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Sample records for acceptor bound exciton

  1. Radiative properties of multicarrier bound excitons in GaAs

    NASA Astrophysics Data System (ADS)

    Karin, Todd; Barbour, Russell J.; Santori, Charles; Yamamoto, Yoshihisa; Hirayama, Yoshiro; Fu, Kai-Mei C.

    2015-04-01

    Excitons in semiconductors can have multiple lifetimes due to spin-dependent oscillator strengths and interference between different recombination pathways. In addition, strain and symmetry effects can further modify lifetimes via the removal of degeneracies. We present a convenient formalism for predicting the optical properties of k =0 excitons with an arbitrary number of charge carriers in different symmetry environments. Using this formalism, we predict three distinct lifetimes for the neutral acceptor bound exciton in GaAs, and confirm this prediction through polarization dependent and time-resolved photoluminescence experiments. We find the acceptor bound-exciton lifetimes to be To×(1 ,3 ,3/4 ) , where To=(0.61 ±0.12 ) ns . Furthermore, we provide an estimate of the intralevel and interlevel exciton spin-relaxation rates.

  2. Ultrafast exciton dissociation at donor/acceptor interfaces

    NASA Astrophysics Data System (ADS)

    Grancini, G.; Fazzi, D.; Binda, M.; Maiuri, M.; Petrozza, A.; Criante, L.; Perissinotto, S.; Egelhaaf, H.-J.; Brida, D.; Cerullo, G.; Lanzani, G.

    2013-09-01

    Charge generation at donor/acceptor interface is a highly debated topic in the organic photovoltaics (OPV) community. The primary photoexcited state evolution happens in few femtosecond timescale, thus making very intriguing their full understanding. In particular charge generation is believed to occur in < 200 fs, but no clear picture emerged so far. In this work we reveal for the first time the actual charge generation mechanism following in real time the exciton dissociation mechanism by means of sub-22 fs pump-probe spectroscopy. We study a low-band-gap polymer: fullerene interface as an ideal system for OPV. We demonstrate that excitons dissociation leads, on a timescale of 20-50 fs, to two byproducts: bound interfacial charge transfer states (CTS) and free charges. The branching ratio of their formation depends on the excess photon energy provided. When high energy singlet polymer states are excited, well above the optical band gap, an ultrafast hot electron transfer happens between the polymer singlet state and the interfacial hot CTS* due to the high electronic coupling between them. Hot exciton dissociation prevails then on internal energy dissipation that occurs within few hundreds of fs. By measuring the internal quantum efficiency of a prototypical device a rising trend with energy is observed, thus indicating that hot exciton dissociation effectively leads to a higher fraction of free charges.

  3. Indirect optical absorption and origin of the emission from β-FeSi2 nanoparticles: Bound exciton (0.809 eV) and band to acceptor impurity (0.795 eV) transitions

    NASA Astrophysics Data System (ADS)

    Lang, R.; Amaral, L.; Meneses, E. A.

    2010-05-01

    We investigated the optical absorption of the fundamental band edge and the origin of the emission from β-FeSi2 nanoparticles synthesized by ion-beam-induced epitaxial crystallization of Fe+ implanted SiO2/Si(100) followed by thermal annealing. From micro-Raman scattering and transmission electron microscopy measurements it was possible to attest the formation of strained β-FeSi2 nanoparticles and its structural quality. The optical absorption near the fundamental gap edge of β-FeSi2 nanoparticles evaluated by spectroscopic ellipsometry showed a step structure characteristic of an indirect fundamental gap material. Photoluminescence spectroscopy measurements at each synthesis stage revealed complex emissions in the 0.7-0.9 eV spectral region, with different intensities and morphologies strongly dependent on thermal treatment temperature. Spectral deconvolution into four transition lines at 0.795, 0.809, 0.851, and 0.873 eV was performed. We concluded that the emission at 0.795 eV may be related to a radiative direct transition from the direct conduction band to an acceptor level and that the emission at 0.809 eV derives from a recombination of an indirect bound exciton to this acceptor level of β-FeSi2. Emissions 0.851 and 0.873 eV were confirmed to be typical dislocation-related photoluminescence centers in Si. From the energy balance we determined the fundamental indirect and direct band gap energies to be 0.856 and 0.867 eV, respectively. An illustrative energy band diagram derived from a proposed model to explain the possible transition processes involved is presented.

  4. Bound exciton and free exciton states in GaSe thin slab

    PubMed Central

    Wei, Chengrong; Chen, Xi; Li, Dian; Su, Huimin; He, Hongtao; Dai, Jun-Feng

    2016-01-01

    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. PMID:27654064

  5. Bound exciton and free exciton states in GaSe thin slab

    NASA Astrophysics Data System (ADS)

    Wei, Chengrong; Chen, Xi; Li, Dian; Su, Huimin; He, Hongtao; Dai, Jun-Feng

    2016-09-01

    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.

  6. Photocurrent generation through electron-exciton interaction at the organic semiconductor donor/acceptor interface.

    PubMed

    Chen, Lijia; Zhang, Qiaoming; Lei, Yanlian; Zhu, Furong; Wu, Bo; Zhang, Ting; Niu, Guoxi; Xiong, Zuhong; Song, Qunliang

    2013-10-21

    In this work, we report our effort to understand the photocurrent generation that is contributed via electron-exciton interaction at the donor/acceptor interface in organic solar cells (OSCs). Donor/acceptor bi-layer heterojunction OSCs, of the indium tin oxide/copper phthalocyanine (CuPc)/fullerene (C60)/molybdenum oxide/Al type, were employed to study the mechanism of photocurrent generation due to the electron-exciton interaction, where CuPc and C60 are the donor and the acceptor, respectively. It is shown that the electron-exciton interaction and the exciton dissociation processes co-exist at the CuPc/C60 interface in OSCs. Compared to conventional donor/acceptor bi-layer OSCs, the cells with the above configuration enable holes to be extracted at the C60 side while electrons can be collected at the CuPc side, resulting in a photocurrent in the reverse direction. The photocurrent thus observed is contributed to primarily by the charge carriers that are generated by the electron-exciton interaction at the CuPc/C60 interface, while charges derived from the exciton dissociation process also exist at the same interface. The mechanism of photocurrent generation due to electron-exciton interaction in the OSCs is further investigated, and it is manifested by the transient photovoltage characteristics and the external quantum efficiency measurements.

  7. Stark effect of intrinsic and extrinsic charge-transfer excitons in a linear donor-acceptor stack: anthracene-pyromellitic dianhydride.

    PubMed

    Weiser, Gerhard; Elschner, Andreas

    2009-06-25

    Anthracene-PMDA single crystals display at 2K about 70 meV below a well-known intrinsic charge-transfer exciton three narrow absorption lines, which are attributed to CT excitons bound to defects of a few 10(-5) concentration. All excitons respond very sensitively to electric fields along the molecular stack because of the large dipole moment, about 2 eA, of an ionized donor-acceptor pair, but only intrinsic excitons observe an optical selection rule. Although the triclinic unit cell contains only one pair of molecules, excitons appear in field-modulated spectra as near-degenerate doublets of different parity with very small splitting. The line shape of the EA spectra and selection rules with respect to the polarization of light and orientation of the field are consistent with the inversion symmetry of the lattice and the molecules. The simple crystal structure enables identification of the defects that are responsible for extrinsic excitons. Symmetry consideration based on translation invariance lead to a new interpretation of intrinsic excitons as true crystal states with charge transfer from the donor to the acceptor sublattice.

  8. Impact of the Crystallite Orientation Distribution on Exciton Transport in Donor-Acceptor Conjugated Polymers.

    PubMed

    Ayzner, Alexander L; Mei, Jianguo; Appleton, Anthony; DeLongchamp, Dean; Nardes, Alexandre; Benight, Stephanie; Kopidakis, Nikos; Toney, Michael F; Bao, Zhenan

    2015-12-30

    Conjugated polymers are widely used materials in organic photovoltaic devices. Owing to their extended electronic wave functions, they often form semicrystalline thin films. In this work, we aim to understand whether distribution of crystallographic orientations affects exciton diffusion using a low-band-gap polymer backbone motif that is representative of the donor/acceptor copolymer class. Using the fact that the polymer side chain can tune the dominant crystallographic orientation in the thin film, we have measured the quenching of polymer photoluminescence, and thus the extent of exciton dissociation, as a function of crystal orientation with respect to a quenching substrate. We find that the crystallite orientation distribution has little effect on the average exciton diffusion length. We suggest several possibilities for the lack of correlation between crystallographic texture and exciton transport in semicrystalline conjugated polymer films.

  9. Charge Transfer Fluorescence and 34 nm Exciton Diffusion Length in Polymers with Electron Acceptor End Traps.

    PubMed

    Zaikowski, Lori; Mauro, Gina; Bird, Matthew; Karten, Brianne; Asaoka, Sadayuki; Wu, Qin; Cook, Andrew R; Miller, John R

    2015-06-18

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17-127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence, and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps, the trap depths are 0.06 (p-xylene), 0.13 (THF), and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization, and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ∼50% of the excitons, and that the exciton diffusion length is LD = 34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. The efficiency of exciton capture depends on chain length but not on trap depth, solvent polarity, or which trap group is present.

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

    SciTech Connect

    Zaikowski, Lori; Mauro, Gina; Bird, Matthew; Karten, Brianne; Asaoka, Sadayuki; Wu, Qin; Cook, Andrew R.; Miller, John R.

    2014-12-22

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.

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

    DOE PAGES

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

    2014-12-22

    Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are asmore » large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.« less

  12. Three holes bound to a double acceptor - Be(+) in germanium

    NASA Technical Reports Server (NTRS)

    Haller, E. E.; Mcmurray, R. E., Jr.; Falicov, L. M.; Haegel, N. M.; Hansen, W. L.

    1983-01-01

    A double acceptor binding three holes has been observed for the first time with photoconductive far-infrared spectroscopy in beryllium-doped germanium single crystals. This new center, Be(+), has a hole binding energy of about 5 meV and is only present when free holes are generated by ionization of either neutral shallow acceptors or neutral Be double acceptors. The Be(+) center thermally ionizes above 4 K. It disappears at a uniaxial stress higher than about a billion dyn/sq cm parallel to (111) as a result of the lifting of the valence-band degeneracy.

  13. Giant permanent dipole moment of two-dimensional excitons bound to a single stacking fault

    NASA Astrophysics Data System (ADS)

    Karin, Todd; Linpeng, Xiayu; Glazov, M. M.; Durnev, M. V.; Ivchenko, E. L.; Harvey, Sarah; Rai, Ashish K.; Ludwig, Arne; Wieck, Andreas D.; Fu, Kai-Mei C.

    2016-07-01

    We investigate the magneto-optical properties of excitons bound to single stacking faults in high-purity GaAs. We find that the two-dimensional stacking fault potential binds an exciton composed of an electron and a heavy hole, and we confirm a vanishing in-plane hole g -factor, consistent with the atomic-scale symmetry of the system. The unprecedented homogeneity of the stacking-fault potential leads to ultranarrow photoluminescence emission lines (with a full width at half-maximum ≲80 μ eV ) and reveals a large magnetic nonreciprocity effect that originates from the magneto-Stark effect for mobile excitons. These measurements unambiguously determine the direction and magnitude of the giant electric dipole moment (≳e ×10 nm ) of the stacking-fault exciton, making stacking faults a promising new platform to study interacting excitonic gases.

  14. A Theory of Exciton Photoluminescence for Two Types of Neutral Acceptors in Silicon - A Study of the Systems Si: (B,In), Si: (Al,In), Si: (Ga,In), Si: (B,Al), Si: (B,Ga), and Si: (Al,Ga).

    DTIC Science & Technology

    1985-02-01

    Schrodinger equation -i2 d 2 Y T + (E - V)W = 0 (25) with the solutions = Aeix + Be - ikx 0 < x a II(x) = Ce- x + DeK x a < x < a + b (26) iii(x) = Eek2x...neutral acceptors, free exciton 20 12 capture cross section, rate equations , oscillator strength, thermal release rate, bound exciton decay rate...airc Lalculated usinc; a simpLe model of an exciton il, a one-dimeinsional. semi-infinite douible potential well. The energy eigerivalue equation for

  15. Reversal-bounded multipushdown machines. [Turing acceptors for context free languages

    NASA Technical Reports Server (NTRS)

    Baker, B. S.; Book, R. V.

    1974-01-01

    Several representations of the recursively enumerable (r.e.) sets are presented. The first states that every r.e. set is the homomorphic image of the intersection of two linear context-free languages. The second states that every r.e. set is accepted by an on-line Turing acceptor with two pushdown stores such that in every computation, each pushdown store can make at most one reversal (that is, one change from 'pushing' to 'popping'). It is shown that this automata theoretic representation cannot be strengthened by restricting the acceptors to be deterministic multitape, nondeterministic one-tape, or nondeterministic multicounter acceptors. This provides evidence that reversal bounds are not a natural measure of computational complexity for multitape Turing acceptors.

  16. Carbon related donor bound exciton transitions in ZnO nanowires

    SciTech Connect

    Mohammadbeigi, F.; Kumar, E. Senthil; Alagha, S.; Anderson, I.; Watkins, S. P.

    2014-08-07

    Several shallow donor bound exciton photoluminescence (PL) transitions are reported in ZnO nanowires doped with carbon. The emission energies are in the range of 3360.8–3361.9 meV, close to previously reported emission lines due to excitons bound to donor point defects, such as Ga, Al, In, and H. The addition of small amounts of hydrogen during growth results in a strong enhancement of the PL of these carbon related emission lines, yet PL and annealing measurements indicate no appreciable bulk hydrogen. The observation of two electron satellites for these emission lines enables the determination of the donor binding energies. The dependence of exciton localization energy on donor binding energy departs somewhat from the usual linear relationship observed for group III donors, indicating a qualitatively different central cell potential, as one would expect for a complex. Emission lines due to excitons bound to ionized donors associated with these defects are also observed. The dependence of the PL emission intensities on temperature and growth conditions demonstrates that the lines are due to distinct complexes and not merely excited states of each other.

  17. Interactions of bound excitons in doped core/shell quantum dot heterostructures

    NASA Astrophysics Data System (ADS)

    Avidan, Assaf; Deutsch, Zvicka; Oron, Dan

    2010-10-01

    Spatial localization to a defect or a dopant of one of the charge carriers comprising an exciton, has a significant effect on the optical properties of bulk semiconductors. It is not clear, however, how these effects would change when considering semiconductor nanocrystals in the strong confinement regime. As we show here, under strong confinement, doping has a dramatic effect on the energetics of multiply excited states, which exhibit a strong size dependence. This is experimentally shown by performing multiexciton spectroscopy of CdSe/CdS and ZnSe/CdS colloidal quantum dot (QD) heterostructures, whose cores are nucleation-doped with few atoms of tellurium, leading to localization of the holes. The biexciton (BX) is shown to be strongly blueshifted relative to the bound exciton, in stark contrast with the corresponding undoped nanocrystals exhibiting a BX redshift. The energetics of the BX is shown to be determined mostly by the energy difference between the dopant state and the valence-band edge while the emission color is mostly determined by quantum confinement in the conduction band. By tailoring the nanocrystal’s structure we can thus independently control the emission color, the radiative decay rate and the BX repulsion. QD heterostructures harboring bound excitons are therefore excellent candidates for colloidal-based gain devices required to operate in the single exciton gain regime.

  18. Repulsively bound exciton-biexciton states in high-spin fermions in optical lattices

    SciTech Connect

    Argueelles, A.; Santos, L.

    2011-03-15

    We show that the interplay between spin-changing collisions and quadratic Zeeman coupling provides a mechanism for the formation of repulsively bound composites in high-spin fermions, which we illustrate by considering spin flips in an initially polarized hard-core one-dimensional Mott insulator of spin-3/2 fermions. We show that after the flips the dynamics is characterized by the creation of two types of exciton-biexciton composites. We analyze the conditions for the existence of these bound states and discuss their intriguing properties. In particular we show that the effective mass and stability of the composites depends nontrivially on spin-changing collisions, on the quadratic Zeeman effect, and on the initial exciton localization. Finally, we show that the composites may remain stable against inelastic collisions, opening the possibility of interesting quantum composite phases.

  19. Magneto-optical properties and recombination dynamics of isoelectronic bound excitons in ZnO

    SciTech Connect

    Chen, S. L.; Chen, W. M.; Buyanova, I. A.

    2014-02-21

    Magneto-optical and time-resolved photoluminescence (PL) spectroscopies are employed to evaluate electronic structure of a bound exciton (BX) responsible for the 3.364 eV line (labeled as I{sub 1}{sup *}) in bulk ZnO. From time-resolved PL spectroscopy, I{sub 1}{sup *} is concluded to originate from the exciton ground state. Based on performed magneto-PL studies, the g-factors of the involved electron and hole are determined as being g{sub e} = 1.98 and g{sub h}{sup ∥}(g{sub h}{sup ⊥}) = 1.2(1.62), respectively. These values are nearly identical to the reported g-factors for the I{sup *} line in ZnO (Phys. Rev. B 86, 235205 (2012)), which proves that I{sub 1}{sup *} should have a similar origin as I{sup *} and should arise from an exciton bound to an isoelectronic center with a hole-attractive potential.

  20. Lowest optical excitations in molecular crystals: bound excitons versus free electron-hole pairs in anthracene.

    PubMed

    Hummer, Kerstin; Puschnig, Peter; Ambrosch-Draxl, Claudia

    2004-04-09

    By solving the Bethe-Salpeter equation for the electron-hole Green function for crystalline anthracene we find the lowest absorption peak generated by strongly bound excitons or by a free electron-hole pair, depending on the polarization direction being parallel to the short or the long molecular axis, respectively. Both excitations are shifted to lower energies by pressure. The physical difference of these excitations is apparent from the electron-hole wave functions. Our findings are a major contribution to solve the long-standing puzzle about the nature of the lowest optical excitations in organic materials.

  1. Evidence of harvesting electricity by exciton recombination in an n-n type solar cell.

    PubMed

    Song, Qun Liang; Yang, Hong Bin; Gan, Ye; Gong, Cheng; Ming Li, Chang

    2010-04-07

    Free electrons and holes bounded by weak interactions in organic molecules must be generated from excitons to produce photocurrent in organic solar cells. Free charge carriers, in either small molecule- or polymer-based solar cells, are generated so far by dissociation of excitons at the donor-acceptor interface through injecting electrons (holes) from a donor (acceptor) into an acceptor (donor) while leaving holes (electrons) in the donor (acceptor). Here we report a new way, intermolecular exciton recombination, to generate free carriers from organic semiconductors. Unlike the exciton dissociation between donor and acceptor, the recombination of electrons from perfluorinated hexadecafluorophthalo-cyaninatozinc (F16ZnPc) with holes from fullerene (C(60)) frees their counterpart carriers. A new organic solar cell based on this intermolecular exciton recombination at the interface is fabricated to clearly demonstrate this new way to produce free carriers and then harvest electricity from sunlight.

  2. Donor bound excitons in ZnSe nanoresonators - Applications in quantum information science

    SciTech Connect

    Pawlis, A.; Lischka, K.; Sanaka, K.; Yamamoto, Y.; Sleiter, D.

    2014-05-15

    Here we summarize the advantages of excitons bound to isolated fluorine donor in ZnSe/ZnMgSe quantum well nano-structures. Devices based on these semiconductors, are particularly suited to implement concepts of the optical manipulation of quantum states in solid-state material. The fluorine donor in ZnSe provides a physical qubit with potential advantages over previously researched qubits. In this context we show several initial demonstrations of devices, such as a low-threshold microdisk laser and an indistinguishable single photon source. Additionally we demonstrate the realization of a controllable three-level-system qubit consisting of a single Fluorine donor in a ZnSe nano-pillar, which provides an optical accessible single electon spin qubit.

  3. Improved Exciton Dissociation at Semiconducting Polymer:ZnO Donor:Acceptor Interfaces via Nitrogen Doping of ZnO

    PubMed Central

    Musselman, Kevin P; Albert-Seifried, Sebastian; Hoye, Robert L Z; Sadhanala, Aditya; Muñoz-Rojas, David; MacManus-Driscoll, Judith L; Friend, Richard H

    2014-01-01

    Exciton dissociation at the zinc oxide/poly(3-hexylthiophene) (ZnO/P3HT) interface as a function of nitrogen doping of the zinc oxide, which decreases the electron concentration from approximately 1019 cm−3 to 1017 cm−3, is reported. Exciton dissociation and device photocurrent are strongly improved with nitrogen doping. This improved dissociation of excitons in the conjugated polymer is found to result from enhanced light-induced de-trapping of electrons from the surface of the nitrogen-doped ZnO. The ability to improve the surface properties of ZnO by introducing a simple nitrogen dopant has general applicability. PMID:25520604

  4. Towards building artificial light harvesting complexes: enhanced singlet-singlet energy transfer between donor and acceptor pairs bound to albumins.

    PubMed

    Kumar, Challa V; Duff, Michael R

    2008-12-01

    Specific donor and acceptor pairs have been assembled in bovine serum albumin (BSA), at neutral pH and room temperature, and these dye-protein complexes indicated efficient donor to acceptor singlet-singlet energy transfer. For example, pyrene-1-butyric acid served as the donor and Coumarin 540A served as the acceptor. Both the donor and the acceptor bind to BSA with affinity constants in excess of 2x10(5) M(-1), as measured in absorption and circular dichroism (CD) spectral titrations. Simultaneous binding of both the donor and the acceptor chromophores was supported by CD spectra and one chromophore did not displace the other from the protein host, even when limited concentrations of the host were used. For example, a 1:1:1 complex between the donor, acceptor and the host can be readily formed, and spectral data clearly show that the binding sites are mutually exclusive. The ternary complexes (two different ligands bound to the same protein molecule) provided opportunities to examine singlet-singlet energy transfer between the protein-bound chromophores. Donor emission was quenched by the addition of the acceptor, in the presence of limited amounts of BSA, while no energy transfer was observed in the absence of the protein host, under the same conditions. The excitation spectra of the donor-acceptor-host complexes clearly show the sensitization of acceptor emission by the donor. Protein denaturation, as induced by the addition of urea or increasing the temperature to 360 K, inhibited energy transfer, which indicate that protein structure plays an important role. Sensitization also proceeded at low temperature (77 K) and diffusion of the donor or the acceptor is not required for energy transfer. Stern-Volmer quenching plots show that the quenching constant is (3.1+/-0.2)x10(4) M(-1), at low acceptor concentrations (<35 microM). Other albumins such as human and porcine proteins also served as good hosts for the above experiments. For the first time, non

  5. Excitons Bound to Nitrogen Pairs in GaAs as Seen by Photoluminescence of High Spectral and Spatial Resolution

    SciTech Connect

    Karaiskaj, D.; Mascarenhas, A.; Klem, J. F.; Volz, K.; Stolz, W.; Adamcyk, M.; Tiedje, T.

