in nanocrystal solids by decreasing the physical separation between nanocrystals and strengthening their electronic coupling. Exciton-delocalizing ligands, which possess frontier molecular orbitals that strongly mix with nanocrystal band-edge states, are well-suited for this role because they can facilitate carrier-wave function extension beyond the nanocrystal core, reducing barriers for energy transfer. This report details the use of the exciton-delocalizing ligand phenyldithiocarbamate (PDTC) to tune the transport rate and diffusion length of excitons in CdSe nanocrystal solids. A film composed of oleate-terminated CdSe nanocrystals is subjected to a solid-state ligand exchange to replace oleate with PDTC. Exciton migration in the films is subsequently investigated by femtosecond transient absorption. Our experiments indicate that the treatment of nanocrystal films with PDTC leads to rapid (∼400 fs) downhill energy migration (∼80 meV), while no such migration occurs in oleate-capped films. Kinetic Monte Carlo simulations allow us to extract both rates and length scales for exciton diffusion in PDTC-treated films. These simulations reproduce dynamics observed in transient absorption measurements over a range of temperatures and confirm excitons hop via a Miller-Abrahams mechanism. Importantly, our experiments and simulations show PDTC treatment increases the exciton hopping rate to 200 fs, an improvement of 5 orders of magnitude relative to oleate-capped films. This exciton hopping rate stands as one of the fastest determined for CdSe solids. The facile, room-temperature processing and improved transport properties offered by the solid-state exchange of exciton-delocalizing ligands show they offer promise for the construction of strongly coupled nanocrystal arrays.

Can Disorder Enhance Incoherent Exciton Diffusion?

PubMed

Lee, Elizabeth M Y; Tisdale, William A; Willard, Adam P

2015-07-30

Recent experiments aimed at probing the dynamics of excitons have revealed that semiconducting films composed of disordered molecular subunits, unlike expectations for their perfectly ordered counterparts, can exhibit a time-dependent diffusivity in which the effective early time diffusion constant is larger than that of the steady state. This observation has led to speculation about what role, if any, microscopic disorder may play in enhancing exciton transport properties. In this article, we present the results of a model study aimed at addressing this point. Specifically, we introduce a general model, based upon Förster theory, for incoherent exciton diffusion in a material composed of independent molecular subunits with static energetic disorder. Energetic disorder leads to heterogeneity in molecule-to-molecule transition rates, which we demonstrate has two important consequences related to exciton transport. First, the distribution of local site-specific hopping rates is broadened in a manner that results in a decrease in average exciton diffusivity relative to that in a perfectly ordered film. Second, since excitons prefer to make transitions that are downhill in energy, the steady state distribution of exciton energies is biased toward low-energy molecular subunits, those that exhibit reduced diffusivity relative to a perfectly ordered film. These effects combine to reduce the net diffusivity in a manner that is time dependent and grows more pronounced as disorder is increased. Notably, however, we demonstrate that the presence of energetic disorder can give rise to a population of molecular subunits with exciton transfer rates exceeding those of subunits in an energetically uniform material. Such enhancements may play an important role in processes that are sensitive to molecular-scale fluctuations in exciton density field.

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.

Acousto-exciton interaction in a gas of 2D indirect dipolar excitons in the presence of disorder

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

Kovalev, V. M.; Chaplik, A. V., E-mail: chaplik@isp.nsc.ru

2016-03-15

A theory for the linear and quadratic responses of a 2D gas of indirect dipolar excitons to an external surface acoustic wave perturbation in the presence of a static random potential is considered. The theory is constructed both for high temperatures, definitely greater than the exciton gas condensation temperature, and at zero temperature by taking into account the Bose–Einstein condensation effects. The particle Green functions, the density–density correlation function, and the quadratic response function are calculated by the “cross” diagram technique. The results obtained are used to calculate the absorption of Rayleigh surface waves and the acoustic exciton gas dragmore » by a Rayleigh wave. The damping of Bogoliubov excitations in an exciton condensate due to theirs scattering by a random potential has also been determined.« less