    2007-01-01

    High resolution photoluminescence (PL) spectroscopy was performed on high quality bulk GaAs, lightly doped with the nitrogen isoelectronic impurity. The shallowest nitrogen pair bound exciton center labeled as X{sub 1} revealed a total of six transitions. The photoluminescence lines from a small ensemble of nitrogen centers showed polarization dependent intensity. High spectral resolution PL spectroscopy was combined with confocal spectroscopy experiments performed on a GaAs:N/AlGaAs heterostructure. The high spatial resolution achieved by this technique enables us to localize and examine individual nitrogen bound excitons. Similar spectral structure and polarization dependence was observed for individual N-pair centers in GaAs. Both techniques support the C{sub 2v} symmetry of such isoelectronic impurity centers. The comparison between the PL spectra from an ensemble of nitrogen pairs and individual centers demonstrate the ability of the single impurity technique to lift the orientational degeneracy.

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

    PubMed Central

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

    2016-01-01

    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. PMID:27974815

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

    PubMed

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

    2016-12-15

    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.

  8. 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.

  9. Holes bound as small polarons to acceptor defects in oxide materials: why are their thermal ionization energies so high?

    NASA Astrophysics Data System (ADS)

    Schirmer, O. F.

    2011-08-01

    Holes bound to acceptor defects in oxide materials usually need comparatively high energies, of the order of 0.5-1.0 eV, to be ionized thermally to the valence band maximum. It is discussed that this has to be attributed to the stabilization of such holes by mainly short range interactions with the surrounding lattice, leading to the formation of small O - polarons. This is tantamount to the localization of the hole at only one of several equivalent oxygen ions next to the defect. The hole stabilizing energies can be determined experimentally from the related intense optical absorption bands. This paper exploits previous phenomenological studies of bound-hole small polarons in order to account for the large hole stabilization energies on this basis. A compilation demonstrates that bound-hole small polarons occur rather often in oxides and also in some related materials. The identification of such systems is based on EPR and optical studies and also on recent advanced electronic structure calculations.

  10. Photoluminescence and the exciton-phonon coupling in hydrothermally grown ZnO

    NASA Astrophysics Data System (ADS)

    Mendelsberg, R. J.; Allen, M. W.; Durbin, S. M.; Reeves, R. J.

    2011-05-01

    Near band-edge photoluminescence (PL) from hydrothermally grown bulk ZnO was studied as a function of temperature along with the effects of simultaneous excitation with below-gap photons, allowing for accurate assignment of the emission features not possible from low-temperature data alone. Free exciton emission was clearly observed at low temperatures and dominated the PL spectrum above 100 K. Emission from A excitons bound to three neutral donors dominated the low-temperature PL spectrum. Recombination of B excitons bound to these same neutral donors were also identified along with A excitons bound to the donors in their ionized state. A clear difference in the redshift of free and bound excitons with increasing temperature was observed and attributed to reduced exciton-phonon coupling for the bound excitons. Additionally, Fano resonance of the 1-LO replica of the dominant bound A exciton was observed to reduce its PL intensity which can lead to the misidentification of the 2-LO replica as a donor-acceptor-pair transition.

  11. Bound states and quantization of screening in the Wannier-Mott excitons

    SciTech Connect

    Makowski, Adam J.

    2011-02-15

    The problem of validity of the simple relation {lambda}=(n+2l)(n+2l+1) between the screening length {lambda} and the number of bound states in the Stern-Howard potential is discussed and the results are compared with those obtained for some potential with the same limiting behavior as the former one. The main conclusion of the present study is that the above relation does not hold for the Stern-Howard potential but most likely it is very close to an unknown relation to be discovered for the potential.

  12. Photoionization absorption and zero-field spin splitting of acceptor-bound magnetic polaron in p-type Hg1-xMnxTe single crystals

    NASA Astrophysics Data System (ADS)

    Zhu, Liangqing; Shao, Jun; Lin, Tie; Lü, Xiang; Zhu, Junyu; Tang, Xiaodong; Chu, Junhao

    2012-04-01

    Temperature-dependent magnetic (2-300 K), DC Hall (10-300 K), and infrared transmission (11.5-300 K) measurements are performed on a series of p-type Hg1-xMnxTe (0.12 ≤ x ≤ 0.26) single crystals in the spin-glass regime. Photoionization absorption (PIA) of acceptor-bound magnetic polarons (acceptor-BMPs) is observed to evolve with temperature, which is better accounted for by the classical oscillator model than by the quantum defect method. At low temperatures, p-type Hg1-xMnxTe manifests distinct phenomena of paramagnetic enhancement, negative magnetoresistance, and decrease of the effective binding energy and blueshift of the PIA of the acceptor-BMPs with nearly the same degree as temperature declines. A spin-splitting model is proposed, which can well reproduce the experimentally observed zero-field spin splitting of the acceptor-BMP level at low temperatures and the increase of the spin splitting as temperature drops. The results suggest that the acceptor-BMPs in Hg1-xMnxTe may have potential applications in light-driven polaronic memories, tunable far-infrared lasers, and detectors.

  13. Optical spectroscopy of single beryllium acceptors in GaAs/AlGaAs quantum well

    NASA Astrophysics Data System (ADS)

    Petrov, P. V.; Kokurin, I. A.; Klimko, G. V.; Ivanov, S. V.; Ivánov, Yu. L.; Koenraad, P. M.; Silov, A. Yu.; Averkiev, N. S.

    2016-09-01

    We carry out microphotoluminescence measurements of an acceptor-bound exciton (A0X ) recombination in the applied magnetic field with a single impurity resolution. In order to describe the obtained spectra we develop a theoretical model taking into account a quantum well (QW) confinement, an electron-hole and hole-hole exchange interaction. By means of fitting the measured data with the model we are able to study the fine structure of individual acceptors inside the QW. The good agreement between our experiments and the model indicates that we observe single acceptors in a pure two-dimensional environment whose states are unstrained in the QW plain.

  14. Exciton luminescence from Cu2SnS3 bulk crystals

    NASA Astrophysics Data System (ADS)

    Aihara, Naoya; Matsumoto, Yusuke; Tanaka, Kunihiko

    2016-02-01

    The optical properties of Cu2SnS3 (CTS) bulk crystals grown by chemical vapor transport were studied by photoluminescence (PL) spectroscopy. The PL spectra from the CTS bulk crystals were analyzed as a function of excitation power and temperature. The main phase of the as-grown samples was determined to be monoclinic CTS by Raman spectroscopy. The observed PL spectra from the CTS bulk crystals were composed of peaks corresponding to free-exciton, two bound-excitons, and donor-acceptor pair recombination luminescence. The peak energies for the free-exciton and two bound-exciton emissions were 0.9317, 0.9291, and 0.9260 eV, respectively, at temperature of 4.2 K. The bound-exciton luminescence was not observed above 30 K. The thermal activation energies for the free-exciton and two bound-exciton emissions were 6.5, 4.8, and 5.2 meV, respectively. The fundamental band gap in the CTS bulk crystals was expected to be ca. 0.94 eV.

  15. Bound excitons and many-body effects in x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Draxl, Claudia

    2015-11-01

    We study x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers (SAMs), investigating excitations from the nitrogen K edge. Azobenzene with H-termination and functionalized with CF3 groups is considered. The Bethe-Salpeter equation is employed to compute the spectra, including excitonic effects, and to determine the character of the near-edge resonances. Our results indicate that core-edge excitations are intense and strongly bound: their binding energies range from about 6 to 4 eV, going from isolated molecules to densely-packed SAMs. Electron-hole correlation rules these excitations, while the exchange interaction plays a negligible role.

  16. Long-range exciton dissociation in organic solar cells.

    PubMed

    Caruso, Domenico; Troisi, Alessandro

    2012-08-21

    It is normally assumed that electrons and holes in organic solar cells are generated by the dissociation of excitons at the interface between donor and acceptor materials in strongly bound hole-electron pairs. We show in this contribution that excitons can dissociate tens of angstroms away from the interface and generate partially separated electrons and holes, which can more easily overcome their coulombic attraction and form free charges. We first establish under what conditions long-range exciton dissociation is likely (using a kinetic model and a microscopic model for the calculation of the long-range electron transfer rate). Then, defining a rather general model Hamiltonian for the donor material, we show that the phenomenon is extremely common in the majority of polymer:fullerene bulk heterojunction solar cells.

  17. Optical Characterization of Strong UV Luminescence Emitted from the Excitonic Edge of Nickel Oxide Nanotowers

    PubMed Central

    Ho, Ching-Hwa; Kuo, Yi-Ming; Chan, Ching-Hsiang; Ma, Yuan-Ron

    2015-01-01

    NiO had been claimed to have the potential for application in transparent conducting oxide, electrochromic device for light control, and nonvolatile memory device. However, the detailed study of excitonic transition and light-emission property of NiO has rarely been explored to date. In this work, we demonstrate strong exciton-complex emission of high-quality NiO nanotowers grown by hot-filament metal-oxide vapor deposition with photoluminescence as an evaluation tool. Fine and clear emission features coming from the excitonic edge of the NiO are obviously observed in the photoluminescence spectra. A main excitonic emission of ~3.25 eV at 300 K can be decomposed into free exciton, bound excitons, and donor-acceptor-pair irradiations at lowered temperatures down to 10 K. The band-edge excitonic structure for the NiO nanocrystals has been evaluated and analyzed by transmission and thermoreflectacne measurements herein. All the experimental results demonstrate the cubic NiO thin-film nanotower is an applicable direct-band-gap material appropriate for UV luminescence and transparent-conducting-oxide applications. PMID:26506907

  18. Effects of sp-d exchange on a bound polaron and the g-factor of the exciton in a GaMnAs quantum dot

    NASA Astrophysics Data System (ADS)

    Lalitha, D.; John Peter, A.; Yoo, Chang Kyoo

    2013-08-01

    Magneto bound polaron in a GaMnAs/Ga0.6Al0.4As quantum dot is investigated with the inclusion of exchange interaction effects due to Mn alloy content and the geometrical confinement. The exciton binding energy and the optical transition energy are computed as functions of dot radius and the magnetic field strength for a fixed Mn alloy content (x = 0.02) in a GaMnAs quantum dot. Numerical calculations are performed using variational method within a single band effective mass approximation. The spin polaronic energy of the heavy hole exciton is studied with the spatial confinement using a mean field theory in the presence of magnetic field strength. The magnetization as a function of dot radius is investigated in a GaMnAs/Ga0.6Al0.4As quantum dot. The magnetic field induced size dependence of g-factor is studied. The effective g-factor of conduction (valence) band electron (hole) is obtained in the GaMnAs quantum dot. The results bring out that (i) the geometrical dependence on sp-d exchange interaction in the GaMnAs/Ga0.6Al0.4As quantum dot has great influence with the magnetic field strength, (ii) the Landé factor is more sensitive if the geometrical confinement effect is included and (iii) the value of g-factor increases when the magnetic field strength is enhanced for all the dot radii. Our results are in good agreement with the other investigators.

  19. Singlet exciton fission photovoltaics.

    PubMed

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

    2013-06-18

    Singlet exciton fission, a process that generates two excitons from a single photon, is perhaps the most efficient of the various multiexciton-generation processes studied to date, offering the potential to increase the efficiency of solar devices. But its unique characteristic, splitting a photogenerated singlet exciton into two dark triplet states, means that the empty absorption region between the singlet and triplet excitons must be filled by adding another material that captures low-energy photons. This has required the development of specialized device architectures. In this Account, we review work to develop devices that harness the theoretical benefits of singlet exciton fission. First, we discuss singlet fission in the archetypal material, pentacene. Pentacene-based photovoltaic devices typically show high external and internal quantum efficiencies. They have enabled researchers to characterize fission, including yield and the impact of competing loss processes, within functional devices. We review in situ probes of singlet fission that modulate the photocurrent using a magnetic field. We also summarize studies of the dissociation of triplet excitons into charge at the pentacene-buckyball (C60) donor-acceptor interface. Multiple independent measurements confirm that pentacene triplet excitons can dissociate at the C60 interface despite their relatively low energy. Because triplet excitons produced by singlet fission each have no more than half the energy of the original photoexcitation, they limit the potential open circuit voltage within a solar cell. Thus, if singlet fission is to increase the overall efficiency of a solar cell and not just double the photocurrent at the cost of halving the voltage, it is necessary to also harvest photons in the absorption gap between the singlet and triplet energies of the singlet fission material. We review two device architectures that attempt this using long-wavelength materials: a three-layer structure that uses

  20. Optical properties of ionized donor-bound excitons confined in strained wurtzite ZnO/MgxZn1-xO quantum dots

    NASA Astrophysics Data System (ADS)

    Dongmei, Zheng; Zongchi, Wang; Boqi, Xiao

    2015-03-01

    Within the framework of the effective-mass approximation and the dipole approximation, considering the three-dimensional confinement of the electron and hole and the strong built-in electric field (BEF) in strained wurtzite ZnO/Mg0.25Zn0.75O quantum dots (QDs), the optical properties of ionized donor-bound excitons (D+, X) are investigated theoretically using a variational method. The computations are performed in the case of finite band offset. Numerical results indicate that the optical properties of (D+, X) complexes sensitively depend on the donor position, the QD size and the BEF. The binding energy of (D+, X) complexes is larger when the donor is located in the vicinity of the left interface of the QDs, and it decreases with increasing QD size. The oscillator strength reduces with an increase in the dot height and increases with an increase in the dot radius. Furthermore, when the QD size decreases, the absorption peak intensity shows a marked increment, and the absorption coefficient peak has a blueshift. The strong BEF causes a redshift of the absorption coefficient peak and causes the absorption peak intensity to decrease remarkably. The physical reasons for these relationships have been analyzed in depth. Project supported by the National Natural Science Foundation for Young Scientists of China (No. 11102100), the Program for New Century Excellent Talents in Fujian Province University (No. JA14285) and the Program for Young Top-Notch Innovative Talents of Fujian Province of China.

  1. Size dependence of the polarizability and Haynes rule for an exciton bound to an ionized donor in a single spherical quantum dot

    SciTech Connect

    Feddi, E. Zouitine, A.; Oukerroum, A.; Zazoui, M.; Dujardin, F.; Assaid, E.

    2015-02-14

    We study the effect of an external electric field on an exciton bound to an ionized donor (D{sup +}, X) confined in a spherical quantum dot using a perturbative-variational method where the wave function and energy are developed in series of powers of the electric field strength. After testing this new approach in the determination of the band gap for some semiconductor materials, we generalize it to the case of (D{sup +}, X) in the presence of the electric field and for several materials ZnO, PbSe, and InAs, with significant values of the mass ratio. Three interesting results can be deduced: First, we show that the present method allows to determine the ground state energy in the presence of a weak electric field in a simple way (E = E{sub 0} − αf{sup 2}) using the energy without electric field E{sub 0} and the polarizability α. The second point is that our theoretical predictions show that the polarizability of (D{sup +}, X) varies proportionally to R{sup 3.5} and follows an ordering α{sub D{sup 0}}<α{sub X}<α{sub (D{sup +},X)}. The last point to highlight is that the Haynes rule remains valid even in the presence of a weak electric field.

  2. Identification of a Deep Acceptor Level in ZnO Due to Silver Doping

    NASA Astrophysics Data System (ADS)

    Chai, J.; Mendelsberg, R. J.; Reeves, R. J.; Kennedy, J.; von Wenckstern, H.; Schmidt, M.; Grundmann, M.; Doyle, K.; Myers, T. H.; Durbin, S. M.

    2010-05-01

    There remains considerable interest in the behavior of acceptors in ZnO, the ultimate goal being the realization of device grade p-type material. Silver is a candidate acceptor, and, in this study, in situ doping of silver was performed during plasma-assisted molecular beam epitaxy. Silver concentrations, as determined by ion beam analysis, ranged between 1018 cm-3and 1020 cm-3, with as much as 94% incorporated substitutionally on Zn lattice sites. Variable magnetic field Hall effect measurements detected no evidence of holes, and 4 K photoluminescence was dominated by donor bound excitons. Transient capacitance measurements, however, suggested that incorporated silver had led to the formation of an acceptor, located approximately 320 meV above the valence band edge, indicating that compensation remains a significant issue in determining the conductivity of ZnO.

  3. Free and bound excitonic effects in Al0.5Ga0.5N/Al0.35Ga0.65N MQWs with different Si-doping levels in the well layers

    PubMed Central

    He, Chenguang; Qin, Zhixin; Xu, Fujun; Hou, Mengjun; Zhang, Shan; Zhang, Lisheng; Wang, Xinqiang; Ge, Weikun; Shen, Bo

    2015-01-01

    Free exciton (FX) and bound exciton (BX) in Al0.5Ga0.5N/Al0.35Ga0.65N multiple quantum wells (MQWs) with different Si-doping levels in the well layers are investigated by photoluminescence (PL) spectra. Low temperature (10 K) PL spectra identify a large binding energy of 87.4 meV for the BX in undoped sample, and 63.6 meV for the BX in Si-doped (2 × 1018 cm−3) sample. They are attributed to O-bound and Si-bound excitons, respectively. The large binding energies of BX are assumed to originate from the strong quantum confinement in the quantum wells, which also leads to a stronger FX PL peak intensity in comparison with BX at 10 K. Si-doping is found to suppress the FX quenching by reducing threading dislocation density (TDD) in the well layers, leading to a significant improvement of IQE from 33.7% to 45%. PMID:26267249

  4. Generation of Multiple Excitons in Ag2S Quantum Dots: Single High-Energy versus Multiple-Photon Excitation.

    PubMed

    Sun, Jingya; Yu, Weili; Usman, Anwar; Isimjan, Tayirjan T; DGobbo, Silvano; Alarousu, Erkki; Takanabe, Kazuhiro; Mohammed, Omar F

    2014-02-20

    We explored biexciton generation via carrier multiplication (or multiple-exciton generation) by high-energy photons and by multiple-photon absorption in Ag2S quantum dots (QDs) using femtosecond broad-band transient absorption spectroscopy. Irrespective of the size of the QDs and how the multiple excitons are generated in the Ag2S QDs, two distinct characteristic time constants of 9.6-10.2 and 135-175 ps are obtained for the nonradiative Auger recombination of the multiple excitons, indicating the existence of two binding excitons, namely, tightly bound and weakly bound excitons. More importantly, the lifetimes of multiple excitons in Ag2S QDs were about 1 and 2 orders of magnitude longer than those of comparable size PbS QDs and single-walled carbon nanotubes, respectively. This result is significant because it suggests that by utilizing an appropriate electron acceptor, there is a higher possibility to extract multiple electron-hole pairs in Ag2S QDs, which should improve the performance of QD-based solar cell devices.

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

    NASA Astrophysics Data System (ADS)

    Shimazaki, Tomomi; Nakajima, Takahito

    2016-06-01

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

  6. 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

  7. DNA-mediated excitonic upconversion FRET switching

    SciTech Connect

    Kellis, Donald L.; Rehn, Sarah M.; Cannon, Brittany L.; Davis, Paul H.; Graugnard, Elton; Lee, Jeunghoon; Yurke, Bernard; Knowlton, William B.

    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 suffers 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.

  8. Ligand-bound Structures and Site-directed Mutagenesis Identify the Acceptor and Secondary Binding Sites of Streptomyces coelicolor Maltosyltransferase GlgE*

    PubMed Central

    Syson, Karl; Stevenson, Clare E. M.; Miah, Farzana; Barclay, J. Elaine; Tang, Minhong; Gorelik, Andrii; Rashid, Abdul M.; Lawson, David M.; Bornemann, Stephen

    2016-01-01

    GlgE is a maltosyltransferase involved in α-glucan biosynthesis in bacteria that has been genetically validated as a target for tuberculosis therapies. Crystals of the Mycobacterium tuberculosis enzyme diffract at low resolution so most structural studies have been with the very similar Streptomyces coelicolor GlgE isoform 1. Although the donor binding site for α-maltose 1-phosphate had been previously structurally defined, the acceptor site had not. Using mutagenesis, kinetics, and protein crystallography of the S. coelicolor enzyme, we have now identified the +1 to +6 subsites of the acceptor/product, which overlap with the known cyclodextrin binding site. The sugar residues in the acceptor subsites +1 to +5 are oriented such that they disfavor the binding of malto-oligosaccharides that bear branches at their 6-positions, consistent with the known acceptor chain specificity of GlgE. A secondary binding site remote from the catalytic center was identified that is distinct from one reported for the M. tuberculosis enzyme. This new site is capable of binding a branched α-glucan and is most likely involved in guiding acceptors toward the donor site because its disruption kinetically compromises the ability of GlgE to extend polymeric substrates. However, disruption of this site, which is conserved in the Streptomyces venezuelae GlgE enzyme, did not affect the growth of S. venezuelae or the structure of the polymeric product. The acceptor subsites +1 to +4 in the S. coelicolor enzyme are well conserved in the M. tuberculosis enzyme so their identification could help inform the design of inhibitors with therapeutic potential. PMID:27531751

  9. Ultrafast exciton dynamics at molecular surfaces

    NASA Astrophysics Data System (ADS)

    Monahan, Nicholas R.

    Further improvements to device performance are necessary to make solar energy conversion a compelling alternative to fossil fuels. Singlet exciton fission and charge separation are two processes that can heavily influence the power conversion efficiency of a solar cell. During exciton fission one singlet excitation converts into two triplet excitons, potentially doubling the photocurrent generated by higher energy photons. There is significant discord over the singlet fission mechanism and of particular interest is whether the process involves a multiexciton intermediate state. I used time-resolved two-photon photoemission to investigate singlet fission in hexacene thin films, a model system with strong electronic coupling. My results indicate that a multiexciton state forms within 40 fs of photoexcitation and loses singlet character on a 280 fs timescale, creating two triplet excitons. This is concordant with the transient absorption spectra of hexacene single crystals and definitively proves that exciton fission in hexacene proceeds through a multiexciton state. This state is likely common to all strongly-coupled systems and my results suggest that a reassessment of the generally-accepted singlet fission mechanism is required. Charge separation is the process of splitting neutral excitons into carriers that occurs at donor-acceptor heterojunctions in organic solar cells. Although this process is essential for device functionality, there are few compelling explanations for why it is highly efficient in certain organic photovoltaic systems. To investigate the charge separation process, I used the model system of charge transfer excitons at hexacene surfaces and time-resolved two-photon photoemission. Charge transfer excitons with sufficient energy spontaneously delocalize, growing from about 14 nm to over 50 nm within 200 fs. Entropy drives this delocalization, as the density of states within the Coulomb potential increases significantly with energy. This charge

  10. Exciton strings in an organic charge-transfer crystal

    NASA Astrophysics Data System (ADS)

    Kuwata-Gonokami, M.; Peyghambarian, N.; Meissner, K.; Fluegel, B.; Sato, Y.; Ema, K.; Shimano, R.; Mazumdar, S.; Guo, F.; Tokihiro, T.; Ezaki, H.; Hanamura, E.