Low-Energy Excitation Spectra in the Excitonic Phase of Cobalt Oxides

NASA Astrophysics Data System (ADS)

Yamaguchi, Tomoki; Sugimoto, Koudai; Ohta, Yukinori

2017-04-01

We study the excitonic phase and low-energy excitation spectra of perovskite cobalt oxides. Constructing the five-orbital Hubbard model defined on the three-dimensional cubic lattice for the 3d bands of Pr0.5Ca0.5CoO3, we calculate the excitonic susceptibility in the normal state in the random-phase approximation (RPA) to show the presence of the instability toward excitonic condensation. On the basis of the excitonic ground state with a magnetic multipole obtained in the mean-field approximation, we calculate the dynamical susceptibility of the excitonic phase in the RPA and find that there appear a gapless collective excitation in the spin-transverse mode (Goldstone mode) and a gapful collective excitation in the spin-longitudinal mode (Higgs mode). The experimental relevance of our results is discussed.

Pressure-induced increase of exciton-LO-phonon coupling in a ZnCdSe/ZnSe quantum well

NASA Astrophysics Data System (ADS)

Guo, Z. Z.; Liang, X. X.; Ban, S. L.

2003-07-01

The possibility of pressure-induced increase of exciton-LO-phonon coupling in ZnCdSe/ZnSe quantum wells is studied. The ground state binding energies of the heavy hole excitons are calculated using a variational method with consideration of the electron-phonon interaction and the pressure dependence of the parameters. The results show that for quantum wells with intermediate well width, the exciton binding energy and the LO-phonon energy may coincide in the course of pressure increasing, resulting in the increase of exciton-LO-phonon coupling. It is also found that among the pressure-dependent parameters, the influence of the lattice constant is the most important one. The changes of both the effective masses and the dielectric constants have obvious effects on the exciton binding energy, but their influences are counterbalanced.

Valley dynamics of intravalley and intervalley multiexcitonic states in monolayer WS2

NASA Astrophysics Data System (ADS)

Fu, Jiyong; Bezerra, Andre; Qu, Fanyao

2018-03-01

We present a comprehensive model comprising of a complete set of rate equations, which account for charge transfer among multiexcitonic channels including excitons, trions, and biexcitons, to investigate valley (locked with spin) dynamics in monolayer WS2. The steady-state photoluminescence (PL) spectra, underlying the laser power dependence of excitonic populations, are also determined. Our computed PL for all excitonic states agrees with the experimental data of Paradisanos et al. [Appl. Phys. Lett. 110, 193102 (2017), 10.1063/1.4983285]. We find that the relative weight of PL, stemmed from different excitonic channels, strongly depends on the laser power even under dynamical conditions. Remarkably, the biexciton channel, having the weakest PL intensity at low laser powers, tends to prevail in PL over other excitonic states as the power strengthens. In addition, by accounting for intervalley scatterings, which enable transfer of excitonic states from one valley to the other, we determine the valley polarization, which strongly depends on intervalley scatterings and the exciton generation rates in the two valleys. On the other hand, the valley polarization for all excitonic channels is found almost independent of the laser power, consistent with experimental measurements as well. Finally, the valley dynamics involving both intra- and intervalley trions is discussed. Our model and numerical outcome should be beneficial to experiments especially featuring the interplay of multiexcitonic channels in, e.g., elucidating experimental data, estimating central excitonic quantities including recombination times and transition rates, and in widening possible new experimental scopes.

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.