    1994-01-01

    COLLECTIVE excitations resulting from many-body Coulomb interactions have been studied extensively in the solid state1: for example, the exchange interaction between the electrons in two excitons (bound electron-hole pairs) can bind the excitons together, forming a biexciton. At the other extreme, if the number of excitons is sufficiently large (~106), they can condense into a degenerate 'liquid' phase known as an electron-hole drop. But in conventional semiconductors, intermediate bound states, consisting of more than two excitons, are not formed. We show here, both theoretically and experimentally, that bound states of multiple excitons can form in the organic charge-transfer solid anthracene-(pyromellitic acid dianhydride). Coulomb interactions along the one-dimensional stacks of this material can stabilize trains of several charge-transfer excitons, and we refer to the resulting collective excitations as exciton strings.

  11. Coherent Exciton Dynamics in Atomically Thin Semiconductors

    NASA Astrophysics Data System (ADS)

    Li, Xiaoqin (Elaine)

    The near band-edge optical response of an emerging class of semiconductors, known as the transitional metal dichalcogenides (TMDs), is dominated by tightly-bound excitons and charged excitons (i.e. trions). A fundamental property of these quasiparticles (excitons and trions) is quantum decoherence time, which reflects irreversible quantum dissipation arising from system (excitons and trions) and bath (vacuum and other quasiparticles) interactions and determines the timescale during which excitons can be coherently manipulated. Dephasing time is also equivalent to the intrinsic homogeneous linewidth of exciton resonance. In addition, excitons in TMDs are localized at the corners of the Brillouin zone and provide a convenient way to optical manipulate the valley degree of freedom, which may act as a useful information carrier analogous to electronic charge or spin. Direct measurement of valley coherence time is challenging because it corresponds to a non-radiative coherence between two degenerate states. Using ultrafast multi-dimensional optical spectroscopy, we investigate the intrinsic homogeneous linewidth of excitons, exciton valley coherence as well as coupling between excitons and trions. Our studies reveal coherent electronic dynamics on the order of ~100 fs in monolayer TMDs. We gratefully acknowledge financial support from NSF, AFOSR, and the Welch Foundation.

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

    SciTech Connect

    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.

  13. Probing dark exciton diffusion using photovoltage

    PubMed Central

    Mullenbach, Tyler K.; Curtin, Ian J.; Zhang, Tao; Holmes, Russell J.

    2017-01-01

    The migration of weakly and non-luminescent (dark) excitons remains an understudied subset of exciton dynamics in molecular thin films. Inaccessible via photoluminescence, these states are often probed using photocurrent methods that require efficient charge collection. Here we probe exciton harvesting in both luminescent and dark materials using a photovoltage-based technique. Transient photovoltage permits a real-time measurement of the number of charges in an organic photovoltaic cell, while avoiding non-geminate recombination losses. The extracted exciton diffusion lengths are found to be similar to those determined using photocurrent. For the luminescent material boron subphthalocyanine chloride, the photovoltage determined diffusion length is less than that extracted from photoluminescence. This indicates that while photovoltage circumvents non-geminate losses, geminate recombination at the donor–acceptor interface remains the primary recombination pathway. Photovoltage thus offers a general approach for extracting a device-relevant diffusion length, while also providing insight in to the dominant carrier recombination pathways. PMID:28128206

  14. Probing dark exciton diffusion using photovoltage

    NASA Astrophysics Data System (ADS)

    Mullenbach, Tyler K.; Curtin, Ian J.; Zhang, Tao; Holmes, Russell J.

    2017-01-01

    The migration of weakly and non-luminescent (dark) excitons remains an understudied subset of exciton dynamics in molecular thin films. Inaccessible via photoluminescence, these states are often probed using photocurrent methods that require efficient charge collection. Here we probe exciton harvesting in both luminescent and dark materials using a photovoltage-based technique. Transient photovoltage permits a real-time measurement of the number of charges in an organic photovoltaic cell, while avoiding non-geminate recombination losses. The extracted exciton diffusion lengths are found to be similar to those determined using photocurrent. For the luminescent material boron subphthalocyanine chloride, the photovoltage determined diffusion length is less than that extracted from photoluminescence. This indicates that while photovoltage circumvents non-geminate losses, geminate recombination at the donor-acceptor interface remains the primary recombination pathway. Photovoltage thus offers a general approach for extracting a device-relevant diffusion length, while also providing insight in to the dominant carrier recombination pathways.

  15. 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.

  16. 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 (WS2 and MoSe2) through a study combining microscopic theory with spectroscopic measurements. We also show that the excitonic coherence lifetimemore » 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 WS2.« less

  17. Excitonic linewidth and coherence lifetime in monolayer transition metal dichalcogenides

    SciTech Connect

    Selig, Malte; Berghäuser, Gunnar; Raja, Archana; Nagler, Philipp; Schüller, Christian; Heinz, Tony F.; Korn, Tobias; Chernikov, Alexey; Malic, Ermin; Knorr, Andreas

    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 (WS2 and MoSe2) through a study combining microscopic theory with spectroscopic measurements. We also show that the excitonic 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 WS2.

  18. Excitonic linewidth and coherence lifetime in monolayer transition metal dichalcogenides

    PubMed Central

    Selig, Malte; Berghäuser, Gunnar; Raja, Archana; Nagler, Philipp; Schüller, Christian; Heinz, Tony F.; Korn, Tobias; Chernikov, Alexey; Malic, Ermin; Knorr, Andreas

    2016-01-01

    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. Here, we investigate the microscopic origin of the excitonic coherence lifetime in two representative materials (WS2 and MoSe2) through a study combining microscopic theory with spectroscopic measurements. We show that the excitonic coherence lifetime is determined by phonon-induced intravalley scattering and intervalley scattering into dark excitonic states. In particular, in WS2, we identify exciton relaxation processes involving phonon emission into lower-lying dark states that are operative at all temperatures. PMID:27819288

  19. Excitons and multi-excitons in single CdTe quantum dots probed by near-field spectroscopy

    NASA Astrophysics Data System (ADS)

    Brun, M.; Huant, S.; Woehl, J. C.; Motte, J.-F.; Marsal, L.; Mariette, H.

    2002-03-01

    A near-field optical spectroscopy study of a single CdTe/ZnTe quantum dot at low temperatures is presented. While the photoluminescence spectrum at low excitation power reveals only one single sharp peak due to the radiative recombination of excitons (X) in the single dot, several additional sharp peaks appear with increasing excitation density. The dominant features are ascribed to exciton complexes and charged exciton complexes such as negatively charged excitons (X -), neutral (2X and 3X) and negative (2X - and 3X -) biexcitons and triexcitons. Exciton charging arises due to efficient hole trapping by residual acceptors in the barrier material. This partly inhibits the formation of biexcitons and triexcitons. A spectral feature appearing close to the X - peak is tentatively assigned to X 2- negative excitons. This feature is found to shift to the red with increasing power: two possible explanations for this unexpected behaviour are proposed.

  20. Strong charge-transfer excitonic effects and the Bose-Einstein exciton condensate in graphane.

    PubMed

    Cudazzo, Pierluigi; Attaccalite, Claudio; Tokatly, Ilya V; Rubio, Angel

    2010-06-04

    Using first principles many-body theory methods (GW+Bethe-Salpeter equation) we demonstrate that the optical properties of graphane are dominated by localized charge-transfer excitations governed by enhanced electron correlations in a two-dimensional dielectric medium. Strong electron-hole interaction leads to the appearance of small radius bound excitons with spatially separated electron and hole, which are localized out of plane and in plane, respectively. The presence of such bound excitons opens the path towards an excitonic Bose-Einstein condensate in graphane that can be observed experimentally.

  1. Theory of core excitons

    SciTech Connect

    Dow, J. D.; Hjalmarson, H. P.; Sankey, O. F.; Allen, R. E.; Buettner, H.

    1980-01-01

    The observation of core excitons with binding energies much larger than those of the valence excitons in the same material has posed a long-standing theoretical problem. A proposed solution to this problem is presented, and Frenkel excitons and Wannier excitons are shown to coexist naturally in a single material. (GHT)

  2. Microscopic theories of excitons and their dynamics

    NASA Astrophysics Data System (ADS)

    Berkelbach, Timothy C.

    This thesis describes the development and application of microscopically-defined theories of excitons in a wide range of semiconducting materials. In Part I, I consider the topic of singlet exciton fission, an organic photophysical process which generates two spin-triplet excitons from one photoexcited spin-singlet exciton. I construct a theoretical framework that couples a realistic treatment of the static electronic structure with finite-temperature quantum relaxation techniques. This framework is applied separately, but consistently, to the problems of singlet fission in pentacene dimers, crystalline pentacene, and crystalline hexacene. Through this program, I am able to rationalize observed behaviors and make non-trivial predictions, some of which have been confirmed by experiment. In Part II, I present theoretical developments on the properties of neutral excitons and charged excitons (trions) in atomically thin transition metal dichalcogenides. This work includes an examination of material trends in exciton binding energies via an effective mass approach. I also present an experimental and theoretical collaboration, which links the unconventional disposition of excitons in the Rydberg series to the peculiar screening properties of atomically thin materials. The light-matter coupling in these materials is examined within low-energy models and is shown to give rise to bright and dark exciton states, which can be qualitatively labeled in analogy with the hydrogen series. In Part III, I explore theories of relaxation dynamics in condensed phase environments, with a focus on methodology development. This work is aimed towards biological processes, including resonant energy transfer in chromophore complexes and electron transfer in donor-bridge-acceptor systems. Specifically, I present a collaborative development of a numerically efficient but highly accurate hybrid approach to reduced dynamics, which exploits a partitioning of environmental degrees of freedom into

  3. Observations of exciton and carrier spin relaxation in Be doped p-type GaAs

    SciTech Connect

    Asaka, Naohiro; Harasawa, Ryo; Tackeuchi, Atsushi; Lu, Shulong; Dai, Pan

    2014-03-17

    We have investigated the exciton and carrier spin relaxation in Be-doped p-type GaAs. Time-resolved spin-dependent photoluminescence (PL) measurements revealed spin relaxation behaviors between 10 and 100 K. Two PL peaks were observed at 1.511 eV (peak 1) and 1.497 eV (peak 2) at 10 K, and are attributed to the recombination of excitons bound to neutral Be acceptors (peak 1) and the band-to-acceptor transition (peak 2). The spin relaxation times of both PL peaks were measured to be 1.3–3.1 ns at 10–100 K, and found to originate from common electron spin relaxation. The observed existence of a carrier density dependence of the spin relaxation time at 10–77 K indicates that the Bir-Aronov-Pikus process is the dominant spin relaxation mechanism.

  4. Efficient organic solar cells with helical perylene diimide electron acceptors.

    PubMed

    Zhong, Yu; Trinh, M Tuan; Chen, Rongsheng; Wang, Wei; Khlyabich, Petr P; Kumar, Bharat; Xu, Qizhi; Nam, Chang-Yong; Sfeir, Matthew Y; Black, Charles; Steigerwald, Michael L; Loo, Yueh-Lin; Xiao, Shengxiong; Ng, Fay; Zhu, X-Y; Nuckolls, Colin

    2014-10-29

    We report an efficiency of 6.1% for a solution-processed non-fullerene solar cell using a helical perylene diimide (PDI) dimer as the electron acceptor. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces, indicating that charge carriers are created from photogenerated excitons in both the electron donor and acceptor phases. Light-intensity-dependent current-voltage measurements suggested different recombination rates under short-circuit and open-circuit conditions.

  5. Exciton-Exciton Interaction in KMnF3

    NASA Astrophysics Data System (ADS)

    Strauss, E.; Maniscalco, W. J.; Yen, W. M.; Kellner, U. C.; Gerhardt, V.

    1980-03-01

    Exciton dynamics in KMnF3 at exciton densities up to 1016 cm-3 are examined with time-resolved emission spectroscopy. The exciton emission line shifts and broadens with increasing exciton density. A nonlinear exciton decay channel is observed. These effects are found to be consistent with an exciton-exciton process. The shift scales with the exciton density and suggests that the effect is dominated by pairwise interactions up to the densities reached in these experiments.

  6. Improving an organic photodiode by incorporating a tunnel barrier between the donor and acceptor layers

    NASA Astrophysics Data System (ADS)

    Campbell, I. H.; Crone, B. K.

    2012-07-01

    We demonstrate increased photocurrent quantum efficiency in a model donor/acceptor (tetracene/C60) photodiode by incorporating an insulating tunnel barrier between the tetracene and C60 layers. Photodiode efficiency results from the interplay of a number of processes which add to or subtract from the overall device efficiency. The positive rates are those of exciton dissociation and charge separation, the negative rates include exciton and charge transfer complex recombination. We show that by introducing a thin insulating layer between the donor and acceptor layers in a photodiode, we can modify the exciton dissociation and charge transfer complex recombination rates and improve device performance.

  7. A new class of collective excitations: Exciton strings

    NASA Astrophysics Data System (ADS)

    Mazumdar, S.; Guo, F.; Meissner, K.; Fluegel, B.; Peyghambarian, N.

    1996-06-01

    Optical excitation in a strongly neutral quasi-one-dimensional mixed-stack charge-transfer solid results in an exciton state, in which the electron and the hole are bound by electrostatic Coulomb interactions that are large compared to the one-electron hopping. We present a joint theoretical-experimental demonstration of a new class of collective excitations, multiexcitons or exciton strings, consisting of a string of several (more than two) bound excitons, in a prototype neutral charge-transfer solid. The stability of the multiexciton states arise from the combined effects of one dimensionality and strong Coulomb interactions. Theoretically, we show that in narrow band one-dimensional semiconductors with long range Coulomb interactions, the occurrence of stable 2-exciton string (biexciton) necessarily implies stable higher multiexcitons. Experimentally, evidence for the multiexciton strings is demonstrated by femtosecond pump-probe spectroscopy of anthracene pyromellitic acid dianhydride. Excellent qualitative agreement is found between the calculated and the measured differential transmission spectra. Photoinduced absorptions to the 2-exciton string at low pump intensity and to the 3-exciton string at high pump intensity are observed, in agreement with the theory of excited state absorption. The 2-exciton string is confirmed also by a direct two-photon absorption measurement. The binding energies of the 2-exciton and the 3-exciton strings are obtained from the experimental data. The larger binding energy of the 3-exciton is in agreement with theory.

  8. Excitons in boron nitride single layer

    NASA Astrophysics Data System (ADS)

    Galvani, Thomas; Paleari, Fulvio; Miranda, Henrique P. C.; Molina-Sánchez, Alejandro; Wirtz, Ludger; Latil, Sylvain; Amara, Hakim; Ducastelle, François

    2016-09-01

    Boron nitride single layer belongs to the family of two-dimensional materials whose optical properties are currently receiving considerable attention. Strong excitonic effects have already been observed in the bulk and still stronger effects are predicted for single layers. We present here a detailed study of these properties by combining ab initio calculations and a tight-binding Wannier analysis in both real and reciprocal space. Due to the simplicity of the band structure with single valence (π ) and conduction (π*) bands the tight-binding analysis becomes quasiquantitative with only two adjustable parameters and provides tools for a detailed analysis of the exciton properties. Strong deviations from the usual hydrogenic model are evidenced. The ground-state exciton is not a genuine Frenkel exciton, but a very localized tightly bound one. The other ones are similar to those found in transition-metal dichalcogenides and, although more localized, can be described within a Wannier-Mott scheme.

  9. Organic photosensitive cells having a reciprocal-carrier exciton blocking layer

    DOEpatents

    Rand, Barry P.; Forrest, Stephen R.; Thompson, Mark E.

    2007-06-12

    A photosensitive cell includes an anode and a cathode; a donor-type organic material and an acceptor-type organic material forming a donor-acceptor junction connected between the anode and the cathode; and an exciton blocking layer connected between the acceptor-type organic material of the donor-acceptor junction and the cathode, the blocking layer consisting essentially of a material that has a hole mobility of at least 10.sup.-7 cm.sup.2/V-sec or higher, where a HOMO of the blocking layer is higher than or equal to a HOMO of the acceptor-type material.

  10. Ghost Fano Resonance of Excitons in Twisted Bilayer Graphene

    NASA Astrophysics Data System (ADS)

    Liang, Yufeng

    2014-03-01

    Metallic systems are generally considered to be unable to harbor tightly bound excitons because of the strong screening effect as well as the absence of a finite band gap. Previously, exception has only been found in one-dimensional metallic carbon nanotubes due to the depressed screening effects and the symmetry gap. We explore the exciton spectra of twisted bilayer graphene (tBLG) and predict the existence of even more strongly bound exciton (with binding energy as large as 0.5eV) in this system despite of its higher dimensionality. Based on our results from first-principles simulations and effective model calculations, a mechanism known as the ghost Fano resonance is proposed for the bound exciton formation in metallic systems beyond the dimensonality-related argument. Our results shed light on engineering the e-h excitations in the few-layer van der Waals heterojunction. NSF Grant No. DMR-1207141.

  11. Acceptor and Excitation Density Dependence of the Ultrafast Polaron Absorption Signal in Donor-Acceptor Organic Solar Cell Blends.

    PubMed

    Zarrabi, Nasim; Burn, Paul L; Meredith, Paul; Shaw, Paul E

    2016-07-21

    Transient absorption spectroscopy on organic semiconductor blends for solar cells typically shows efficient charge generation within ∼100 fs, accounting for the majority of the charge carriers. In this Letter, we show using transient absorption spectroscopy on blends containing a broad range of acceptor content (0.01-50% by weight) that the rise of the polaron signal is dependent on the acceptor concentration. For low acceptor content (<10% by weight), the polaron signal rises gradually over ∼1 ps with most polarons generated after 200 fs, while for higher acceptor concentrations (>10%) most polarons are generated within 200 fs. The rise time in blends with low acceptor content was also found to be sensitive to the pump fluence, decreasing with increasing excitation density. These results indicate that the sub-100 fs rise of the polaron signal is a natural consequence of both the high acceptor concentrations in many donor-acceptor blends and the high excitation densities needed for transient absorption spectroscopy, which results in a short average distance between the exciton and the donor-acceptor interface.

  12. Dirac cones and Dirac saddle points of bright excitons in monolayer transition metal dichalcogenides.

    PubMed

    Yu, Hongyi; Liu, Gui-Bin; Gong, Pu; Xu, Xiaodong; Yao, Wang

    2014-05-12

    In monolayer transition metal dichalcogenides, tightly bound excitons have been discovered with a valley pseudospin optically addressable through polarization selection rules. Here, we show that this valley pseudospin is strongly coupled to the exciton centre-of-mass motion through electron-hole exchange. This coupling realizes a massless Dirac cone with chirality index I = 2 for excitons inside the light cone, that is, bright excitons. Under moderate strain, the I = 2 Dirac cone splits into two degenerate I = 1 Dirac cones, and saddle points with a linear Dirac spectrum emerge. After binding an extra electron, the charged exciton becomes a massive Dirac particle associated with a large valley Hall effect protected from intervalley scattering. Our results point to unique opportunities to study Dirac physics, with exciton's optical addressability at specifiable momentum, energy and pseudospin. The strain-tunable valley-orbit coupling also implies new structures of exciton condensates, new functionalities of excitonic circuits and mechanical control of valley pseudospin.

  13. Hydrogen-related excitons and their excited-state transitions in ZnO

    NASA Astrophysics Data System (ADS)

    Heinhold, R.; Neiman, A.; Kennedy, J. V.; Markwitz, A.; Reeves, R. J.; Allen, M. W.

    2017-02-01

    The role of hydrogen in the photoluminescence (PL) of ZnO was investigated using four different types of bulk ZnO single crystal, with varying concentrations of unintentional hydrogen donor and Group I acceptor impurities. Photoluminescence spectra were measured at 3 K, with emission energies determined to ±50 μeV, before and after separate annealing in O2, N2, and H2 atmospheres. Using this approach, several new hydrogen-related neutral-donor-bound excitons, and their corresponding B exciton, ionized donor, and two electron satellite (TES) excited state transitions were identified and their properties further investigated using hydrogen and deuterium ion implantation. The commonly observed I4 (3.36272 eV) emission due to excitons bound to multicoordinated hydrogen inside an oxygen vacancy (HO), that is present in most ZnO material, was noticeably absent in hydrothermally grown (HT) ZnO and instead was replaced by a doublet of two closely lying recombination lines I4 b ,c (3.36219, 3.36237 eV) due to a hydrogen-related donor with a binding energy (ED) of 47.7 meV. A new and usually dominant recombination line I6 -H (3.36085 eV) due to a different hydrogen-related defect complex with an ED of 49.5 meV was also identified in HT ZnO. Here, I4 b ,c and I6 -H were stable up to approximately 400 and 600 °C, respectively, indicating that they are likely to contribute to the unintentional n -type conductivity of ZnO. Another doublet I5 (3.36137, 3.36148 eV) was identified in hydrogenated HT ZnO single crystals with low Li concentrations, and this was associated with a defect complex with an ED of 49.1 meV. A broad near band edge (NBE) emission centered at 3.366 eV was associated with excitons bound to subsurface hydrogen. We further demonstrate that hydrogen incorporates on different lattice sites for different annealing conditions and show that the new features I4 b ,c, I6 -H, and I5 most likely originate from the lithium-hydrogen defect complexes L iZn-HO , A l

  14. Identification of singlet and triplet states of negatively charged excitons in CdTe-based quantum wells

    NASA Astrophysics Data System (ADS)

    Astakhov, G. V.; Yakovlev, D. R.; Crooker, S. A.; Ossau, W.; Christianen, P. C. M.; Rudenkov, V. V.; Karczewski, G.; Wojtowicz, T.; Kossut, J.

    2004-02-01

    We present comprehensive study of negatively charged exciton in high magnetic fields for filling factors < 1. In magneto-optical spectra the fine structure was found to be contributed by neutral exciton and different a set of bound states of charged exciton. These states were identified due to their unique polarization properties charecteristics in emission and absorption spectra.

  15. The role of deep acceptor centers in the oxidation of acceptor-doped wide-band-gap perovskites ABO3

    NASA Astrophysics Data System (ADS)

    Putilov, L. P.; Tsidilkovski, V. I.

    2017-03-01

    The impact of deep acceptor centers on defect thermodynamics and oxidation of wide-band-gap acceptor-doped perovskites without mixed-valence cations is studied. These deep centers are formed by the acceptor-bound small hole polarons whose stabilization energy can be high enough (significantly higher than the hole-acceptor Coulomb interaction energy). It is shown that the oxidation enthalpy ΔHox of oxide is determined by the energy εA of acceptor-bound states along with the formation energy EV of oxygen vacancies. The oxidation reaction is demonstrated to be either endothermic or exothermic, and the regions of εA and EV values corresponding to the positive or negative ΔHox are determined. The contribution of acceptor-bound holes to the defect thermodynamics strongly depends on the acceptor states depth εA: it becomes negligible at εA less than a certain value (at which the acceptor levels are still deep). With increasing εA, the concentration of acceptor-bound small hole polarons can reach the values comparable to the dopant content. The results are illustrated with the acceptor-doped BaZrO3 as an example. It is shown that the experimental data on the bulk hole conductivity of barium zirconate can be described both in the band transport model and in the model of hopping small polarons localized on oxygen ions away from the acceptor centers. Depending on the εA magnitude, the oxidation reaction can be either endothermic or exothermic for both mobility mechanisms.

  16. Probing excitonic dark states in single-layer tungsten disulphide

    NASA Astrophysics Data System (ADS)

    Ye, Ziliang; Cao, Ting; O'Brien, Kevin; Zhu, Hanyu; Yin, Xiaobo; Wang, Yuan; Louie, Steven G.; Zhang, Xiang

    2014-09-01

    Transition metal dichalcogenide (TMDC) monolayers have recently emerged as an important class of two-dimensional semiconductors with potential for electronic and optoelectronic devices. Unlike semi-metallic graphene, layered TMDCs have a sizeable bandgap. More interestingly, when thinned down to a monolayer, TMDCs transform from indirect-bandgap to direct-bandgap semiconductors, exhibiting a number of intriguing optical phenomena such as valley-selective circular dichroism, doping-dependent charged excitons and strong photocurrent responses. However, the fundamental mechanism underlying such a strong light-matter interaction is still under intensive investigation. First-principles calculations have predicted a quasiparticle bandgap much larger than the measured optical gap, and an optical response dominated by excitonic effects. In particular, a recent study based on a GW plus Bethe-Salpeter equation (GW-BSE) approach, which employed many-body Green's-function methodology to address electron-electron and electron-hole interactions, theoretically predicted a diversity of strongly bound excitons. Here we report experimental evidence of a series of excitonic dark states in single-layer WS2 using two-photon excitation spectroscopy. In combination with GW-BSE theory, we prove that the excitons are of Wannier type, meaning that each exciton wavefunction extends over multiple unit cells, but with extraordinarily large binding energy (~0.7 electronvolts), leading to a quasiparticle bandgap of 2.7 electronvolts. These strongly bound exciton states are observed to be stable even at room temperature. We reveal an exciton series that deviates substantially from hydrogen models, with a novel energy dependence on the orbital angular momentum. These excitonic energy levels are experimentally found to be robust against environmental perturbations. The discovery of excitonic dark states and exceptionally large binding energy not only sheds light on the importance of many

  17. Theory of exciton transfer and diffusion in conjugated polymers

    SciTech Connect

    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

  18. Control of exciton fluxes in an excitonic integrated circuit.

    PubMed

    High, Alex A; Novitskaya, Ekaterina E; Butov, Leonid V; Hanson, Micah; Gossard, Arthur C

    2008-07-11

    Efficient signal communication uses photons. Signal processing, however, uses an optically inactive medium, electrons. Therefore, an interconnection between electronic signal processing and optical communication is required at the integrated circuit level. We demonstrated control of exciton fluxes in an excitonic integrated circuit. The circuit consists of three exciton optoelectronic transistors and performs operations with exciton fluxes, such as directional switching and merging. Photons transform into excitons at the circuit input, and the excitons transform into photons at the circuit output. The exciton flux from the input to the output is controlled by a pattern of the electrode voltages. The direct coupling of photons, used in communication, to excitons, used as the device-operation medium, may lead to the development of efficient exciton-based optoelectronic devices.

  19. Control of Radiative Exciton Recombination by Charge Transfer Induced Surface Dipoles in MoS2 and WS2 Monolayers

    PubMed Central

    Hu, Peng; Ye, Jun; He, Xuexia; Du, Kezhao; Zhang, Keke K.; Wang, Xingzhi; Xiong, Qihua; Liu, Zheng; Jiang, Hui; Kloc, Christian

    2016-01-01

    Due to the two dimensional confinement of electrons in a monolayer of 2D materials, the properties of monolayer can be controlled by electrical field formed on the monolayer surface. F4TCNQ was evaporated on MoS2 and WS2 monolayer forming dipoles between strong acceptor, F4TCNQ, and monolayers of MoS2 or WS2. The strong acceptor attracts electrons (charge transfer) and decreases the number of the ionized excitons. Free excitons undergo radiative recombination in both MoS2 and WS2. Moreover, the photoluminescence enhancement is stronger in WS2 where the exciton-phonon coupling is weaker. The theoretical model indicates that the surface dipole controls the radiative exciton recombination and enhances photoluminescence radiation. Deposition of F4TCNQ on the 2D monolayers enables a convenient control of the radiative exciton recombination and leads to the applications of these materials in lasers or LEDs. PMID:27053440

  20. The convergence of longitudinal excitons onto the Γ5 transverse exciton in GaN and the thermal activation energy of longitudinal excitons

    NASA Astrophysics Data System (ADS)

    Elgawadi, Amal; Gainer, Gordon; Krasinski, Jerzy

    2013-08-01

    The crystal orientation dependence of GaN excitons was investigated via the photoluminescence (PL) technique. The PL emissions at a temperature of 10 K were obtained from two experimental configurations where the emission K vector (the propagation vector) was either parallel (K ∥ c) or perpendicular (K ∥ c) to the crystal c-axis. Longitudinal, transverse and donor-bound excitons were observed in the two configurations. However, the longitudinal excitons converged onto the transverse free exciton Γ5 in the K⊥c emission. This behavior was discussed in terms of electron screening due to the scattering of electrons moving perpendicular to charged dislocation lines. Additionally, the thermal activation energy of the longitudinal excitons was calculated from the temperature dependent PL measurements collected from the K ∥ c emission, and was found to be 5 to 6 times as high as the binding energy of the free excitons. This high energy was interpreted tentatively in view of the creation of polaritons in strong exciton-photon coupling regimes. These findings present fundamental concepts for applications such as vertical cavity surface-emitting lasers (VCSELs) and polariton lasers.

  1. Organic photovoltaic cell incorporating electron conducting exciton blocking layers

    SciTech Connect

    Forrest, Stephen R.; Lassiter, Brian E.

    2014-08-26

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

  2. Alternansucrase acceptor products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The regioselectivity of alternansucrase (EC 2.4.1.140) differs from dextransucrase (EC 2.4.1.5) in ways that can be useful for the synthesis of novel oligosaccharide structures. For example, it has been recently shown that the major oligosaccharides produced when maltose is the acceptor include one...

  3. Large excitonic effects in group-IV sulfide monolayers

    NASA Astrophysics Data System (ADS)

    Tuttle, Blair R.; Alhassan, Saeed M.; Pantelides, Sokrates T.

    2015-12-01

    Large exciton binding energies are a distinguishing feature of two-dimensional semiconductors because of reduced screening, potentially leading to unique optoelectronic applications. Here we use electronic structure methods to calculate the properties of a two-dimensional material class: group-IV monosulfides including SiS, GeS, and SnS. Bulk SiS is predicted to be a metastable layered material. Quasiparticle excitations are calculated with the G0W0 method and the Bethe-Salpeter equation is are used to include electron-hole interactions. For monolayers, strongly bound excitons are found below the quasiparticle absorption edge. The predicted excitonic binding energies are as high as 0.7 eV. Due to large excitonic effects, these group-IV sulfide monolayers have great potential for nanoscale optoelectronic applications.

  4. Exciton-induced degradation of photocurrent in small-molecule organic solar cells

    NASA Astrophysics Data System (ADS)

    Tong, Xiaoran; Wang, Nana; Slootsky, Michael; Forrest, Stephen

    2013-03-01

    The reliability of organic photovoltaic cells (OPVs) has become a focus of research. In this work, the intrinsic degradation mechanism of archetypal subphthalocyanine/fullerene OPVs in the absence of water and oxygen is studied. We focus on the initial burn-in period (<10h) during which there is no significant change in fill factor or open-circuit voltage, suggesting stable interfacial and bulk morphology. In planar OPVs employing C60 as the acceptor, the efficiency drop is primarily due to a reduction of photocurrent contributed by C60, as observed in the spectrally-resolved external quantum efficiency (EQE). The current loss occurs after the cell is illuminated in the C60 absorption range, regardless of intensity and proportional to the total number of C60-absorbed photons. The degradation over time is modeled as due to an increasing density of exciton-induced quenching sites that hinder exciton diffusion to the donor-acceptor interface. Experimentally, we find this mechanism can be effectively mitigated by employing a mixed donor-acceptor active layer where excitons are rapidly dissociated and the steady-state exciton density is reduced. The trap formation rate and exciton dynamics will be discussed in detail. Degradation of different OPV systems will be compared. Optoelectronic Information, University of Electronic Science and Technology of China, Chengdu, China

  5. Control of Exciton Photon Coupling in Nano-structures

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoze

    In this thesis, we study the interaction of excitons with photons and plasmons and methods to control and enhance this interaction. This study is categorized in three parts: light-matter interaction in microcavity structures, direct dipole-dipole interactions, and plasmon-exciton interaction in metal-semiconductor systems. In the microcavity structures, the light-matter interactions become significant when the excitonic energy is in resonance with microcavity photons. New hybrid quantum states named polariton states will be formed if the strong coupling regime is achieved, where the interaction rate is faster than the average decay rate of the excitons and photons. Polaritons have been investigated in zinc oxide (ZnO) nanoparticles based microcavity at room temperature and stimulated emission of the polaritons has also been observed with a low optical pump threshold. Exictons in organic semiconductors (modeled as Frenkel excitons) are tightly bound to molecular sites, and differ considerably from loosely bound hydrogen atom-like inorganic excitons (modeled as Wannier-Mott excitons). This fundamental difference results in distinct optoelectronic properties. Not only strongly coupled to Wannier-Mott excitons in ZnO, the microcavity photons have also been observed to be simultaneously coupled to Frenkel excitons in 3,4,7,8-naphthalene tetracarboxylic dianhydride (NTCDA). The photons here act like a glue combining Wannier-Mott and Frenkel excitons into new hybrid polaritons taking the best from both constituents. Two-dimensional (2D) excitons in monolayer transition metal dichalcogenides (TMDs) have emerged as a new and fascinating type of Wannier-Mott-like excitons due to direct bandgap transition, huge oscillator strength and large binding energy. Monolayer molybdenum disulfide (MoS2) has been incorporated into the microcavity structure and 2D exciton-polaritons have been observed for the first time with directional emission in the strong coupling regime. Valley

  6. Indirect excitons in hydrogen-doped ZnO

    NASA Astrophysics Data System (ADS)

    Zhu, Liangchen; Lem, Laurent L. C.; Nguyen, Thien-Phap; Fair, Kit; Ali, Sajid; Ford, Michael J.; Phillips, Matthew R.; Ton-That, Cuong

    2017-03-01

    We present a correlative experimental and theoretical study of bound excitons in hydrogen-doped ZnO, with a particular focus on the dynamics of their metastable state confined in the sub-surface region, using a combination of surface-sensitive characterisation techniques and density functional theory calculations. A metastable sub-surface emission at 3.31 eV found in H-doped ZnO is attributed to the radiative recombination of indirect excitons localised at basal plane stacking faults (BSFs) where the excitonic transition involves electrons bound to bond-centre hydrogen donors in the potential well of the BSF. Additionally, our work shows the electrical transport of ZnO Schottky junctions is dominated by electrons confined at BSFs in the near-surface region.

  7. Nature of excitons bound to inversion domain boundaries: Origin of the 3.45-eV luminescence lines in spontaneously formed GaN nanowires on Si(111)

    NASA Astrophysics Data System (ADS)

    Pfüller, Carsten; Corfdir, Pierre; Hauswald, Christian; Flissikowski, Timur; Kong, Xiang; Zettler, Johannes K.; Fernández-Garrido, Sergio; Doǧan, Pınar; Grahn, Holger T.; Trampert, Achim; Geelhaar, Lutz; Brandt, Oliver

    2016-10-01

    We investigate the 3.45-eV luminescence band of spontaneously formed GaN nanowires on Si(111) by photoluminescence and cathodoluminescence spectroscopy. This band is found to be particularly prominent for samples synthesized at comparatively low temperatures. At the same time, these samples exhibit a peculiar morphology, namely, isolated long nanowires are interspersed within a dense matrix of short ones. Cathodoluminescence intensity maps reveal the 3.45-eV band to originate primarily from the long nanowires. Transmission electron microscopy shows that these long nanowires are either Ga polar and are joined by an inversion domain boundary with their short N-polar neighbors, or exhibit a Ga-polar core surrounded by a N-polar shell with a tubular inversion domain boundary at the core/shell interface. For samples grown at high temperatures, which exhibit a uniform nanowire morphology, the 3.45-eV band is also found to originate from particular nanowires in the ensemble and thus presumably from inversion domain boundaries stemming from the coexistence of N- and Ga-polar nanowires. For several of the investigated samples, the 3.45-eV band splits into a doublet. We demonstrate that the higher-energy component of this doublet arises from the recombination of two-dimensional excitons free to move in the plane of the inversion domain boundary. In contrast, the lower-energy component of the doublet originates from excitons localized in the plane of the inversion domain boundary. We propose that this in-plane localization is due to shallow donors in the vicinity of the inversion domain boundaries.

  8. Role of strain on the coherent properties of GaAs excitons and biexcitons

    NASA Astrophysics Data System (ADS)

    Wilmer, Brian L.; Webber, Daniel; Ashley, Joseph M.; Hall, Kimberley C.; Bristow, Alan D.

    2016-08-01

    Polarization-dependent two-dimensional Fourier-transform spectroscopy (2DFTS) is performed on excitons in strained bulk GaAs layers, probing the coherent response for differing amounts of strain. Uniaxial tensile strain lifts the degeneracy of heavy-hole (HH) and light-hole (LH) valence states, leading to an observed splitting of the associated excitons at low temperature. Increasing the strain increases the magnitude of the HH/LH exciton peak splitting, induces an asymmetry in the off-diagonal interaction coherences, increases the difference in the HH and LH 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 LH, HH, and mixed biexcitons.

  9. Interlayer Exciton Optoelectronics in a 2D Heterostructure p-n Junction.

    PubMed

    Ross, Jason S; Rivera, Pasqual; Schaibley, John; Lee-Wong, Eric; Yu, Hongyi; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jiaqiang; Mandrus, David; Cobden, David; Yao, Wang; Xu, Xiaodong

    2017-02-08

    Semiconductor heterostructures are backbones for solid-state-based optoelectronic devices. Recent advances in assembly techniques for van der Waals heterostructures have enabled the band engineering of semiconductor heterojunctions for atomically thin optoelectronic devices. In two-dimensional heterostructures with type II band alignment, interlayer excitons, where Coulomb bound electrons and holes are confined to opposite layers, have shown promising properties for novel excitonic devices, including a large binding energy, micron-scale in-plane drift-diffusion, and a long population and valley polarization lifetime. Here, we demonstrate interlayer exciton optoelectronics based on electrostatically defined lateral p-n junctions in a MoSe2-WSe2 heterobilayer. Applying a forward bias enables the first observation of electroluminescence from interlayer excitons. At zero bias, the p-n junction functions as a highly sensitive photodetector, where the wavelength-dependent photocurrent measurement allows the direct observation of resonant optical excitation of the interlayer exciton. The resulting photocurrent amplitude from the interlayer exciton is about 200 times smaller than the resonant excitation of intralayer exciton. This implies that the interlayer exciton oscillator strength is 2 orders of magnitude smaller than that of the intralayer exciton due to the spatial separation of electron and hole to the opposite layers. These results lay the foundation for exploiting the interlayer exciton in future 2D heterostructure optoelectronic devices.

  10. Enabling valley selective exciton scattering in monolayer WSe2 through upconversion.

    PubMed

    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

    2017-04-03

    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.

  11. Interlayer Exciton Optoelectronics in a 2D Heterostructure p–n Junction

    NASA Astrophysics Data System (ADS)

    Ross, Jason S.; Rivera, Pasqual; Schaibley, John; Lee-Wong, Eric; Yu, Hongyi; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jiaqiang; Mandrus, David; Cobden, David; Yao, Wang; Xu, Xiaodong

    2017-02-01

    Semiconductor heterostructures are backbones for solid state based optoelectronic devices. Recent advances in assembly techniques for van der Waals heterostructures has enabled the band engineering of semiconductor heterojunctions for atomically thin optoelectronic devices. In two-dimensional heterostructures with type II band alignment, interlayer excitons, where Coulomb-bound electrons and holes are confined to opposite layers, have shown promising properties for novel excitonic devices, including a large binding energy, micron-scale in-plane drift-diffusion, and long population and valley polarization lifetime. Here, we demonstrate interlayer exciton optoelectronics based on electrostatically defined lateral p-n junctions in a MoSe2-WSe2 heterobilayer. Applying a forward bias enables the first observation of electroluminescence from interlayer excitons. At zero bias, the p-n junction functions as a highly sensitive photodetector, where the wavelength-dependent photocurrent measurement allows the direct observation of resonant optical excitation of the interlayer exciton. The resulting photocurrent amplitude from the interlayer exciton is about 200 times smaller compared to the resonant excitation of intralayer exciton. This implies that the interlayer exciton oscillator strength is two orders of magnitude smaller than that of the intralayer exciton due to the spatial separation of electron and hole to opposite layers. These results lay the foundation for exploiting the interlayer exciton in future 2D heterostructure optoelectronic devices.

  12. Calculation of rates of exciton dissociation into hot charge-transfer states in model organic photovoltaic interfaces

    NASA Astrophysics Data System (ADS)

    Vázquez, Héctor; Troisi, Alessandro

    2013-11-01

    We investigate the process of exciton dissociation in ordered and disordered model donor/acceptor systems and describe a method to calculate exciton dissociation rates. We consider a one-dimensional system with Frenkel states in the donor material and states where charge transfer has taken place between donor and acceptor. We introduce a Green's function approach to calculate the generation rates of charge-transfer states. For disorder in the Frenkel states we find a clear exponential dependence of charge dissociation rates with exciton-interface distance, with a distance decay constant β that increases linearly with the amount of disorder. Disorder in the parameters that describe (final) charge-transfer states has little effect on the rates. Exciton dissociation invariably leads to partially separated charges. In all cases final states are “hot” charge-transfer states, with electron and hole located far from the interface.

  13. Semiconducting monolayer materials as a tunable platform for excitonic solar cells.

    PubMed

    Bernardi, Marco; Palummo, Maurizia; Grossman, Jeffrey C

    2012-11-27

    The recent advent of two-dimensional monolayer materials with tunable optical properties and high carrier mobility offers renewed opportunities for efficient, ultrathin excitonic solar cells alternative to those based on conjugated polymer and small molecule donors. Using first-principles density functional theory and many-body calculations, we demonstrate that monolayers of hexagonal BN and graphene (CBN) combined with commonly used acceptors such as PCBM fullerene or semiconducting carbon nanotubes can provide excitonic solar cells with tunable absorber gap, donor-acceptor interface band alignment, and power conversion efficiency, as well as novel device architectures. For the case of CBN-PCBM devices, we predict power conversion efficiency limits in the 10-20% range depending on the CBN monolayer structure. Our results demonstrate the possibility of using monolayer materials in tunable, efficient, ultrathin solar cells in which unexplored exciton and carrier transport regimes are at play.

  14. Origin of simultaneous donor-acceptor emission in single molecules of peryleneimide-terrylenediimide labeled polyphenylene dendrimers.

    PubMed

    Melnikov, Sergey M; Yeow, Edwin K L; Uji-i, Hiroshi; Cotlet, Mircea; Müllen, Klaus; De Schryver, Frans C; Enderlein, Jörg; Hofkens, Johan

    2007-02-01

    Förster type resonance energy transfer (FRET) in donor-acceptor peryleneimide-terrylenediimide dendrimers has been examined at the single molecule level. Very efficient energy transfer between the donor and the acceptor prevent the detection of donor emission before photobleaching of the acceptor. Indeed, in solution, on exciting the donor, only acceptor emission is detected. However, at the single molecule level, an important fraction of the investigated individual molecules (about 10-15%) show simultaneous emission from both donor and acceptor chromophores. The effect becomes apparent mostly after photobleaching of the majority of donors. Single molecule photon flux correlation measurements in combination with computer simulations and a variety of excitation conditions were used to determine the contribution of an exciton blockade to this two-color emission. Two-color defocused wide-field imaging showed that the two-color emission goes hand in hand with an unfavorable orientation between one of the donors and the acceptor chromophore.

  15. Probing the origin of excitonic states in monolayer WSe2

    PubMed Central

    Huang, Jiani; Hoang, Thang B.; Mikkelsen, Maiken H.

    2016-01-01

    Two-dimensional transition metal dichalcogenides (TMDCs) have spurred excitement for potential applications in optoelectronic and valleytronic devices; however, the origin of the dynamics of excitons, trions, and other localized states in these low dimensional materials is not well-understood. Here, we experimentally probed the dynamics of excitonic states in monolayer WSe2 by investigating the temperature and polarization dependent photoluminescence (PL) spectra. Four pronounced PL peaks were identified below a temperature of 60 K at near-resonant excitation and assigned to exciton, trion and localized states from excitation power dependence measurements. We find that the localized states vanish above 65 K, while exciton and trion emission peaks remain up to room temperature. This can be explained by a multi-level model developed for conventional semiconductors and applied to monolayer TMDCs for the first time here. From this model, we estimated a lower bound of the exciton binding energy of 198 meV for monolayer WSe2 and explained the vanishing of the localized states. Additionally, we observed a rapid decrease in the degree of circular polarization of the PL at increasing temperatures indicating a relatively strong electron-phonon coupling and impurity-related scattering. Our results reveal further insight into the excitonic states in monolayer WSe2 which is critical for future practical applications. PMID:26940069

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

    PubMed

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

    2013-10-23

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

  17. Photoluminescence study of Be acceptors in GaInNAs epilayers

    NASA Astrophysics Data System (ADS)

    Tsai, Y.; Barman, B.; Scrace, T.; Petrou, A.; Fukuda, M.; Sellers, I. R.; Leroux, M.; Khalfioui, M. A.

    2014-03-01

    We have studied the photoluminescence (PL) spectra from MBE grown GaInNAs epilayers doped p-type with Beryllium acceptors. The measurements were carried out in the 5 K - 70 K temperature range and in magnetic fields (B) up to 7 tesla. The PL spectra contain two features at T = 5 K: The exciton at 1093 meV and a second broader feature at 1058 meV. The intensity of this feature decreases with increasing temperature and disappears completely by 70K while the excitonic feature persists. The emission at 1058meV is identified as the conduction band to Beryllium acceptor transition. If we take into account the binding energy of the exciton [3] we get a value of 23 meV for the Beryllium acceptor binding energy. The acceptor related transition was studied as a function of magnetic field; the energy of this transition has a linear dependence on B with a slope of 055 meV/T. Research supported by Amethyst Research In. through the State of Oklahoma, ONAP program.