Fermi-edge exciton-polaritons in doped semiconductor microcavities with finite hole mass

NASA Astrophysics Data System (ADS)

Pimenov, Dimitri; von Delft, Jan; Glazman, Leonid; Goldstein, Moshe

2017-10-01

The coupling between a 2D semiconductor quantum well and an optical cavity gives rise to combined light-matter excitations, the exciton-polaritons. These were usually measured when the conduction band is empty, making the single polariton physics a simple single-body problem. The situation is dramatically different in the presence of a finite conduction-band population, where the creation or annihilation of a single exciton involves a many-body shakeup of the Fermi sea. Recent experiments in this regime revealed a strong modification of the exciton-polariton spectrum. Previous theoretical studies concerned with nonzero Fermi energy mostly relied on the approximation of an immobile valence-band hole with infinite mass, which is appropriate for low-mobility samples only; for high-mobility samples, one needs to consider a mobile hole with large but finite mass. To bridge this gap, we present an analytical diagrammatic approach and tackle a model with short-ranged (screened) electron-hole interaction, studying it in two complementary regimes. We find that the finite hole mass has opposite effects on the exciton-polariton spectra in the two regimes: in the first, where the Fermi energy is much smaller than the exciton binding energy, excitonic features are enhanced by the finite mass. In the second regime, where the Fermi energy is much larger than the exciton binding energy, finite mass effects cut off the excitonic features in the polariton spectra, in qualitative agreement with recent experiments.

Excitonic Phase Diagram of the Three-Chain Hubbard Model for Semiconducting and Semimetallic Ta2NiSe5

NASA Astrophysics Data System (ADS)

Domon, Kaoru; Yamada, Takemi; Ōno, Yoshiaki

2018-05-01

Transition metal chalcogenide Ta2NiSe5, a promising material for the excitonic insulator, is investigated on the basis of the three-chain Hubbard model with two conduction (c) bands and one valence (f) band. In the semimetallic case where only one of two c bands and the f band cross the Fermi level, the transition from the c-f compensated semimetal to the uniform excitonic order, the so-called excitonic insulator, takes place at low temperature as the same as in the semiconducting case. On the other hand, when another c band also crosses the Fermi level, the system shows three types of Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) excitonic orders characterized by the condensation of excitons with finite center-of-mass momentum q corresponding to the three types of nesting vectors between the imbalanced two c and one f Fermi surfaces. The obtained FFLO excitonic states are metallic in contrast to the excitonic insulator and are expected to be observed in the semimetallic Ta2NiSe5 under high pressure. The effect of the electron-lattice coupling is also discussed briefly and is found to induce the monoclinic distortion not only in the uniform excitonic state but also in the FFLO one resulting in the orthorhombic-monoclinic structural phase transition for both cases as observed in Ta2NiSe5 for both low-pressure semiconducting and high-pressure semimetallic regimes.

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

DOE PAGES

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan; ...

2017-02-21

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Transport of Indirect Excitons in High Magnetic Fields

NASA Astrophysics Data System (ADS)

Dorow, C. J.; Kuznetsova, Y. Y.; Calman, E. V.; Butov, L. V.; Wilkes, J.; Campman, K. L.; Gossard, A. C.

Spatially- and spectrally-resolved photoluminescence measurements of indirect excitons in high magnetic fields are presented. The high magnetic field regime for excitons is realized when the cyclotron splitting compares to the exciton binding energy. Due to small mass and binding energy, the high magnetic field regime for excitons is achievable in lab, requiring a few Tesla. Long indirect exciton lifetimes allow large exciton transport distances before recombination, giving an opportunity to study transport and relaxation kinetics of indirect magnetoexcitons via optical imaging. Indirect excitons in several Landau level states are realized. 0e -0h indirect magnetoexcitons (formed from electrons and holes at zeroth Landau levels) travel over large distances and form an emission ring around the excitation spot. In contrast, the 1e -1h and 2e -2h states do not exhibit long transport distances, and the spatial profiles of the emission closely follow the laser excitation. The 0e -0h indirect magnetoexciton transport distance reduces with increasing magnetic field. Accompanying theoretical work explains these effects in terms of magnetoexciton energy relaxation and effective mass enhancement. Supported by NSF Grant No. 1407277. J.W. was supported by the EPSRC (Grant EP/L022990/1). C.J.D. was supported by the NSF Graduate Research Fellowship Program under Grant No. DGE-1144086.

Enormous excitonic effects in bulk, mono- and bi- layers of cuprous halides using many-body perturbation technique

NASA Astrophysics Data System (ADS)

Azhikodan, Dilna; Nautiyal, Tashi

2017-10-01

Cuprous halides (CuX with X = Cl, Br, I), intensely studied about four decades ago by experimentalists for excitons, are again drawing attention of researchers recently. Potential of cuprous halide systems for device applications has not yet been fully explored. We go beyond the one-particle picture to capture the two-particle physics (electron-hole interaction to form excitons). We have deployed the full tool kit of many-body perturbation technique, GW approximation + Bethe Salpeter equation, to unfurl the rich excitonic physics of the bulk as well as layers of CuX. The negative spin-orbit contribution at the valence band top in CuCl, compared to CuBr and CuI, is in good agreement with experiments. We note that CuX have exceptionally strong excitons, defying the linear fit (between the excitonic binding energy and band gap) encompassing many semiconductors. The mono- and bi- layers of cuprous halides are predicted to be rich in excitons, with exceptionally large binding energies and the resonance energies in UV/visible region. Hence this work projects CuX layers as good candidates for optoelectronic applications. With advancement of technology, we look forward to experimental realization of CuX layers and harnessing of their rich excitonic potential.

Excitons and Davydov splitting in sexithiophene from first-principles many-body Green's function theory

NASA Astrophysics Data System (ADS)

Leng, Xia; Yin, Huabing; Liang, Dongmei; Ma, Yuchen

2015-09-01

Organic semiconductors have promising and broad applications in optoelectronics. Understanding their electronic excited states is important to help us control their spectroscopic properties and performance of devices. There have been a large amount of experimental investigations on spectroscopies of organic semiconductors, but theoretical calculation from first principles on this respect is still limited. Here, we use density functional theory (DFT) and many-body Green's function theory, which includes the GW method and Bethe-Salpeter equation, to study the electronic excited-state properties and spectroscopies of one prototypical organic semiconductor, sexithiophene. The exciton energies of sexithiophene in both the gas and bulk crystalline phases are very sensitive to the exchange-correlation functionals used in DFT for ground-state structure relaxation. We investigated the influence of dynamical screening in the electron-hole interaction on exciton energies, which is found to be very pronounced for triplet excitons and has to be taken into account in first principles calculations. In the sexithiophene single crystal, the energy of the lowest triplet exciton is close to half the energy of the lowest singlet one. While lower-energy singlet and triplet excitons are intramolecular Frenkel excitons, higher-energy excitons are of intermolecular charge-transfer type. The calculated optical absorption spectra and Davydov splitting are in good agreement with experiments.

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

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

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Promoting Singlet/triplet Exciton Transformation in Organic Optoelectronic Molecules: Role of Excited State Transition Configuration.

PubMed

Chen, Runfeng; Tang, Yuting; Wan, Yifang; Chen, Ting; Zheng, Chao; Qi, Yuanyuan; Cheng, Yuanfang; Huang, Wei

2017-07-24

Exciton transformation, a non-radiative process in changing the spin multiplicity of an exciton usually between singlet and triplet forms, has received much attention recently due to its crucial effects in manipulating optoelectronic properties for various applications. However, current understanding of exciton transformation mechanism does not extend far beyond a thermal equilibrium of two states with different multiplicity and it is a significant challenge to probe what exactly control the transformation between the highly active excited states. Here, based on the recent developments of three types of purely organic molecules capable of efficient spin-flipping, we perform ab initio structure/energy optimization and similarity/overlap extent analysis to theoretically explore the critical factors in controlling the transformation process of the excited states. The results suggest that the states having close energy levels and similar exciton characteristics with same transition configurations and high heteroatom participation are prone to facilitating exciton transformation. A basic guideline towards the molecular design of purely organic materials with facile exciton transformation ability is also proposed. Our discovery highlights systematically the critical importance of vertical transition configuration of excited states in promoting the singlet/triplet exciton transformation, making a key step forward in excited state tuning of purely organic optoelectronic materials.

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.