  18. Probing excitonic dark states in single-layer tungsten disulphide.

    PubMed

    Ye, Ziliang; Cao, Ting; O'Brien, Kevin; Zhu, Hanyu; Yin, Xiaobo; Wang, Yuan; Louie, Steven G; Zhang, Xiang

    2014-09-11

    Transition metal dichalcogenide (TMDC) monolayers have recently emerged as an important class of two-dimensional semiconductors with potential for electronic and optoelectronic devices. Unlike semi-metallic graphene, layered TMDCs have a sizeable bandgap. More interestingly, when thinned down to a monolayer, TMDCs transform from indirect-bandgap to direct-bandgap semiconductors, exhibiting a number of intriguing optical phenomena such as valley-selective circular dichroism, doping-dependent charged excitons and strong photocurrent responses. However, the fundamental mechanism underlying such a strong light-matter interaction is still under intensive investigation. First-principles calculations have predicted a quasiparticle bandgap much larger than the measured optical gap, and an optical response dominated by excitonic effects. In particular, a recent study based on a GW plus Bethe-Salpeter equation (GW-BSE) approach, which employed many-body Green's-function methodology to address electron-electron and electron-hole interactions, theoretically predicted a diversity of strongly bound excitons. Here we report experimental evidence of a series of excitonic dark states in single-layer WS2 using two-photon excitation spectroscopy. In combination with GW-BSE theory, we prove that the excitons are of Wannier type, meaning that each exciton wavefunction extends over multiple unit cells, but with extraordinarily large binding energy (∼0.7 electronvolts), leading to a quasiparticle bandgap of 2.7 electronvolts. These strongly bound exciton states are observed to be stable even at room temperature. We reveal an exciton series that deviates substantially from hydrogen models, with a novel energy dependence on the orbital angular momentum. These excitonic energy levels are experimentally found to be robust against environmental perturbations. The discovery of excitonic dark states and exceptionally large binding energy not only sheds light on the importance of many

  19. Valley excitons in two-dimensional semiconductors

    SciTech Connect

    Yu, Hongyi; Cui, Xiaodong; Xu, Xiaodong; Yao, Wang

    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 exhibit 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.

  20. 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

  1. Evidence of Hybrid Excitons in Weakly Interacting Nanopeapods

    PubMed Central

    2013-01-01

    Nanopeapods, consisting of optically active π-conjugated molecules encapsulated inside of the cavity of carbon nanotubes, exhibit efficient photon emission in the visible spectral range. Combining optical experiments with ab initio theory, we show that the puzzling features observed in photoluminescence spectra are of excitonic nature. The subunits though being van der Waals bound are demonstrated to interact in the excited state, giving rise to the formation of hybrid excitons. We rationalize why this many-body effect makes such nanohybrids useful for optoelectronic devices. PMID:23991266

  2. Photovoltaic properties of Au-merocyanine-TiO2 sandwich cells. II. Properties of illuminated cells and effects of doping with electron acceptors

    NASA Astrophysics Data System (ADS)

    Skotheim, T.; Yang, J.-M.; Otvos, J.; Klein, M. P.

    1982-12-01

    Photocurrent generation in thin films of a merocyanine photosensitizing dye sandwiched between a TiO2 single crystal doped n type and an Au overlayer has been studied using photovoltaic techniques. A theoretical model was developed to explain the observed photovoltaic properties. The model assumes that the principal route for the formation of charge carriers is via singlet excitons diffusing to the merocyanine-TiO2 interface followed by dissociation of the excitons into electron-hole pairs, the electrons being injected into the TiO2 conduction band and the holes into the merocyanine. The model also incorporates field dependence of the quantum efficiency for charge generation. An exciton diffusion length of 79 Å was determined by analyzing the short circuit action spectra using the theoretical model developed. The low fill factor of 0.35 for these cells was attributed to the field dependence of the quantum efficiency and the high series resistance of the undoped merocyanine films. Doping the merocyanine films with iodine was found to increase both the dark conductivity and the steady state photoconductivity, the latter by as much as a factor of 5. This resulted in a quantum yield of 12% for a 500 Å thick film and an increase in the fill factor to 0.44 giving a monochromatic power conversion efficiency of 0.4% at 520 nm. The carrier generation in iodine doped films is shown to result from a bulk process, possibly involving collisions between singlet excitons and acceptor-hole complexes resulting in activation out of the bound states formed by the charge-transfer complex. The quenching of excitons in the immediate vicinity of the metal surface was studied by monitoring the photoconductive response of a 200 Å merocyanine film with varying thickness of perylene sandwiched between the metal and the merocyanine. Perylene was shown to be able to transport the photoexcited holes from the merocyanine to the Au electrode. The quantum efficiency for photocarrier production

  3. PHOTOVOLTAIC PROPERTIES OF AU-MEROCYANINE-TiO2 SANDWICH CELLS. II. PROPERTIES OF ILLUMINATED CELLS AND EFFECTS OF DOPING WITH ELECTRON ACCEPTORS

    SciTech Connect

    Skotheim, T.; Yang, J.-M.; Otvos, J.; Klein, M.P.

    1980-07-01

    Photocurrent generation in thin films of a merocyanine photosensitizing dye sandwiched between a TiO{sub 2} single crystal doped n type and an Au overlayer has been studied using photovoltaic techniques. A theoretical model was developed to explain the observed photovoltaic properties. The model assumes that the principal route for the formation of charge carriers is via singlet excitons diffusing to the merocyanine - TiO{sub 2} interface followed by dissociation of the excitons into electron-hole pairs, the electrons being injected into the TiO{sub 2} conduction band and the holes into the merocyanine. The model also incorporates field dependence of the quantum efficiency for charge generation. An exciton diffusion length of 79 {angstrom} was determined by analyzing the short circuit action spectra using the theoretical model developed. The low fill factor of 0.35 for these cells was attributed to the field dependence of the quantum efficiency and the high series resistance of the undoped merocyanine films. Doping the merocyanine films with iodine was found to increase both the dark conductivity and the steady state photoconductivity, the latter by as much as a factor of 5. This resulted in a quantum yield of 12% for a 500 {angstrom} thick film and an increase in the fill factor to 0.44 giving a monochromatic power conversion efficiency of 0.4% at 520 nm. The carrier generation in iodine doped films is shown to result from a bulk process, possibly involving collisions between singlet excitons and acceptor-hole complexes resulting in activation out of the bound states formed by the charge-transfer complex. The quenching of excitons in the immediate vicinity of the metal surface was studied by monitoring the photoconductive response of a 200 {angstrom} merocyanine film with varying thickness of perylene sandwiched between the metal and the merocyanine. Perylene was shown to be able to transport the photoexcited holes from the merocyanine to the Au electrode. The

  4. Free Carrier Generation in Organic Photovoltaic Bulk Heterojunctions of Conjugated Polymers with Molecular Acceptors: Planar versus Spherical Acceptors

    SciTech Connect

    Nardes, Alexandre M.; Ferguson, Andrew J.; Wolfer, Pascal; Gui, Kurt; Burn, Paul L.; Meredith, Paul; Kopidakis, Nikos

    2014-03-05

    We present a comparative study of the photophysical performance of the prototypical fullerene derivative PC61BM with a planar small-molecule acceptor in an organic photovoltaic device. The small-molecule planar acceptor is 2-[{7-(9,9-di-n-propyl-9H-fluoren-2-yl)benzo[c][1,2,5]thiadiazol-4-yl}methylene]malononitrile, termed K12. We discuss photoinduced free charge-carrier generation and transport in blends of PC61BM or K12 with poly(3-n-hexylthiophene) (P3HT), surveying literature results for P3HT:PC61BM and presenting new results on P3HT:K12. For both systems we also review previous work on film structure and correlate the structural and photophysical results. In both cases, a disordered mixed phase is formed between P3HT and the acceptor, although the photophysical properties of this mixed phase differ markedly for PC61BM and K12. In the case of PC61BM the mixed phase acts as a free carrier generation region that can efficiently shuttle carriers to the pure polymer and fullerene domains. As a result, the vast majority of excitons quenched in P3HT:PC61BM blends yield free carriers detected by the contactless time-resolved microwave conductivity (TRMC) method. In contrast, approximately 85 % of the excitons quenched in P3HT:K12 do not result in free carriers over the nanosecond timescale of the TRMC experiment. We attribute this to poor electron-transport properties in the mixed P3HT:K12 phase. Here, we propose that the observed differences can be traced to the respective shapes of PC61BM and K12: the three-dimensional nature of the fullerene cage facilitates coupling between PC61BM molecules irrespective of their relative orientation, whereas for K12 strong electronic coupling is only expected for molecules oriented with their π systems parallel to each other. Comparison between the eutectic compositions of the P3HT:PC61BM and P3HT:K12 shows that the former contains enough fullerene to form a percolation pathway for electrons, whereas the latter contains a sub

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

    PubMed

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

    2013-06-18

    generated via singlet fission in pentacene can be dissociated at an interface with a suitable electron acceptor, such as fullerenes and infrared-absorbing inorganic semiconducting quantum dots. We highlight our recent reports of a pentacene/PbSe hybrid solar cell with a power conversion efficiency of 4.7% and of a pentacene/PbSe/amorphous silicon photovoltaic device. Although substantive challenges remain, both to better our understanding of the mechanism of singlet exciton fission and to optimize device performance, this realization of a solar cell where photocurrent is simultaneously contributed from a blue-absorbing fission-capable material and an infrared-absorbing conventional cell is an important step towards a dual-bandgap, single-junction, fission-enhanced photovoltaic device, which could one day surpass the Shockley-Queisser limit.

  6. Controlling exciton photophysics in single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Sarpkaya, Ibrahim

    Single-walled carbon nanotubes (SWCNTs) have been studied extensively by scientists and engineers due to their unique mechanical, optical, electronic and thermal properties that make them attractive for both fundamental research and device applications. Specifically, important optical properties of SWCNTs such as formation of strongly bound excitons (electron-hole pairs), being stable at room temperature, and bandgap-tunable light emission from visible to telecom wavelengths make them a promising material for optoelectronic and nanophotonic devices. However, the photophysics of excitons in SWCNTs is not yet fully understood and is largely affected by detrimental extrinsic effects, which give rise to strongly reduced device performance. This dissertation demonstrates novel methods and techniques to better understand and to control the photophysics of excitons in SWCNTs. The first part presents novel ways to completely remove detrimental spectral diffusion and blinking in the optical emission of surfactant dispersed SWCNTs on millisecond time scales and also demonstrates 50-fold enhanced exciton emission. Furthermore, pronounced photon antibunching is observed for the first time under resonant excitation. The demonstrated single photon emission is promising for applications in quantum cryptography, while the achieved stable long term emission is important for optoelectronic devices. The second part demonstrates a new regime of intrinsic exciton photophysics in ultra-clean SWCNTs that is characterized by ultra-narrow exciton linewidth and prolonged emission times up to 18 ns. These lifetimes are two orders of magnitude better than prior measurements and in agreement with values predicted by theorists a decade ago. Moreover, I measure for the first time exciton decoherence times of individual nanotubes in the time-domain and demonstrate fourfold prolonged values up to 2 ps compared to previous ensemble studies. Finally, I demonstrate a novel method which controls

  7. Reconfigurable exciton-plasmon interconversion for nanophotonic circuits.

    PubMed

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

    2016-11-28

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

  8. Reconfigurable exciton-plasmon interconversion for nanophotonic circuits

    PubMed Central

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

    2016-01-01

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

  9. Reconfigurable exciton-plasmon interconversion for nanophotonic circuits

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  10. Exciton diffusion, end quenching, and exciton-exciton annihilation in individual air-suspended carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Ishii, A.; Yoshida, M.; Kato, Y. K.

    2015-03-01

    Luminescence properties of carbon nanotubes are strongly affected by exciton diffusion, which plays an important role in various nonradiative decay processes. Here we perform photoluminescence microscopy on hundreds of individual air-suspended carbon nanotubes to elucidate the interplay between exciton diffusion, end quenching, and exciton-exciton annihilation processes. A model derived from random-walk theory as well as Monte Carlo simulations are utilized to analyze nanotube length dependence and excitation power dependence of emission intensity. We have obtained the values of exciton diffusion length and absorption cross section for different chiralities, and diameter-dependent photoluminescence quantum yields have been observed. The simulations have also revealed the nature of a one-dimensional coalescence process, and an analytical expression for the power dependence of emission intensity is given.

  11. Exciton transport, charge extraction, and loss mechanisms in organic photovoltaics

    NASA Astrophysics Data System (ADS)

    Scully, Shawn Ryan

    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.

  12. 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.

  13. A photoluminescence study of excitonic grade CuInSe{sub 2} single crystals irradiated with 6 MeV electrons

    SciTech Connect

    Yakushev, M. V.; Mudryi, A. V.; Borodavchenko, O. M.; Volkov, V. A.; Martin, R. W.

    2015-10-21

    High-quality single crystals of CuInSe{sub 2} with near-stoichiometric elemental compositions were irradiated with 6 MeV electrons, at doses from 10{sup 15} to 3 × 10{sup 18 }cm{sup −2}, and studied using photoluminescence (PL) at temperatures from 4.2 to 300 K. Before irradiation, the photoluminescence spectra reveal a number of sharp and well resolved lines associated with free- and bound-excitons. The spectra also show broader bands relating to free-to-bound transitions and their phonon replicas in the lower energy region below 1.0 eV. The irradiation with 6 MeV electrons reduces the intensity of the free- and the majority of the bound-exciton peaks. Such a reduction can be seen for doses above 10{sup 16 }cm{sup −2}. The irradiation induces new PL lines at 1.0215 eV and 0.9909 eV and also enhances the intensity of the lines at 1.0325 and 1.0102 eV present in the photoluminescence spectra before the irradiation. Two broad bands at 0.902 and 0.972 eV, respectively, are tentatively associated with two acceptor-type defects: namely, interstitial selenium (Se{sub i}) and copper on indium site (Cu{sub In}). After irradiation, these become more intense suggesting an increase in the concentration of these defects due to irradiation.

  14. A study of polaritonic transparency in couplers made from excitonic materials

    SciTech Connect

    Singh, Mahi R.; Racknor, Chris

    2015-03-14

    We have studied light matter interaction in quantum dot and exciton-polaritonic coupler hybrid systems. The coupler is made by embedding two slabs of an excitonic material (CdS) into a host excitonic material (ZnO). An ensemble of non-interacting quantum dots is doped in the coupler. The bound exciton polariton states are calculated in the coupler using the transfer matrix method in the presence of the coupling between the external light (photons) and excitons. These bound exciton-polaritons interact with the excitons present in the quantum dots and the coupler is acting as a reservoir. The Schrödinger equation method has been used to calculate the absorption coefficient in quantum dots. It is found that when the distance between two slabs (CdS) is greater than decay length of evanescent waves the absorption spectrum has two peaks and one minimum. The minimum corresponds to a transparent state in the system. However, when the distance between the slabs is smaller than the decay length of evanescent waves, the absorption spectra has three peaks and two transparent states. In other words, one transparent state can be switched to two transparent states when the distance between the two layers is modified. This could be achieved by applying stress and strain fields. It is also found that transparent states can be switched on and off by applying an external control laser field.

  15. Ultrafast exciton dissociation followed by nongeminate charge recombination in PCDTBT:PCBM photovoltaic blends.

    PubMed

    Etzold, Fabian; Howard, Ian A; Mauer, Ralf; Meister, Michael; Kim, Tae-Dong; Lee, Kwang-Sup; Baek, Nam Seob; Laquai, Frédéric

    2011-06-22

    The precise mechanism and dynamics of charge generation and recombination in bulk heterojunction polymer:fullerene blend films typically used in organic photovoltaic devices have been intensively studied by many research groups, but nonetheless remain debated. In particular the role of interfacial charge-transfer (CT) states in the generation of free charge carriers, an important step for the understanding of device function, is still under active discussion. In this article we present direct optical probes of the exciton dynamics in pristine films of a prototypic polycarbazole-based photovoltaic donor polymer, namely poly[N-11''-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), as well as the charge generation and recombination dynamics in as-cast and annealed photovoltaic blend films using methanofullerene (PC(61)BM) as electron acceptor. In contrast to earlier studies we use broadband (500-1100 nm) transient absorption spectroscopy including the previously unobserved but very important time range between 2 ns and 1 ms, which allows us not only to observe the entire charge carrier recombination dynamics but also to quantify the existing decay channels. We determine that ultrafast exciton dissociation occurs in blends and leads to two separate pools of products, namely Coulombically bound charge-transfer (CT) states and unbound (free) charge carriers. The recombination dynamics are analyzed within the framework of a previously reported model for poly(3-hexylthiophene):PCBM (Howard, I. A. J. Am. Chem. Soc. 2010, 132, 14866) based on concomitant geminate recombination of CT states and nongeminate recombination of free charge carriers. The results reveal that only ~11% of the initial photoexcitations generate interfacial CT states that recombine exclusively by fast nanosecond geminate recombination and thus do not contribute to the photocurrent, whereas ~89% of excitons create free charge carriers on an ultrafast time scale

  16. 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.

  17. Exciton migration in conjugated dendrimers: a joint experimental and theoretical study.

    PubMed

    Köse, Muhammet E; Graf, Peter; Kopidakis, Nikos; Shaheen, Sean E; Kim, Kwiseon; Rumbles, Garry

    2009-12-21

    We report a joint experimental and theoretical investigation of exciton diffusion in phenyl-cored thiophene dendrimers. Experimental exciton diffusion lengths of the dendrimers vary between 8 and 17 nm, increasing with the size of the dendrimer. A theoretical methodology is developed to estimate exciton diffusion lengths for conjugated small molecules in a simulated amorphous film. The theoretical approach exploits Fermi's Golden Rule to estimate the energy transfer rates for a large ensemble of bimolecular complexes in random relative orientations. Utilization of Poisson's equation in the evaluation of the Coulomb integral leads to very efficient calculation of excitonic couplings between the donor and the acceptor chromophores. Electronic coupling calculations with delocalized transition densities revealed efficient coupling pathways in the bulk of the material, but do not result in strong couplings between the chromophores which are calculated for more localized transition densities. The molecular structures of dendrimers seem to be playing a significant role in the magnitude of electronic coupling between chromophores. Simulated diffusion lengths correlate well with the experimental data. The chemical structure of the chromophore, the shape of the transition densities and the exciton lifetime are found to be the most important factors in determining the size of the exciton diffusion length in amorphous films of conjugated materials.

  18. Energy Migration in Organic Thin Films--From Excitons to Polarons

    NASA Astrophysics Data System (ADS)

    Mullenbach, Tyler K.

    The rise of organic photovoltaic devices (OPVs) and organic light-emitting devices has generated interest in the physics governing exciton and polaron dynamics in thin films. Energy transfer has been well studied in dilute solutions, but there are emergent properties in thin films and greater complications due to complex morphologies which must be better understood. Despite the intense interest in energy transport in thin films, experimental limitations have slowed discoveries. Here, a new perspective of OPV operation is presented where photovoltage, instead of photocurrent, plays the fundamental role. By exploiting this new vantage point the first method of measuring the diffusion length (LD) of dark (non-luminescent) excitons is developed, a novel photodetector is invented, and the ability to watch exciton arrival, in real-time, at the donor-acceptor heterojunction is presented. Using an enhanced understanding of exciton migration in thin films, paradigms for enhancing LD by molecular modifications are discovered, and the first exciton gate is experimentally and theoretically demonstrated. Generation of polarons from exciton dissociation represents a second phase of energy migration in OPVs that remains understudied. Current approaches are capable of measuring the rate of charge carrier recombination only at open-circuit. To enable a better understanding of polaron dynamics in thin films, two new approaches are presented which are capable of measuring both the charge carrier recombination and transit rates at any OPV operating voltage. These techniques pave the way for a more complete understanding of charge carrier kinetics in molecular thin films.

  19. Acceptor conductivity in bulk zinc oxide (0001) crystals

    NASA Astrophysics Data System (ADS)

    Adekore, Bababunmi Tolu

    ZnO is a promising wide bandgap semiconductor. Its renowned and prominent properties as its bandgap of 3.37eV at 4.2K; its very high excitonic binding energy, 60meV; its high melting temperature, 2248K constitute the basis for the recently renewed and sustained scientific interests in the material. In addition to the foregoing, the availability of bulk substrates of industrially relevant sizes provides important opportunities such as homoepitaxial deposition of the material which is a technological asset in the production of efficient optoelectronic and electronic devices. The nemesis of wide bandgap materials cannot be more exemplified than in ZnO. The notorious limitation of asymmetric doping and the haunting plague of electrically active point defects dim the bright future of the material. In this case, the search for reliable and consistent acceptor conductivity in bulk substrates has been hitherto, unsuccessful. In the dissertation that now follows, our efforts have been concerted in the search for a reliable acceptor. We have carefully investigated the science of point defects in the material, especially those responsible for the high donor conductivity. We also investigated and herein report variety of techniques of introducing acceptors into the material. We employ the most relevant and informative characterization techniques in verifying both the intended conductivity and the response of intrinsic crystals to variation in temperature and strain. And finally we explain deviations, where they exist, from ideal acceptor characteristics. Our work on reliable acceptor has been articulated in four papers. The first establishing capacitance based methods of monitoring electrically active donor defects. The second investigates the nature of anion acceptors on the oxygen sublattice. A study similar to the preceding study was conducted for cation acceptors on the zinc sublattice and reported in the third paper. Finally, an analysis of the response of the crystal to

  20. Bimolecular Recombination Kinetics of an Exciton-Trion Gas

    DTIC Science & Technology

    2015-07-01

    Coulomb radius” 2 / 4 0r q kTC = πεε as a boundary between Langevin’s carrier approach and the “ black hole ” where the carriers recombine. We plan to...describe kinetic processes in highly photoexcited semiconductors. In this description, the pairs of electrons and holes generated by photons from the...secondary components such as neutral excitons and so-called trions, which consist of exciton–electron and exciton– hole bound states. The

  1. Ultrafast Non-Förster Intramolecular Donor-Acceptor Excitation Energy Transfer.

    PubMed

    Athanasopoulos, Stavros; Alfonso Hernandez, Laura; Beljonne, David; Fernandez-Alberti, Sebastian; Tretiak, Sergei

    2017-04-06

    Ultrafast intramolecular electronic energy transfer in a conjugated donor-acceptor system is simulated using nonadiabatic excited-state molecular dynamics. After initial site-selective photoexcitation of the donor, transition density localization is monitored throughout the S2 → S1 internal conversion process, revealing an efficient unidirectional donor → acceptor energy-transfer process. Detailed analysis of the excited-state trajectories uncovers several salient features of the energy-transfer dynamics. While a weak temperature dependence is observed during the entire electronic energy relaxation, an ultrafast initially temperature-independent process allows the molecular system to approach the S2-S1 potential energy crossing seam within the first ten femtoseconds. Efficient energy transfer occurs in the absence of spectral overlap between the donor and acceptor units and is assisted by a transient delocalization phenomenon of the excited-state wave function acquiring Frenkel-exciton character at the moment of quantum transition.