Solid state carbon nanotube device for controllable trion electroluminescence emission

NASA Astrophysics Data System (ADS)

Liang, Shuang; Ma, Ze; Wei, Nan; Liu, Huaping; Wang, Sheng; Peng, Lian-Mao

2016-03-01

Semiconducting carbon nanotubes (CNTs) have a direct chirality-dependent bandgap and reduced dimensionality-related quantum confinement effects, which are closely related to the performance of optoelectronic devices. Here, taking advantage of the large energy separations between neutral singlet excitons and charged excitons, i.e. trions in CNTs, we have achieved for the first time all trion electroluminescence (EL) emission from chirality-sorted (8,3) and (8,4) CNT-based solid state devices. We showed that strong trion emission can be obtained as a result of localized impact excitation and electrically injected holes, with an estimated efficiency of ~5 × 10-4 photons per injected hole. The importance of contact-controlled carrier injection (including symmetric and asymmetric contact configurations) and EL spectral stability for gradually increasing bias were also investigated. The realization of electrically induced pure trion emission opens up a new opportunity for CNT film-based optoelectronic devices, providing a new degree of freedom in controlling the devices to extend potential applications in spin or magnetic optoelectronics fields.Semiconducting carbon nanotubes (CNTs) have a direct chirality-dependent bandgap and reduced dimensionality-related quantum confinement effects, which are closely related to the performance of optoelectronic devices. Here, taking advantage of the large energy separations between neutral singlet excitons and charged excitons, i.e. trions in CNTs, we have achieved for the first time all trion electroluminescence (EL) emission from chirality-sorted (8,3) and (8,4) CNT-based solid state devices. We showed that strong trion emission can be obtained as a result of localized impact excitation and electrically injected holes, with an estimated efficiency of ~5 × 10-4 photons per injected hole. The importance of contact-controlled carrier injection (including symmetric and asymmetric contact configurations) and EL spectral stability for gradually increasing bias were also investigated. The realization of electrically induced pure trion emission opens up a new opportunity for CNT film-based optoelectronic devices, providing a new degree of freedom in controlling the devices to extend potential applications in spin or magnetic optoelectronics fields. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07468a

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.

Quantum confined stark effect on the binding energy of exciton in type II quantum heterostructure

NASA Astrophysics Data System (ADS)

Suseel, Rahul K.; Mathew, Vincent

2018-05-01

In this work, we have investigated the effect of external electric field on the strongly confined excitonic properties of CdTe/CdSe/CdTe/CdSe type-II quantum dot heterostructures. Within the effective mass approximation, we solved the Poisson-Schrodinger equations of the exciton in nanostructure using relaxation method in a self-consistent iterative manner. We changed both the external electric field and core radius of the quantum dot, to study the behavior of binding energy of exciton. Our studies show that the external electric field destroys the positional flipped state of exciton by modifying the confining potentials of electron and hole.

Influence of the dark exciton state on the optical and quantum optical properties of single quantum dots.

PubMed

Reischle, M; Beirne, G J; Rossbach, R; Jetter, M; Michler, P

2008-10-03

The dark exciton state strongly affects the optical and quantum optical properties of flat InP/GaInP quantum dots. The exciton intensity drops sharply compared to the biexciton with rising pulsed laser excitation power while the opposite is true with temperature. Also, the decay rate is faster for the exciton than the biexciton and the dark-to-bright state spin flip is enhanced with temperature. Furthermore, long-lived dark state related memory effects are observed in second-order cross-correlation measurements between the exciton and biexciton and have been simulated using a rate-equation model.

Primary photoexcitations and the origin of the photocurrent in rubrene single crystals.

PubMed

Najafov, Hikmat; Biaggio, Ivan; Podzorov, Vitaly; Calhoun, Matthew F; Gershenson, Michael E

2006-02-10

By simultaneously measuring the excitation spectra of transient luminescence and transient photoconductivity after picosecond pulsed excitation in rubrene single crystals, we show that free excitons are photoexcited starting at photon energies above 2.0 eV. We observe a competition between photoexcitation of free excitons and photoexcitation into vibronic states that subsequently decays into free carriers, while molecular excitons are instead formed predominantly through the free exciton. At photon energies below 2.25 eV, free charge carriers are created only through a long-lived intermediate state with a lifetime of up to 0.1 ms and no free carriers appear during the exciton lifetime.