  2. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

    DOE PAGES

    Yu M. Zhong; Nam, Chang -Yong; Trinh, M. Tuan; ...

    2015-09-18

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealedmore » both electron and hole transfer processes at the donor–acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. As a result, this study describes a new motif for designing highly efficient acceptors for organic solar cells.« less

  3. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Zhong, Yu; Trinh, M. Tuan; Chen, Rongsheng; Purdum, Geoffrey E.; Khlyabich, Petr P.; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Nam, Chang-Yong; Sfeir, Matthew Y.; Black, Charles T.; Steigerwald, Michael L.; Loo, Yueh-Lin; Ng, Fay; Zhu, X.-Y.; Nuckolls, Colin

    2015-09-01

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells.

  4. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells.

    PubMed

    Zhong, Yu; Trinh, M Tuan; Chen, Rongsheng; Purdum, Geoffrey E; Khlyabich, Petr P; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Nam, Chang-Yong; Sfeir, Matthew Y; Black, Charles T; Steigerwald, Michael L; Loo, Yueh-Lin; Ng, Fay; Zhu, X-Y; Nuckolls, Colin

    2015-09-18

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells.

  5. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

    SciTech Connect

    Yu M. Zhong; Nam, Chang -Yong; Trinh, M. Tuan; Chen, Rongsheng; Purdum, Geoffrey E.; Khlyabich, Petr P.; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Sfeir, Matthew Y.; Black, Charles T.; Steigerwald, Michael L.; Loo, Yueh -Lin; Ng, Fay; Zhu, X. -Y.; Nuckolls, Colin

    2015-09-18

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor–acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. As a result, this study describes a new motif for designing highly efficient acceptors for organic solar cells.

  6. Direct Observation of Ultrafast Exciton Formation in a Monolayer of WSe2.

    PubMed

    Steinleitner, Philipp; Merkl, Philipp; Nagler, Philipp; Mornhinweg, Joshua; Schüller, Christian; Korn, Tobias; Chernikov, Alexey; Huber, Rupert

    2017-03-08

    Many of the fundamental optical and electronic properties of atomically thin transition metal dichalcogenides are dominated by strong Coulomb interactions between electrons and holes, forming tightly bound atom-like states called excitons. Here, we directly trace the ultrafast formation of excitons by monitoring the absolute densities of bound and unbound electron-hole pairs in single monolayers of WSe2 on a diamond substrate following femtosecond nonresonant optical excitation. To this end, phase-locked mid-infrared probe pulses and field-sensitive electro-optic sampling are used to map out the full complex-valued optical conductivity of the nonequilibrium system and to discern the hallmark low-energy responses of bound and unbound pairs. While the spectral shape of the infrared response immediately after above-bandgap injection is dominated by free charge carriers, up to 60% of the electron-hole pairs are bound into excitons already on a subpicosecond time scale, evidencing extremely fast and efficient exciton formation. During the subsequent recombination phase, we still find a large density of free carriers in addition to excitons, indicating a nonequilibrium state of the photoexcited electron-hole system.

  7. Photosynthetic light harvesting: excitons and coherence

    PubMed Central

    Fassioli, Francesca; Dinshaw, Rayomond; Arpin, Paul C.; Scholes, Gregory D.

    2014-01-01

    Photosynthesis begins with light harvesting, where specialized pigment–protein complexes transform sunlight into electronic excitations delivered to reaction centres to initiate charge separation. There is evidence that quantum coherence between electronic excited states plays a role in energy transfer. In this review, we discuss how quantum coherence manifests in photosynthetic light harvesting and its implications. We begin by examining the concept of an exciton, an excited electronic state delocalized over several spatially separated molecules, which is the most widely available signature of quantum coherence in light harvesting. We then discuss recent results concerning the possibility that quantum coherence between electronically excited states of donors and acceptors may give rise to a quantum coherent evolution of excitations, modifying the traditional incoherent picture of energy transfer. Key to this (partially) coherent energy transfer appears to be the structure of the environment, in particular the participation of non-equilibrium vibrational modes. We discuss the open questions and controversies regarding quantum coherent energy transfer and how these can be addressed using new experimental techniques. PMID:24352671

  8. Acceptors in ZnO

    SciTech Connect

    Mccluskey, Matthew D.; Corolewski, Caleb; Lv, Jinpeng; Tarun, Marianne C.; Teklemichael, Samuel T.; Walter, Eric D.; Norton, M. G.; Harrison, Kale W.; Ha, Su Y.

    2015-03-21

    Zinc oxide (ZnO) has potential for a range of applications in the area of optoelectronics. The quest for p-type ZnO has focused much attention on acceptors. In this paper, Cu, N, and Li acceptor impurities are discussed. Experimental evidence shows that these point defects have acceptor levels 3.2, 1.5, and 0.8 eV above the valence-band maximum, respectively. The levels are deep because the ZnO valence band is quite low compared to conventional, non-oxide semiconductors. Using MoO2 contacts, the electrical resistivity of ZnO:Li was measured and showed behavior consistent with bulk hole conduction for temperatures above 400 K. A photoluminescence peak in ZnO nanocrystals has been attributed to an acceptor, which may involve a zinc vacancy. High field (W-band) electron paramagnetic resonance measurements on the nanocrystals revealed an axial center with g = 2.0033 and g = 2.0075, along with an isotropic center at g = 2.0053.

  9. Acceptors in ZnO

    SciTech Connect

    McCluskey, Matthew D. Corolewski, Caleb D.; Lv, Jinpeng; Tarun, Marianne C.; Teklemichael, Samuel T.; Walter, Eric D.; Norton, M. Grant; Harrison, Kale W.; Ha, Su

    2015-03-21

    Zinc oxide (ZnO) has potential for a range of applications in the area of optoelectronics. The quest for p-type ZnO has focused much attention on acceptors. In this paper, Cu, N, and Li acceptor impurities are discussed. Experimental evidence indicates these point defects have acceptor levels 3.2, 1.4, and 0.8 eV above the valence-band maximum, respectively. The levels are deep because the ZnO valence band is quite low compared to conventional, non-oxide semiconductors. Using MoO{sub 2} contacts, the electrical resistivity of ZnO:Li was measured and showed behavior consistent with bulk hole conduction for temperatures above 400 K. A photoluminescence peak in ZnO nanocrystals is attributed to an acceptor, which may involve a Zn vacancy. High field (W-band) electron paramagnetic resonance measurements on the nanocrystals revealed an axial center with g{sub ⊥} = 2.0015 and g{sub //} = 2.0056, along with an isotropic center at g = 2.0035.

  10. Exciton dispersion in molecular solids.

    PubMed

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

    2015-03-25

    The investigation of the exciton dispersion (i.e. the exciton energy dependence as a function of the momentum carried by the electron-hole pair) is a powerful approach to identify the exciton character, ranging from the strongly localised Frenkel to the delocalised Wannier-Mott limiting cases. We illustrate this possibility at the example of four prototypical molecular solids (picene, pentacene, tetracene and coronene) on the basis of the parameter-free solution of the many-body Bethe-Salpeter equation. We discuss the mixing between Frenkel and charge-transfer excitons and the origin of their Davydov splitting in the framework of many-body perturbation theory and establish a link with model approaches based on molecular states. Finally, we show how the interplay between the electronic band dispersion and the exchange electron-hole interaction plays a fundamental role in setting the nature of the exciton. This analysis has a general validity holding also for other systems in which the electron wavefunctions are strongly localized, as in strongly correlated insulators.

  11. Exciton dispersion in molecular solids

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    The investigation of the exciton dispersion (i.e. the exciton energy dependence as a function of the momentum carried by the electron-hole pair) is a powerful approach to identify the exciton character, ranging from the strongly localised Frenkel to the delocalised Wannier-Mott limiting cases. We illustrate this possibility at the example of four prototypical molecular solids (picene, pentacene, tetracene and coronene) on the basis of the parameter-free solution of the many-body Bethe-Salpeter equation. We discuss the mixing between Frenkel and charge-transfer excitons and the origin of their Davydov splitting in the framework of many-body perturbation theory and establish a link with model approaches based on molecular states. Finally, we show how the interplay between the electronic band dispersion and the exchange electron-hole interaction plays a fundamental role in setting the nature of the exciton. This analysis has a general validity holding also for other systems in which the electron wavefunctions are strongly localized, as in strongly correlated insulators.

  12. Tuning excitons in monolayer and few-layer MoS2

    NASA Astrophysics Data System (ADS)

    Qiu, Diana Y.; da Jornada, Felipe H.; Louie, Steven G.

    2014-03-01

    Our recent ab initio GW-BSE calculations showed that monolayer MoS2 is a computationally challenging system, requiring a large number of empty bands and very fine k-point sampling to converge its quasiparticle band structure and optical properties. Careful convergence of a GW-BSE calculation reveals that MoS2 has a large number of bound excitons with varying k-space characteristics. Specifically, there are two series of excitons: a low-energy series with k-space wavefunctions localized at the K/K' valleys in the Brillouin zone and a higher energy series localized in a ring around the Γ point. There is very little hybridization between these two exciton series in monolayer MoS2, but changes in electronic structure and screening due to additional layers, strain, or doping can lead to changes in exciton binding energies, character, and hybridization. Thus, we have carried out ab initio GW-BSE calculations to study the excitonic properties of few-layer MoS2. We find that layering and straining MoS2 systematically changes the exciton binding energies, the peak positions and amount of absorbance in the optical spectrum, and the character and hybridization of the excitons near Γ. This work was supported by NSF grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231.

  13. Dynamical reconstruction of the exciton in LiF with inelastic x-ray scattering

    SciTech Connect

    Abbamonte, Peter; Graber, Tim; Reed, James P.; Smadici, Serban; Yeh, Chen-Lin; Shukla, Abhay; Rueff, Jean-Pascal; Ku, Wei

    2008-11-03

    The absorption of light by materials proceeds through the formation of excitons, which are states in which an excited electron is bound to the valence hole it vacated. Understanding the structure and dynamics of excitons is important, for example, for developing technologies for light-emitting diodes or solar energy conversion. However, there has never been an experimental means to study the time-dependent structure of excitons directly. Here, we use causality-inverted inelastic x-ray scattering (IXS) to image the charge-transfer exciton in the prototype insulator LiF, with resolutions {Delta}t = 20.67 as (2.067 x 10{sup -17} s) in time and {Delta}x = 0.533 {angstrom} (5.33 x 10{sup -11} m) in space. Our results show that the exciton has a modulated internal structure and is coherently delocalized over two unit cells of the LiF crystal ({approx}8 {angstrom}). This structure changes only modestly during the course of its life, which establishes it unambiguously as a Frenkel exciton and thus amenable to a simplified theoretical description. Our results resolve an old controversy about excitons in the alkali halides and demonstrate the utility of IXS for imaging attosecond electron dynamics in condensed matter.

  14. An Infinite Order Discrete Variable Representation of an Effective Mass Hamiltonian: Application to Exciton Wave Functions in Quantum Confined Nanostructures.

    PubMed

    Kaledin, Alexey L; Lian, Tianquan; Hill, Craig L; Musaev, Djamaladdin G

    2014-08-12

    We describe an extension of the conventional Fourier grid discrete variable representation (DVR) to the bound state problem of a particle with a position-dependent mass. An infinite order DVR, derived for a variable mass kinetic energy operator, coupled with an efficient grid contraction scheme yields essentially exact eigenvalues for a chosen grid spacing. Implementation of the method is shown to be very practical due to the fact that in a DVR no integral evaluation is necessary and that the resultant kinetic energy matrix is sparse. Numerical calculations are presented for exciton states of spherical, cylindrical, and toric Type I (CdSe/ZnS) core-shell quantum dots. In these examples, electron-hole interaction is treated explicitly by solving a self-consistent Schrödinger-Poisson equation on a contracted DVR grid. Prospective applications of the developed approach to calculating electron transfer rates between adsorbed molecular acceptors and quantum confined nanocrystals of generic shape, dimensionality, and composition are also discussed.

  15. 8.4% efficient fullerene-free organic solar cells exploiting long-range exciton energy transfer.

    PubMed

    Cnops, Kjell; Rand, Barry P; Cheyns, David; Verreet, Bregt; Empl, Max A; Heremans, Paul

    2014-03-07

    In order to increase the power conversion efficiency of organic solar cells, their absorption spectrum should be broadened while maintaining efficient exciton harvesting. This requires the use of multiple complementary absorbers, usually incorporated in tandem cells or in cascaded exciton-dissociating heterojunctions. Here we present a simple three-layer architecture comprising two non-fullerene acceptors and a donor, in which an energy-relay cascade enables an efficient two-step exciton dissociation process. Excitons generated in the remote wide-bandgap acceptor are transferred by long-range Förster energy transfer to the smaller-bandgap acceptor, and subsequently dissociate at the donor interface. The photocurrent originates from all three complementary absorbing materials, resulting in a quantum efficiency above 75% between 400 and 720 nm. With an open-circuit voltage close to 1 V, this leads to a remarkable power conversion efficiency of 8.4%. These results confirm that multilayer cascade structures are a promising alternative to conventional donor-fullerene organic solar cells.

  16. Novel Exciton States in Monolayer MoS2: Unconventional Effective Hamiltonian

    NASA Astrophysics Data System (ADS)

    da Jornada, Felipe; Qiu, Diana; Louie, Steven

    2014-03-01

    Recent well-converged ab inito GW-BSE calculations show that monolayer MoS2 has a large number of strongly bound excitons with varying characters. We show that these excitonic states cannot be even qualitatively described by an effective mass hydrogenic model without a detailed understanding of the 2D screening. Additionally, we identify and analyze one exciton series having an unusually high binding energy, which originates around the Γ point of the Brillouin zone. We show that this excitonic series arises from a fundamentally different effective Hamiltonian with a kinetic energy term resembling a Mexican hat in momentum space, which is responsible for the unusual ordering of the energy levels and distribution of oscillator strength. This work was supported by NSF grant No. DMR10-1006184 and the U.S. DOE under Contract No. DE-AC02-05CH11231.

  17. Excitonic polaritons in Fibonacci quasicrystals.

    PubMed

    Hendrickson, J; Richards, B C; Sweet, J; Khitrova, G; Poddubny, A N; Ivchenko, E L; Wegener, M; Gibbs, H M

    2008-09-29

    The fabrication and characterization of light-emitting one-dimensional photonic quasicrystals based on excitonic resonances is reported. The structures consist of high-quality GaAs/AlGaAs quantum wells grown by molecular-beam epitaxy with wavelength-scale spacings satisfying a Fibonacci sequence. The polaritonic (resonant light-matter coupling) effects and light emission originate from the quantum well excitonic resonances. Measured reflectivity spectra as a function of detuning between emission and Bragg wavelength are in good agreement with excitonic polariton theory. Photoluminescence experiments show that active photonic quasicrystals, unlike photonic crystals, can be good light emitters: While their long-range order results in a stopband similar to that of photonic crystals, the lack of periodicity results in strong emission.

  18. 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

  19. Excitons in a mirror: Formation of “optical bilayers” using MoS{sub 2} monolayers on gold substrates

    SciTech Connect

    Mertens, Jan; Baumberg, Jeremy J.; Shi, Yumeng; Yang, Hui Ying; Molina-Sánchez, Alejandro; Wirtz, Ludger

    2014-05-12

    We report coupling of excitons in monolayers of molybdenum disulphide to their mirror image in an underlying gold substrate. Excitons at the direct band gap are little affected by the substrate whereas strongly bound C-excitons associated with a van-Hove singularity change drastically. On quartz substrates only one C-exciton is visible (in the blue) but on gold substrates a strong red-shifted extra resonance in the green is seen. Exciton coupling to its image leads to formation of a “mirror biexciton” with enhanced binding energy. Estimates of this energy shift in an emitter-gold system match experiments well. The absorption spectrum of MoS{sub 2} on gold thus resembles a bilayer of MoS{sub 2} which has been created by optical coupling. Additional top-mirrors produce an “optical bulk.”.

  20. Tuning the driving force for exciton dissociation in single-walled carbon nanotube heterojunctions

    NASA Astrophysics Data System (ADS)

    Ihly, Rachelle; Mistry, Kevin S.; Ferguson, Andrew J.; Clikeman, Tyler T.; Larson, Bryon W.; Reid, Obadiah; Boltalina, Olga V.; Strauss, Steven H.; Rumbles, Garry; Blackburn, Jeffrey L.

    2016-06-01

    Understanding the kinetics and energetics of interfacial electron transfer in molecular systems is crucial for the development of a broad array of technologies, including photovoltaics, solar fuel systems and energy storage. The Marcus formulation for electron transfer relates the thermodynamic driving force and reorganization energy for charge transfer between a given donor/acceptor pair to the kinetics and yield of electron transfer. Here we investigated the influence of the thermodynamic driving force for photoinduced electron transfer (PET) between single-walled carbon nanotubes (SWCNTs) and fullerene derivatives by employing time-resolved microwave conductivity as a sensitive probe of interfacial exciton dissociation. For the first time, we observed the Marcus inverted region (in which driving force exceeds reorganization energy) and quantified the reorganization energy for PET for a model SWCNT/acceptor system. The small reorganization energies (about 130 meV, most of which probably arises from the fullerene acceptors) are beneficial in minimizing energy loss in photoconversion schemes.

  1. Tuning the driving force for exciton dissociation in single-walled carbon nanotube heterojunctions

    SciTech Connect

    Ihly, Rachelle; Mistry, Kevin S.; Ferguson, Andrew J.; Clikeman, Tyler T.; Larson, Bryon W.; Reid, Obadiah; Boltalina, Olga V.; Strauss, Steven H.; Rumbles, Garry; Blackburn, Jeffrey L.

    2016-04-25

    Understanding the kinetics and energetics of interfacial electron transfer in molecular systems is crucial for the development of a broad array of technologies, including photovoltaics, solar fuel systems and energy storage. The Marcus formulation for electron transfer relates the thermodynamic driving force and reorganization energy for charge transfer between a given donor/acceptor pair to the kinetics and yield of electron transfer. Here we investigated the influence of the thermodynamic driving force for photoinduced electron transfer (PET) between single-walled carbon nanotubes (SWCNTs) and fullerene derivatives by employing time-resolved microwave conductivity as a sensitive probe of interfacial exciton dissociation. For the first time, we observed the Marcus inverted region (in which driving force exceeds reorganization energy) and quantified the reorganization energy for PET for a model SWCNT/acceptor system. The small reorganization energies (about 130 meV, most of which probably arises from the fullerene acceptors) are beneficial in minimizing energy loss in photoconversion schemes.

  2. Multiple exciton collection in a sensitized photovoltaic system.

    PubMed

    Sambur, Justin B; Novet, Thomas; Parkinson, B A

    2010-10-01

    Multiple exciton generation, the creation of two electron-hole pairs from one high-energy photon, is well established in bulk semiconductors, but assessments of the efficiency of this effect remain controversial in quantum-confined systems like semiconductor nanocrystals. We used a photoelectrochemical system composed of PbS nanocrystals chemically bound to TiO(2) single crystals to demonstrate the collection of photocurrents with quantum yields greater than one electron per photon. The strong electronic coupling and favorable energy level alignment between PbS nanocrystals and bulk TiO(2) facilitate extraction of multiple excitons more quickly than they recombine, as well as collection of hot electrons from higher quantum dot excited states. Our results have implications for increasing the efficiency of photovoltaic devices by avoiding losses resulting from the thermalization of photogenerated carriers.

  3. Measurement of exciton correlations using electrostatic lattices

    NASA Astrophysics Data System (ADS)

    Remeika, M.; Leonard, J. R.; Dorow, C. J.; Fogler, M. M.; Butov, L. V.; Hanson, M.; Gossard, A. C.

    2015-09-01

    We present a method for determining correlations in a gas of indirect excitons in a semiconductor quantum well structure. The method involves subjecting the excitons to a periodic electrostatic potential that causes modulations of the exciton density and photoluminescence (PL). Experimentally measured amplitudes of energy and intensity modulations of exciton PL serve as an input to a theoretical estimate of the exciton correlation parameter and temperature. We also present a proof-of-principle demonstration of the method for determining the correlation parameter and discuss how its accuracy can be improved.

  4. 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.

  5. Exciton size and quantum transport in nanoplatelets

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  6. Exciton size and quantum transport in nanoplatelets

    SciTech Connect

    Pelzer, Kenley M. Gray, Stephen K.; Darling, Seth B.; 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.

  7. Excitonic effects in two-dimensional semiconductors: Path integral Monte Carlo approach

    SciTech Connect

    Velizhanin, Kirill A.; Saxena, Avadh

    2015-11-01

    The most striking features of novel two-dimensional semiconductors (e.g., transition metal dichalcogenide monolayers or phosphorene) is a strong Coulomb interaction between charge carriers resulting in large excitonic effects. In particular, this leads to the formation of multicarrier bound states upon photoexcitation (e.g., excitons, trions, and biexcitons), which could remain stable at near-room temperatures and contribute significantly to the optical properties of such materials. In our work we have used the path integral Monte Carlo methodology to numerically study properties of multicarrier bound states in two-dimensional semiconductors. Specifically, we have accurately investigated and tabulated the dependence of single-exciton, trion, and biexciton binding energies on the strength of dielectric screening, including the limiting cases of very strong and very weak screening. Our results of this work are potentially useful in the analysis of experimental data and benchmarking of theoretical and computational models.

  8. Excitonic effects in two-dimensional semiconductors: Path integral Monte Carlo approach

    DOE PAGES

    Velizhanin, Kirill A.; Saxena, Avadh

    2015-11-01

    The most striking features of novel two-dimensional semiconductors (e.g., transition metal dichalcogenide monolayers or phosphorene) is a strong Coulomb interaction between charge carriers resulting in large excitonic effects. In particular, this leads to the formation of multicarrier bound states upon photoexcitation (e.g., excitons, trions, and biexcitons), which could remain stable at near-room temperatures and contribute significantly to the optical properties of such materials. In our work we have used the path integral Monte Carlo methodology to numerically study properties of multicarrier bound states in two-dimensional semiconductors. Specifically, we have accurately investigated and tabulated the dependence of single-exciton, trion, and biexcitonmore » binding energies on the strength of dielectric screening, including the limiting cases of very strong and very weak screening. Our results of this work are potentially useful in the analysis of experimental data and benchmarking of theoretical and computational models.« less

  9. 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

  10. Spatially indirect excitons in coupled quantum wells

    SciTech Connect

    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 opportunities 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

  11. Effective tight-binding models for excitons in branched conjugated molecules

    NASA Astrophysics Data System (ADS)

    Li, Hao; Malinin, Sergey V.; Tretiak, Sergei; Chernyak, Vladimir Y.

    2013-08-01

    Effective tight-binding models have been introduced to describe vertical electronic excitations in branched conjugated molecules. The excited-state electronic structure is characterized by quantum particles (excitons) that reside on an irregular lattice (graph) that reflects the molecular structure. The methodology allows for the exciton spectra and energy-dependent exciton scattering matrices to be described in terms of a small number of lattice parameters which can be obtained from quantum-chemical computations using the exciton scattering approach as a tool. We illustrate the tight-binding model approach using the time-dependent Hartree-Fock computations in phenylacetylene oligomers. The on-site energies and hopping constants have been identified from the exciton dispersion and scattering matrices. In particular, resonant, as well as bound states, are reproduced for a symmetric quadruple branching center. The capability of the tight-binding model approach to describe the exciton-phonon coupling and energetic disorder in large branched conjugated molecules is briefly discussed.

  12. Probing excitonic states in suspended two-dimensional semiconductors by photocurrent spectroscopy

    NASA Astrophysics Data System (ADS)

    Klots, A. R.; Newaz, A. K. M.; Wang, Bin; Prasai, D.; Krzyzanowska, H.; Lin, Junhao; Caudel, D.; Ghimire, N. J.; Yan, J.; Ivanov, B. L.; Velizhanin, K. A.; Burger, A.; Mandrus, D. G.; Tolk, N. H.; Pantelides, S. T.; Bolotin, K. I.

    2014-10-01

    The optical response of semiconducting monolayer transition-metal dichalcogenides (TMDCs) is dominated by strongly bound excitons that are stable even at room temperature. However, substrate-related effects such as screening and disorder in currently available specimens mask many anticipated physical phenomena and limit device applications of TMDCs. Here, we demonstrate that that these undesirable effects are strongly suppressed in suspended devices. Extremely robust (photogain > 1,000) and fast (response time < 1 ms) photoresponse allow us to study, for the first time, the formation, binding energies, and dissociation mechanisms of excitons in TMDCs through photocurrent spectroscopy. By analyzing the spectral positions of peaks in the photocurrent and by comparing them with first-principles calculations, we obtain binding energies, band gaps and spin-orbit splitting in monolayer TMDCs. For monolayer MoS2, in particular, we obtain an extremely large binding energy for band-edge excitons, Ebind >= 570 meV. Along with band-edge excitons, we observe excitons associated with a van Hove singularity of rather unique nature. The analysis of the source-drain voltage dependence of photocurrent spectra reveals exciton dissociation and photoconversion mechanisms in TMDCs.

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

    NASA Astrophysics Data System (ADS)

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

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

  14. Ultrafast formation of interlayer hot excitons in atomically thin MoS2/WS2 heterostructures

    PubMed Central

    Chen, Hailong; Wen, Xiewen; Zhang, Jing; Wu, Tianmin; Gong, Yongji; Zhang, Xiang; Yuan, Jiangtan; Yi, Chongyue; Lou, Jun; Ajayan, Pulickel M.; Zhuang, Wei; Zhang, Guangyu; Zheng, Junrong

    2016-01-01

    Van der Waals heterostructures composed of two-dimensional transition-metal dichalcogenides layers have recently emerged as a new family of materials, with great potential for atomically thin opto-electronic and photovoltaic applications. It is puzzling, however, that the photocurrent is yielded so efficiently in these structures, despite the apparent momentum mismatch between the intralayer/interlayer excitons during the charge transfer, as well as the tightly bound nature of the excitons in 2D geometry. Using the energy-state-resolved ultrafast visible/infrared microspectroscopy, we herein obtain unambiguous experimental evidence of the charge transfer intermediate state with excess energy, during the transition from an intralayer exciton to an interlayer exciton at the interface of a WS2/MoS2 heterostructure, and free carriers moving across the interface much faster than recombining into the intralayer excitons. The observations therefore explain how the remarkable charge transfer rate and photocurrent generation are achieved even with the aforementioned momentum mismatch and excitonic localization in 2D heterostructures and devices. PMID:27539942

  15. Probing excitonic states in suspended two-dimensional semiconductors by photocurrent spectroscopy

    SciTech Connect

    Klots, A. R.; Newaz, A. K. M.; Wang, Bin; Prasai, D.; Krzyzanowska, H.; Lin, Junhao; Caudel, D.; Ghimire, N. J.; Yan, J.; Ivanov, B. L.; Velizhanin, K. A.; Burger, A.; Mandrus, D. G.; Tolk, N. H.; Pantelides, S. T.; Bolotin, K. I.

    2014-10-16

    The optical response of semiconducting monolayer transition-metal dichalcogenides (TMDCs) is dominated by strongly bound excitons that are stable even at room temperature. However, substrate-related effects such as screening and disorder in currently available specimens mask many anticipated physical phenomena and limit device applications of TMDCs. Here, we demonstrate that that these undesirable effects are strongly suppressed in suspended devices. Extremely robust (photogain > 1,000) and fast (response time < 1 ms) photoresponse allow us to study, for the first time, the formation, binding energies, and dissociation mechanisms of excitons in TMDCs through photocurrent spectroscopy. By analyzing the spectral positions of peaks in the photocurrent and by comparing them with first-principles calculations, we obtain binding energies, band gaps and spin-orbit splitting in monolayer TMDCs. For monolayer MoS2, in particular, we obtain an extremely large binding energy for band-edge excitons, Ebind ≥ 570 meV. Along with band-edge excitons, we observe excitons associated with a van Hove singularity of rather unique nature. In conclusion, the analysis of the source-drain voltage dependence of photocurrent spectra reveals exciton dissociation and photoconversion mechanisms in TMDCs.

  16. Probing excitonic states in suspended two-dimensional semiconductors by photocurrent spectroscopy

    DOE PAGES

    Klots, A. R.; Newaz, A. K. M.; Wang, Bin; ...

    2014-10-16

    The optical response of semiconducting monolayer transition-metal dichalcogenides (TMDCs) is dominated by strongly bound excitons that are stable even at room temperature. However, substrate-related effects such as screening and disorder in currently available specimens mask many anticipated physical phenomena and limit device applications of TMDCs. Here, we demonstrate that that these undesirable effects are strongly suppressed in suspended devices. Extremely robust (photogain > 1,000) and fast (response time < 1 ms) photoresponse allow us to study, for the first time, the formation, binding energies, and dissociation mechanisms of excitons in TMDCs through photocurrent spectroscopy. By analyzing the spectral positions ofmore » peaks in the photocurrent and by comparing them with first-principles calculations, we obtain binding energies, band gaps and spin-orbit splitting in monolayer TMDCs. For monolayer MoS2, in particular, we obtain an extremely large binding energy for band-edge excitons, Ebind ≥ 570 meV. Along with band-edge excitons, we observe excitons associated with a van Hove singularity of rather unique nature. In conclusion, the analysis of the source-drain voltage dependence of photocurrent spectra reveals exciton dissociation and photoconversion mechanisms in TMDCs.« less

  17. Contrastive analysis of multiple exciton generation theories

    NASA Astrophysics Data System (ADS)

    Tan, Hengyu; Chang, Qing

    2015-10-01

    Multiple exciton generation (MEG) is an effect that semiconductor nanocrystals (NCs) quantum dots (QDs) generate multiple excitons (electron-hole pairs) through absorbing a single high energy photon. It can translate the excess photon energy of bandgap (Eg) into new excitons instead of heat loss and improve the photovoltaic performance of solar cells. However, the theories of MEG are not uniform. The main MEG theories can be divided into three types. The first is impact ionization. It explains MEG through a conventional way that a photogenerated exciton becomes multiple excitons by Coulomb interactions between carriers. The Second is coherent superposition of excitonic states. Multiple excitons are generated by the coherent superposition of single photogenerated exciton state with enough excess momentum and the two-exciton state with the same momentum. The third is excitation via virtual excitonic states. The nanocrystals vacuum generates a virtual biexciton by coulomb coupling between two valence band electrons. The virtual biexciton absorbing a photon with an intraband optical transition is converted into a real biexciton. This paper describes the MEG influence on solar photoelectric conversion efficiency, concludes and analyzes the fundamentals of different MEG theories, the MEG experimental measure, their merits and demerits, calculation methods of generation efficiency.

  18. Electronic structure disorder, vibronic coupling, and charge transfer excitons in poly(fluorene-alt-bithiophene):fullerene films

    SciTech Connect

    Riisness, I.; Gordon, M. J.

    2013-03-18

    Charge transfer processes in conjugated polymer:fullerene blends play an important role in the operation of organic solar cells and organic light emitting diodes. Herein, near-infrared emission from poly-(9,9-dioctylfluorene-alt-bithiophene) (F8T2) and [6,6]-phenyl-C{sub 61}-butyric acid methyl ester blends was studied and attributed to charge transfer exciton (CTX) recombination. Polymer and CTX emission were monitored via low-temperature/transient photoluminescence and absorbance to elucidate the effects of annealing and composition on donor-acceptor morphology. CTX emission decreased and F8T2 vibronic structure was partially restored due to lower fullerene dispersion and polymer realignment upon annealing. Differences in the temperature-dependent emissions of the polymer singlet vs. CTX were attributed to exciton diffusion in the polymer phase vs. enhanced quenching at the donor-acceptor interface, respectively.

  19. Reduced exchange narrowing caused by gate-induced charge carriers in high-mobility donor-acceptor copolymers

    NASA Astrophysics Data System (ADS)

    Tsutsumi, Jun'ya; Matsuoka, Satoshi; Osaka, Itaru; Kumai, Reiji; Hasegawa, Tatsuo

    2017-03-01

    Variations in exciton absorption resulting from charge accumulation in various semiconducting donor-acceptor (DA) copolymer thin films were systematically investigated by gate modulation (GM) spectroscopy by using the field-effect transistor device structure. The GM spectra obtained for high-mobility DA copolymer thin films exhibited second-derivative like line shapes due to an effect of spectral broadening of ordinary exciton absorption spectra by accumulated charges. In contrast, the GM spectra obtained for relatively low-mobility DA copolymer thin films exhibited simple bleaching of exciton absorption spectra, as well as observed for non-DA-type polymers like poly(3-hexylthiophene-2,5-diyl) (P3HT). From a systematic comparison of the GM spectra with temperature-dependent absorption spectra for the polymers in solution, we found that the spectral broadening observed in the GM spectra can be attributed to a reduced effect on the exchange narrowing where excitonic transitions of individual polymer chains are coherently coupled within highly ordered crystalline domains in the polymer thin films. We discuss that the gate-induced charge accumulation in the polymer films effects to suppress the exciton coherence length, which contributes to the reduced exchange narrowing. We also discuss that the whole feature of the GM spectra can be understood in terms of a decomposition into ordered and disordered polymers and that the GM spectra can be used as fine probes for a degree of structural ordering in semiconductor channels of polymer field-effect transistors.

  20. Exciton-polariton integrated circuits

    NASA Astrophysics Data System (ADS)

    Liew, T. C. H.; Kavokin, A. V.; Ostatnický, T.; Kaliteevski, M.; Shelykh, I. A.; Abram, R. A.

    2010-07-01

    We show that logical signals encoded in bistable states in semiconductor microcavities can be generated and controlled electronically by exploiting the electrical sensitivity of Tamm-plasmon-exciton-polariton modes. The signals can be transported along polariton neurons, created with a patterned metal surface. Using the Gross-Pitaevskii equations, we simulate an electrically controlled transistor and find that high repetition rates (10 GHz) are possible.

  1. Electronic absorption of Frenkel excitons in topologically disordered systems

    NASA Astrophysics Data System (ADS)

    Schweizer, Kenneth S.

    1986-10-01

    A self-consistent effective medium theory of the electronic absorption spectra of tightly bound dipolar excitons in simple fluids is developed within the adiabatic picture. The theoretical approach is based on the isomorphism between the path-integral formulation of quantum theory and classical statistical mechanics and is an extension of previous work [D. Chandler, K. S. Schweizer, and P. G. Wolynes, Phys. Rev. Lett. 49, 1100 (1982)]. The consequences of fluid structural disorder on resonant excitation transfer and the statistical fluctuations of single molecule energy levels are simultaneously treated. Detailed numerical calculations are performed to establish the dependence of the absorption spectrum on fluid density, short range order, and the relative magnitude of the resonant transfer vs the single site disorder. The density dependence of the spectral features are found to be a sensitive function of fluid structure and the relative strength of the localizing vs the delocalizing interactions. By comparing the liquid state results with the corresponding crystalline solid behavior, the consequences of topological disorder on the exciton spectrum are identified. The relevance of the theoretical predictions to spectroscopic probes of exciton delocalization in molecular liquids and glasses is discussed.

  2. Exciton Seebeck effect in molecular systems.

    PubMed

    Yan, Yun-An; 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. This phenomenon is similar to the Seebeck effect as well as spin Seebeck effect and can be named as exciton Seebeck effect.

  3. Exciton Seebeck effect in molecular systems

    SciTech Connect

    Yan, Yun-An; 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. This phenomenon is similar to the Seebeck effect as well as spin Seebeck effect and can be named as exciton Seebeck effect.

  4. Distinct exciton dissociation behavior of organolead trihalide perovskite and excitonic semiconductors studied in the same system.

    PubMed

    Hu, Miao; Bi, Cheng; Yuan, Yongbo; Xiao, Zhengguo; Dong, Qingfeng; Shao, Yuchuan; Huang, Jinsong

    2015-05-13

    The nonexcitonic character for organometal trihalide perovskites is demonstrated by examining the field-dependent exciton dissociation behavior. 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.

  5. 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.

  6. Ground state energy of N Frenkel excitons

    NASA Astrophysics Data System (ADS)

    Pogosov, W.; Combescot, M.

    2009-03-01

    By using the composite many-body theory for Frenkel excitons we have recently developed, we here derive the ground state energy of N Frenkel excitons in the Born approximation through the Hamiltonian mean value in a state made of N identical Q = 0 excitons. While this quantity reads as a density expansion in the case of Wannier excitons, due to many-body effects induced by fermion exchanges between N composite particles, we show that the Hamiltonian mean value for N Frenkel excitons only contains a first order term in density, just as for elementary bosons. Such a simple result comes from a subtle balance, difficult to guess a priori, between fermion exchanges for two or more Frenkel excitons appearing in Coulomb term and the ones appearing in the N exciton normalization factor - the cancellation being exact within terms in 1/Ns where Ns is the number of atomic sites in the sample. This result could make us naively believe that, due to the tight binding approximation on which Frenkel excitons are based, these excitons are just bare elementary bosons while their composite nature definitely appears at various stages in the precise calculation of the Hamiltonian mean value.

  7. Ballistic spin transport in exciton gases

    NASA Astrophysics Data System (ADS)

    Kavokin, A. V.; Vladimirova, M.; Jouault, B.; Liew, T. C. H.; Leonard, J. R.; Butov, L. V.

    2013-11-01

    Traditional spintronics relies on spin transport by charge carriers, such as electrons in semiconductor crystals. The challenges for the realization of long-range electron spin transport include rapid spin relaxation due to electron scattering. Scattering and, in turn, spin relaxation can be effectively suppressed in excitonic devices where the spin currents are carried by electrically neutral bosonic quasiparticles: excitons or exciton-polaritons. They can form coherent quantum liquids that carry spins over macroscopic distances. The price to pay is a finite lifetime of the bosonic spin carriers. We present the theory of exciton ballistic spin transport which may be applied to a range of systems supporting bosonic spin transport, in particular to indirect excitons in coupled quantum wells. We describe the effect of spin-orbit interaction for the electron and the hole on the exciton spin, account for the Zeeman effect induced by external magnetic fields and long-range and short-range exchange splittings of the exciton resonances. We also consider exciton transport in the nonlinear regime and discuss the definitions of the exciton spin current, polarization current, and spin conductivity.

  8. Exciton spin dynamics in GaSe

    SciTech Connect

    Tang, Yanhao; Xie, Wei; McGuire, John A. Lai, Chih Wei; Mandal, Krishna C.

    2015-09-21

    We analyze exciton spin dynamics in GaSe under nonresonant circularly polarized optical pumping with an exciton spin-flip rate-equation model. The model reproduces polarized time-dependent photoluminescence measurements in which the initial circular polarization approaches unity even when pumping with 0.15 eV excess energy. At T = 10 K, the exciton spin relaxation exhibits a biexponential decay with sub-20 ps and >500 ps time constants, which are also reproduced by the rate-equation model assuming distinct spin-relaxation rates for hot (nonequilibrium) and cold band-edge excitons.

  9. Excitons in solids with non-empirical hybrid time-dependent density-functional theory

    NASA Astrophysics Data System (ADS)

    Ullrich, Carsten; Yang, Zeng-Hui; Sottile, Francesco

    2015-03-01

    The Bethe-Salpeter equation (BSE) accurately describes the optical properties of solids, but is computationally expensive. Time-dependent density-functional theory (TDDFT) is more efficient, but standard functionals do not produce excitons in extended systems. We present a new, non-empirical hybrid TDDFT approach whose computational cost is much less than BSE, while the accuracy for both bound excitons and the continuum spectra is comparable to that of the BSE. Good performance is observed for both small-gap semiconductors and large-gap insulators. Work supported by NSF Grant DMR-1408904.

  10. Solution-grown organic single-crystalline donor-acceptor heterojunctions for photovoltaics.

    PubMed

    Li, Hanying; Fan, Congcheng; Fu, Weifei; Xin, Huolin L; Chen, Hongzheng

    2015-01-12

    Organic single crystals are ideal candidates for high-performance photovoltaics due to their high charge mobility and long exciton diffusion length; however, they have not been largely considered for photovoltaics due to the practical difficulty in making a heterojunction between donor and acceptor single crystals. Here, we demonstrate that extended single-crystalline heterojunctions with a consistent donor-top and acceptor-bottom structure throughout the substrate can be simply obtained from a mixed solution of C60 (acceptor) and 3,6-bis(5-(4-n-butylphenyl)thiophene-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione (donor). 46 photovoltaic devices were studied with the power conversion efficiency of (0.255±0.095)% under 1 sun, which is significantly higher than the previously reported value for a vapor-grown organic single-crystalline donor-acceptor heterojunction (0.007%). As such, this work opens a practical avenue for the study of organic photovoltaics based on single crystals.

  11. Charge Generation Pathways in Organic Solar Cells: Assessing the Contribution from the Electron Acceptor.

    PubMed

    Stoltzfus, Dani M; Donaghey, Jenny E; Armin, Ardalan; Shaw, Paul E; Burn, Paul L; Meredith, Paul

    2016-11-09

    Photocurrent generation in organic bulk heterojunction (BHJ) solar cells is most commonly understood as a process which predominantly involves photoexcitation of the lower ionization potential species (donor) followed by electron transfer to the higher electron affinity material (acceptor) [i.e., photoinduced electron transfer (PET), which we term Channel I]. A mirror process also occurs in which photocurrent is generated through photoexcitation of the acceptor followed by hole transfer to the nonexcited donor or photoinduced hole transfer (PHT), which we term Channel II. The role of Channel II photocurrent generation has often been neglected due to overlap of the individual absorption spectra of the donor and acceptor materials that are commonly used. More recently Channel II charge generation has been explored for several reasons. First, many of the new high-efficiency polymeric donors are used as the minority component in bulk heterojunction blends, and therefore, the acceptor absorption is a significant fraction of the total; second, nonfullerene acceptors have been prepared, which through careful design, allow for spectral separation from the donor material, facilitating fundamental studies on charge generation. In this article, we review the methodologies for investigating the two charge generation channels. We also discuss the factors that affect charge generation via Channel I and II pathways, including energy levels of the materials involved, exciton diffusion, and other considerations. Finally, we take a comprehensive look at the nonfullerene acceptor literature and discuss what information about Channel I and Channel II can be obtained from the experiments conducted and what other experiments could be undertaken to provide further information about the operational efficiencies of Channels I and II.

  12. Features of exciton dynamics in molecular nanoclusters (J-aggregates): Exciton self-trapping (Review Article)

    NASA Astrophysics Data System (ADS)

    Malyukin, Yu. V.; Sorokin, A. V.; Semynozhenko, V. P.

    2016-06-01

    We present thoroughly analyzed experimental results that demonstrate the anomalous manifestation of the exciton self-trapping effect, which is already well-known in bulk crystals, in ordered molecular nanoclusters called J-aggregates. Weakly-coupled one-dimensional (1D) molecular chains are the main structural feature of J-aggregates, wherein the electron excitations are manifested as 1D Frenkel excitons. According to the continuum theory of Rashba-Toyozawa, J-aggregates can have only self-trapped excitons, because 1D excitons must adhere to barrier-free self-trapping at any exciton-phonon coupling constant g = ɛLR/2β, wherein ɛLR is the lattice relaxation energy, and 2β is the half-width of the exciton band. In contrast, very often only the luminescence of free, mobile excitons would manifest in experiments involving J-aggregates. Using the Urbach rule in order to analyze the low-frequency region of the low-temperature exciton absorption spectra has shown that J-aggregates can have both a weak (g < 1) and a strong (g > 1) exciton-phonon coupling. Moreover, it is experimentally demonstrated that under certain conditions, the J-aggregate excited state can have both free and self-trapped excitons, i.e., we establish the existence of a self-trapping barrier for 1D Frenkel excitons. We demonstrate and analyze the reasons behind the anomalous existence of both free and self-trapped excitons in J-aggregates, and demonstrate how exciton-self trapping efficiency can be managed in J-aggregates by varying the values of g, which is fundamentally impossible in bulk crystals. We discuss how the exciton-self trapping phenomenon can be used as an alternate interpretation of the wide band emission of some J-aggregates, which has thus far been explained by the strongly localized exciton model.

  13. Josephson effects in condensates of excitons and exciton polaritons

    SciTech Connect

    Shelykh, I. A.; Solnyshkov, D. D.; Pavlovic, G.; Malpuech, G.

    2008-07-15

    We analyze theoretically the phenomena related to the Josephson effect for exciton and polariton condensates, taking into account their specific spin degrees of freedom. We distinguish between two types of Josephson effects: the extrinsic effect, related to the coherent tunneling of particles with the same spin between two spatially separated potential traps, and the intrinsic effect, related to the 'tunneling' between different spinor components of the condensate within the same trap. We show that the Josephson effect in the nonlinear regime can lead to nontrivial polarization dynamics and produce spontaneous separation of the condensates with opposite polarization in real space.

  14. Macrocrystals of Colloidal Quantum Dots in Anthracene: Exciton Transfer and Polarized Emission.

    PubMed

    Soran-Erdem, Zeliha; Erdem, Talha; Hernandez-Martinez, Pedro Ludwig; Akgul, Mehmet Zafer; Gaponik, Nikolai; Demir, Hilmi Volkan

    2015-05-07

    In this work, centimeter-scale macrocrystals of nonpolar colloidal quantum dots (QDs) incorporated into anthracene were grown for the first time. The exciton transfer from the anthracene host to acceptor QDs was systematically investigated, and anisotropic emission from the isotropic QDs in the anthracene macrocrystals was discovered. Results showed a decreasing photoluminescence lifetime of the donor anthracene, indicating a strengthening energy transfer with increasing QD concentration in the macrocrystals. With the anisotropy study, QDs inside the anthracene host acquired a polarization ratio of ~1.5 at 0° collection angle, and this increases to ~2.5 at the collection angle of 60°. A proof-of-concept application of these excitonic macrocrystals as tunable color converters on light-emitting diodes was also demonstrated.