Long exciton lifetimes in stacking-fault-free wurtzite GaAs nanowires

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

Furthmeier, Stephan, E-mail: stephan.furthmeier@ur.de; Dirnberger, Florian; Hubmann, Joachim

We present a combined photoluminescence and transmission electron microscopy study of single GaAs nanowires. Each wire was characterized both in microscopy and spectroscopy, allowing a direct correlation of the optical and the structural properties. By tuning the growth parameters, the nanowire crystal structure is optimized from a highly mixed zincblende–wurtzite structure to pure wurtzite. We find the latter one to be stacking-fault-free over nanowire lengths up to 4.1 μm. We observe the emission of purely wurtzite nanowires to occur only with polarization directions perpendicular to the wurtzite c{sup ^}-axis, as expected from the hexagonal unit cell symmetry. The free exciton recombinationmore » energy in the wurtzite structure is 1.518 eV at 5 K with a narrow linewidth of 4 meV. Most notably, these pure wurtzite nanowires display long carrier recombination lifetimes of up to 11.2 ns, exceeding reported lifetimes in bulk GaAs and state-of-the-art 2D GaAs/AlGaAs heterostructures.« less

Aggregation-induced emission in lamellar solids of colloidal perovskite quantum wells

PubMed Central

Jagielski, Jakub; Kumar, Sudhir; Wang, Mingchao; Scullion, Declan; Lawrence, Robert; Li, Yen-Ting; Yakunin, Sergii; Tian, Tian; Kovalenko, Maksym V.; Chiu, Yu-Cheng; Santos, Elton J. G.; Lin, Shangchao; Shih, Chih-Jen

2017-01-01

The outstanding excitonic properties, including photoluminescence quantum yield (ηPL), of individual, quantum-confined semiconductor nanoparticles are often significantly quenched upon aggregation, representing the main obstacle toward scalable photonic devices. We report aggregation-induced emission phenomena in lamellar solids containing layer-controlled colloidal quantum wells (QWs) of hybrid organic-inorganic lead bromide perovskites, resulting in anomalously high solid-state ηPL of up to 94%. Upon forming the QW solids, we observe an inverse correlation between exciton lifetime and ηPL, distinct from that in typical quantum dot solid systems. Our multiscale theoretical analysis reveals that, in a lamellar solid, the collective motion of the surface organic cations is more restricted to orient along the [100] direction, thereby inducing a more direct bandgap that facilitates radiative recombination. Using the QW solids, we demonstrate ultrapure green emission by completely downconverting a blue gallium nitride light-emitting diode at room temperature, with a luminous efficacy higher than 90 lumen W−1 at 5000 cd m−2, which has never been reached in any nanomaterial assemblies by far. PMID:29282451

Coupling single giant nanocrystal quantum dots to the fundamental mode of patch nanoantennas through fringe field

DOE PAGES

Wang, Feng; Karan, Niladri S.; Minh Nguyen, Hue; ...

2015-09-23

Through single dot spectroscopy and numerical simulation studies, we demonstrate that the fundamental mode of gold patch nanoantennas have fringe-field resonance capable of enhancing the nano-emitters coupled around the edge of the patch antenna. This fringe-field coupling is used to enhance the radiative rates of core/thick-shell nanocrystal quantum dots (g-NQDs) that cannot be embedded into the ultra-thin dielectric gap of patch nanoantennas due to their large sizes. We attain 14 and 3 times enhancements in single exciton radiative decay rate and bi-exciton emission efficiencies of g-NQDs respectively, with no detectable metal quenching. Our numerical studies confirmed our experimental results andmore » further reveal that patch nanoantennas can provide strong emission enhancement for dipoles lying not only in radial direction of the circular patches but also in the direction normal to the antennas surface. Finally, this provides a distinct advantage over the parallel gap-bar antennas that can provide enhancement only for the dipoles oriented across the gap.« less