  15. Molecular nitrogen acceptors in ZnO nanowires induced by nitrogen plasma annealing

    NASA Astrophysics Data System (ADS)

    Ton-That, C.; Zhu, L.; Lockrey, M. N.; Phillips, M. R.; Cowie, B. C. C.; Tadich, A.; Thomsen, L.; Khachadorian, S.; Schlichting, S.; Jankowski, N.; Hoffmann, A.

    2015-07-01

    X-ray absorption near-edge spectroscopy, photoluminescence, cathodoluminescence, and Raman spectroscopy have been used to investigate the chemical states of nitrogen dopants in ZnO nanowires. It is found that nitrogen exists in multiple states: NO,NZn, and loosely bound N2 molecule. The results establish a direct link between a donor-acceptor pair emission at 3.232 eV and the concentration of loosely bound N2. This work confirms that N2 at Zn site is a potential candidate for producing a shallow acceptor state in N-doped ZnO as theoretically predicted by Lambrecht and Boonchun [Phys. Rev. B 87, 195207 (2013), 10.1103/PhysRevB.87.195207]. Additionally, shallow acceptor states arising from NO complexes have been ruled out in this paper.

  16. Anaerobic electron acceptor chemotaxis in Shewanella putrefaciens.

    PubMed

    Nealson, K H; Moser, D P; Saffarini, D A

    1995-04-01

    Shewanella putrefaciens MR-1 can grow either aerobically or anaerobically at the expense of many different electron acceptors and is often found in abundance at redox interfaces in nature. Such redox interfaces are often characterized by very strong gradients of electron acceptors resulting from rapid microbial metabolism. The coincidence of S. putrefaciens abundance with environmental gradients prompted an examination of the ability of MR-1 to sense and respond to electron acceptor gradients in the laboratory. In these experiments, taxis to the majority of the electron acceptors that S. putrefaciens utilizes for anaerobic growth was seen. All anaerobic electron acceptor taxis was eliminated by the presence of oxygen, nitrate, nitrite, elemental sulfur, or dimethyl sulfoxide, even though taxis to the latter was very weak and nitrate and nitrite respiration was normal in the presence of dimethyl sulfoxide. Studies with respiratory mutants of MR-1 revealed that several electron acceptors that could not be used for anaerobic growth nevertheless elicited normal anaerobic taxis. Mutant M56, which was unable to respire nitrite, showed normal taxis to nitrite, as well as the inhibition of taxis to other electron acceptors by nitrite. These results indicate that electron acceptor taxis in S. putrefaciens does not conform to the paradigm established for Escherichia coli and several other bacteria. Carbon chemo-taxis was also unusual in this organism: of all carbon compounds tested, the only positive response observed was to formate under anaerobic conditions.

  17. Anaerobic electron acceptor chemotaxis in Shewanella putrefaciens

    NASA Technical Reports Server (NTRS)

    Nealson, K. H.; Moser, D. P.; Saffarini, D. A.

    1995-01-01

    Shewanella putrefaciens MR-1 can grow either aerobically or anaerobically at the expense of many different electron acceptors and is often found in abundance at redox interfaces in nature. Such redox interfaces are often characterized by very strong gradients of electron acceptors resulting from rapid microbial metabolism. The coincidence of S. putrefaciens abundance with environmental gradients prompted an examination of the ability of MR-1 to sense and respond to electron acceptor gradients in the laboratory. In these experiments, taxis to the majority of the electron acceptors that S. putrefaciens utilizes for anaerobic growth was seen. All anaerobic electron acceptor taxis was eliminated by the presence of oxygen, nitrate, nitrite, elemental sulfur, or dimethyl sulfoxide, even though taxis to the latter was very weak and nitrate and nitrite respiration was normal in the presence of dimethyl sulfoxide. Studies with respiratory mutants of MR-1 revealed that several electron acceptors that could not be used for anaerobic growth nevertheless elicited normal anaerobic taxis. Mutant M56, which was unable to respire nitrite, showed normal taxis to nitrite, as well as the inhibition of taxis to other electron acceptors by nitrite. These results indicate that electron acceptor taxis in S. putrefaciens does not conform to the paradigm established for Escherichia coli and several other bacteria. Carbon chemo-taxis was also unusual in this organism: of all carbon compounds tested, the only positive response observed was to formate under anaerobic conditions.

  18. Exciton photoluminescence and energy in a percolation cluster of ZnSe quantum dots as a fractal object

    SciTech Connect

    Bondar, N. V. Brodyn, M. S.

    2012-05-15

    The results of studies of samples containing ZnSe quantum dots with a density corresponding to or considerably higher than the exciton percolation threshold, at which quantum dots form conglomerates, are reported. Excitonic emission from a percolation cluster of bound quantum dots as a fractal object is observed for the first time. Analysis of the structure of the photoluminescence spectra shows that the spectra are determined by the contribution of exciton states that belong to different structural elements of the percolation cluster, specifically, to the skeleton (backbone), dangling (dead) ends, and internal hollow spaces. A qualitative model is proposed to interpret the dependence of the exciton energy in these structural elements on the concentration of quantum dots in the material.

  19. Excitonic luminescence of SiGe/Si quantum wells δ-doped with boron

    SciTech Connect

    Bagaev, V. S.; Nikolaev, S. N.; Onishchenko, E. E.; Pruchkina, A. A.; Krivobok, V. S.; Novikov, A. V.

    2015-05-14

    Low-temperature photoluminescence of undoped and moderately δ-doped Si{sub 1−x}Ge{sub x}/Si (x < 0.1) quantum wells has been studied. The influence of boron δ-layer on the excitonic luminescence and the luminescence caused by a dense electron plasma was demonstrated. The conditions under which the luminescence spectra of quantum wells are dominated by impurity-bound excitons (BE) have been established. Some unusual properties of these BE are explained in terms of type II band-offset in Si{sub 1−x}Ge{sub x}/Si (x < 0.1) quantum wells, which favors a spatial separation of electrons and holes. It is shown that the temperature dependence of an excitonic emission in the quantum wells allows to calculate the BE-related density of states and, thus, can be used for contactless estimation of the impurity concentration in quantum wells.

  20. Splitting between bright and dark excitons in transition metal dichalcogenide monolayers

    NASA Astrophysics Data System (ADS)

    Echeverry, J. P.; Urbaszek, B.; Amand, T.; Marie, X.; Gerber, I. C.

    2016-03-01

    The optical properties of transition metal dichalcogenide monolayers such as the two-dimensional semiconductors MoS2 and WSe2 are dominated by excitons, Coulomb bound electron-hole pairs. The light emission yield depends on whether the electron-hole transitions are optically allowed (bright) or forbidden (dark). By solving the Bethe-Salpeter equation on top of G W wave functions in density functional theory calculations, we determine the sign and amplitude of the splitting between bright and dark exciton states. We evaluate the influence of the spin-orbit coupling on the optical spectra and clearly demonstrate the strong impact of the intra-valley Coulomb exchange term on the dark-bright exciton fine structure splitting.

  1. Cavity-less on-chip optomechanics using excitonic transitions in semiconductor heterostructures

    PubMed Central

    Okamoto, Hajime; Watanabe, Takayuki; Ohta, Ryuichi; Onomitsu, Koji; Gotoh, Hideki; Sogawa, Tetsuomi; Yamaguchi, Hiroshi

    2015-01-01

    The hybridization of semiconductor optoelectronic devices and nanomechanical resonators provides a new class of optomechanical systems in which mechanical motion can be coupled to light without any optical cavities. Such cavity-less optomechanical systems interconnect photons, phonons and electrons (holes) in a highly integrable platform, opening up the development of functional integrated nanomechanical devices. Here we report on a semiconductor modulation-doped heterostructure–cantilever hybrid system, which realizes efficient cavity-less optomechanical transduction through excitons. The opto-piezoelectric backaction from the bound electron–hole pairs enables us to probe excitonic transition simply with a sub-nanowatt power of light, realizing high-sensitivity optomechanical spectroscopy. Detuning the photon energy from the exciton resonance results in self-feedback cooling and amplification of the thermomechanical motion. This cavity-less on-chip coupling enables highly tunable and addressable control of nanomechanical resonators, allowing high-speed programmable manipulation of nanomechanical devices and sensor arrays. PMID:26477487

  2. Exciton-polaritons condensate in a microwire

    NASA Astrophysics Data System (ADS)

    Kamoun, O.; Jaziri, S.

    2013-12-01

    Recently, polariton condensation has been claimed in microwires. Numerical solutions of the time-dependent Gross-Pitaevskii equation that describes the behavior of the condensate in a trap and exciton-polariton interaction, have been obtained. In this work we study theoretically exciton-polariton one dimensional condensation in several quantized states.

  3. Achieving effective terminal exciton delivery in quantum dot antenna-sensitized multistep DNA photonic wires.

    PubMed

    Spillmann, Christopher M; Ancona, Mario G; Buckhout-White, Susan; Algar, W Russ; Stewart, Michael H; Susumu, Kimihiro; Huston, Alan L; Goldman, Ellen R; Medintz, Igor L

    2013-08-27

    Assembling DNA-based photonic wires around semiconductor quantum dots (QDs) creates optically active hybrid architectures that exploit the unique properties of both components. DNA hybridization allows positioning of multiple, carefully arranged fluorophores that can engage in sequential energy transfer steps while the QDs provide a superior energy harvesting antenna capacity that drives a Förster resonance energy transfer (FRET) cascade through the structures. Although the first generation of these composites demonstrated four-sequential energy transfer steps across a distance >150 Å, the exciton transfer efficiency reaching the final, terminal dye was estimated to be only ~0.7% with no concomitant sensitized emission observed. Had the terminal Cy7 dye utilized in that construct provided a sensitized emission, we estimate that this would have equated to an overall end-to-end ET efficiency of ≤ 0.1%. In this report, we demonstrate that overall energy flow through a second generation hybrid architecture can be significantly improved by reengineering four key aspects of the composite structure: (1) making the initial DNA modification chemistry smaller and more facile to implement, (2) optimizing donor-acceptor dye pairings, (3) varying donor-acceptor dye spacing as a function of the Förster distance R0, and (4) increasing the number of DNA wires displayed around each central QD donor. These cumulative changes lead to a 2 orders of magnitude improvement in the exciton transfer efficiency to the final terminal dye in comparison to the first-generation construct. The overall end-to-end efficiency through the optimized, five-fluorophore/four-step cascaded energy transfer system now approaches 10%. The results are analyzed using Förster theory with various sources of randomness accounted for by averaging over ensembles of modeled constructs. Fits to the spectra suggest near-ideal behavior when the photonic wires have two sequential acceptor dyes (Cy3 and Cy3.5) and

  4. Correlation between charge transfer exciton recombination and photocurrent in polymer/fullerene solar cells

    SciTech Connect

    Hallermann, Markus; Da Como, Enrico; Feldmann, Jochen; Izquierdo, Marta; Filippone, Salvatore; Martin, Nazario; Juechter, Sabrina; Hauff, Elizabeth von

    2010-07-12

    We correlate carrier recombination via charge transfer excitons (CTEs) with the short circuit current, J{sub sc}, in polymer/fullerene solar cells. Near infrared photoluminescence spectroscopy of CTE in three blends differing for the fullerene acceptor, gives unique insights into solar cell characteristics. The energetic position of the CTE is directly correlated with the open-circuit voltage, V{sub oc}, and more important J{sub sc} decreases with increasing CTE emission intensity. CTE emission intensity is discussed from the perspective of blend morphology. The work points out the fundamental role of CTE recombination and how optical spectroscopy can be used to derive information on solar cell performances.

  5. Excitons and optical spectra of phosphorene nanoribbons

    NASA Astrophysics Data System (ADS)

    Nourbakhsh, Zahra; Asgari, Reza

    2016-07-01

    On the basis of many-body ab initio calculations, using the single-shot G0W0 method and Bethe-Salpeter equation, we study phosphorene nanoribbons (PNRs) in the two typical zigzag and armchair directions. The electronic structure, optical absorption, electron-hole (exciton) binding energy, exciton exchange splitting, and exciton wave functions are calculated for different sizes of PNRs. The typically strong splitting between singlet and triplet excitonic states make PNRs favorable systems for optoelectronic applications. Quantum confinement occurs in both kinds of PNRs, and it is stronger in the zPNRs, which behave like quasi-zero-dimensional systems. Scaling laws are investigated for the size-dependent behaviors of PNRs. The first bright excitonic state in PNRs is explored in detail.

  6. Excitonic magnetism in d6 perovskites

    NASA Astrophysics Data System (ADS)

    Afonso, J. Fernández; Kuneš, J.

    2017-03-01

    We use the LDA+U method to study the possibility of exciton condensation in perovskites of transition metals with the d6 electronic configuration such as LaCoO3. For realistic interaction parameters we find several distinct solutions exhibiting a spin-triplet exciton condensate, which gives rise to a local spin density distribution while the ordered moments are vanishingly small. Rhombohedral distortion from the ideal cubic structure suppresses the ordered state, contrary to the spin-orbit coupling which enhances the excitonic condensation energy. We explain the trends observed in the numerical simulations with the help of a simplified strong-coupling model. Our results indicate that LaCoO3 is close to the excitonic instability and suggest ways how to achieve the exciton condensation.

  7. Bright Solid-State Emission of Disilane-Bridged Donor-Acceptor-Donor and Acceptor-Donor-Acceptor Chromophores.

    PubMed

    Shimada, Masaki; Tsuchiya, Mizuho; Sakamoto, Ryota; Yamanoi, Yoshinori; Nishibori, Eiji; Sugimoto, Kunihisa; Nishihara, Hiroshi

    2016-02-24

    The development of disilane-bridged donor-acceptor-donor (D-Si-Si-A-Si-Si-D) and acceptor-donor-acceptor (A-Si-Si-D-Si-Si-A) compounds is described. Both types of compound showed strong emission (λem =ca. 500 and ca. 400 nm, respectively) in the solid state with high quantum yields (Φ: up to 0.85). Compound 4 exhibited aggregation-induced emission enhancement in solution. X-ray diffraction revealed that the crystal structures of 2, 4, and 12 had no intermolecular π-π interactions to suppress the nonradiative transition in the solid state.

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

    SciTech Connect

    Allendorf, Mark D.; Azoulay, Jason; Ford, Alexandra Caroline; Foster, Michael E.; El Gabaly Marquez, Farid; Leonard, Francois Leonard; Leong-Hau, Kirsty; Stavila, Vitalie; Talin, Albert Alec; Wong, Brian M.; Brumbach, Michael T.; Van Gough, D.; Lambert, Timothy N.; Rodriguez, Mark A.; Spoerke, Erik David; Wheeler, David Roger; Deaton, Joseph C.; Centrone, Andrea; Haney, Paul; Kinney, R.; Szalai, Veronika; Yoon, Heayoung P.

    2014-09-01

    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.

  9. Photocurrent spectroscopy of exciton and free particle optical transitions in suspended carbon nanotube pn-junctions

    SciTech Connect

    Chang, Shun-Wen; Theiss, Jesse; Hazra, Jubin; Aykol, Mehmet; Kapadia, Rehan; Cronin, Stephen B.

    2015-08-03

    We study photocurrent generation in individual, suspended carbon nanotube pn-junction diodes formed by electrostatic doping using two gate electrodes. Photocurrent spectra collected under various electrostatic doping concentrations reveal distinctive behaviors for free particle optical transitions and excitonic transitions. In particular, the photocurrent generated by excitonic transitions exhibits a strong gate doping dependence, while that of the free particle transitions is gate independent. Here, the built-in potential of the pn-junction is required to separate the strongly bound electron-hole pairs of the excitons, while free particle excitations do not require this field-assisted charge separation. We observe a sharp, well defined E{sub 11} free particle interband transition in contrast with previous photocurrent studies. Several steps are taken to ensure that the active charge separating region of these pn-junctions is suspended off the substrate in a suspended region that is substantially longer than the exciton diffusion length and, therefore, the photocurrent does not originate from a Schottky junction. We present a detailed model of the built-in fields in these pn-junctions, which, together with phonon-assistant exciton dissociation, predicts photocurrents on the same order of those observed experimentally.

  10. Ultrafast exciton migration in an HJ-aggregate: Potential surfaces and quantum dynamics

    NASA Astrophysics Data System (ADS)

    Binder, Robert; Polkehn, Matthias; Ma, Tianji; Burghardt, Irene

    2017-01-01

    Quantum dynamical and electronic structure calculations are combined to investigate the mechanism of exciton migration in an oligothiophene HJ aggregate, i.e., a combination of oligomer chains (J-type aggregates) and stacked aggregates of such chains (H-type aggregates). To this end, a Frenkel exciton model is parametrized by a recently introduced procedure [Binder et al., J. Chem. Phys. 141, 014101 (2014)] which uses oligomer excited-state calculations to perform an exact, point-wise mapping of coupled potential energy surfaces to an effective Frenkel model. Based upon this parametrization, the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method is employed to investigate ultrafast dynamics of exciton transfer in a small, asymmetric HJ aggregate model composed of 30 sites and 30 active modes. For a partially delocalized initial condition, it is shown that a torsional defect confines the trapped initial exciton, and planarization induces an ultrafast resonant transition between an HJ-aggregated segment and a covalently bound "dangling chain" end. This model is a minimal realization of experimentally investigated mixed systems exhibiting ultrafast exciton transfer between aggregated, highly planarized chains and neighboring disordered segments.

  11. Spectrum of a lattice exciton in a transverse magnetic field: Emergence of full translational symmetry

    NASA Astrophysics Data System (ADS)

    Berciu, Mona

    2014-06-01

    We show that even in the presence of a transverse magnetic field, the eigenstates of an exciton remain invariant to the full lattice translation group. This is expected if the exciton is viewed as a neutral quasiparticle, but not if one views it as a bound electron-hole pair. Single electron and hole wave functions are invariant only to the magnetic translation group, and their momenta are restricted to the magnetic Brillouin zone; the associated folding is the origin of their Hofstadter butterfly spectra. We find that such folding is not necessary for exciton eigenstates, which are characterized by momenta in the full Brillouin zone and thus have higher symmetry than the Hamiltonian. The magnetic field can have a significant effect on the shape of the exciton dispersion, however. While similar effects have been noted in continuous models, we find qualitatively different behavior for Frenkel excitons, whose origin we clarify. We also derive an analytical solution for the Hofstadter butterfly on a square lattice and analyze its dispersion in the full Brillouin zone.

  12. Exciton scattering approach for optical spectra calculations in branched conjugated macromolecules

    NASA Astrophysics Data System (ADS)

    Li, Hao; Wu, Chao; Malinin, Sergey V.; Tretiak, Sergei; Chernyak, Vladimir Y.

    2016-12-01

    The exciton scattering (ES) technique is a multiscale approach based on the concept of a particle in a box and developed for efficient calculations of excited-state electronic structure and optical spectra in low-dimensional conjugated macromolecules. Within the ES method, electronic excitations in molecular structure are attributed to standing waves representing quantum quasi-particles (excitons), which reside on the graph whose edges and nodes stand for the molecular linear segments and vertices, respectively. Exciton propagation on the linear segments is characterized by the exciton dispersion, whereas exciton scattering at the branching centers is determined by the energy-dependent scattering matrices. Using these ES energetic parameters, the excitation energies are then found by solving a set of generalized "particle in a box" problems on the graph that represents the molecule. Similarly, unique energy-dependent ES dipolar parameters permit calculations of the corresponding oscillator strengths, thus, completing optical spectra modeling. Both the energetic and dipolar parameters can be extracted from quantum-chemical computations in small molecular fragments and tabulated in the ES library for further applications. Subsequently, spectroscopic modeling for any macrostructure within a considered molecular family could be performed with negligible numerical effort. We demonstrate the ES method application to molecular families of branched conjugated phenylacetylenes and ladder poly-para-phenylenes, as well as structures with electron donor and acceptor chemical substituents. Time-dependent density functional theory (TD-DFT) is used as a reference model for electronic structure. The ES calculations accurately reproduce the optical spectra compared to the reference quantum chemistry results, and make possible to predict spectra of complex macromolecules, where conventional electronic structure calculations are unfeasible.

  13. Biexciton formation and exciton coherent coupling in layered GaSe

    SciTech Connect

    Dey, P.; Paul, J.; Stevens, C. E.; Glikin, N.; Karaiskaj, D.; Moody, G.; Kovalyuk, Z. D.; Kudrynskyi, Z. R.; Romero, A. H.; Cantarero, A.; Hilton, D. J.

    2015-06-07

    Nonlinear two-dimensional Fourier transform (2DFT) and linear absorption spectroscopy are used to study the electronic structure and optical properties of excitons in the layered semiconductor GaSe. At the 1s exciton resonance, two peaks are identified in the absorption spectra, which are assigned to splitting of the exciton ground state into the triplet and singlet states. 2DFT spectra acquired for co-linear polarization of the excitation pulses feature an additional peak originating from coherent energy transfer between the singlet and triplet. At cross-linear polarization of the excitation pulses, the 2DFT spectra expose a new peak likely originating from bound biexcitons. The polarization dependent 2DFT spectra are well reproduced by simulations using the optical Bloch equations for a four level system, where many-body effects are included phenomenologically. Although biexciton effects are thought to be strong in this material, only moderate contributions from bound biexciton creation can be observed. The biexciton binding energy of ∼2 meV was estimated from the separation of the peaks in the 2DFT spectra. Temperature dependent absorption and 2DFT measurements, combined with “ab initio” theoretical calculations of the phonon spectra, indicate strong interaction with the A{sub 1}{sup ′} phonon mode. Excitation density dependent 2DFT measurements reveal excitation induced dephasing and provide a lower limit for the homogeneous linewidth of the excitons in the present GaSe crystal.

  14. Excitonic polaritons of zinc diarsenide single crystals

    NASA Astrophysics Data System (ADS)

    Syrbu, N. N.; Stamov, I. G.; Zalamai, V. V.; Dorogan, A.

    2017-02-01

    Excitonic polaritons of ZnAs2 single crystals had been investigated. Parameters of singlet excitons with D2bar(z) symmetry and orthoexcitons 2D1bar(y)+D2bar(x) had been determined. Spectral dependencies of ordinary and extraordinary dispersion of refractive index had been calculated using interferential reflection and transmittance spectra. It was shown, that A excitonic series were due to hole (V1) and electron (C1) bands. The values of effective masses of electrons (mc*=0.10 m0) and holes (mv1*=0.89 m0) had been estimated. It was revealed that the hole mass mv1* changes from 1.03 m0 to 0.55 m0 at temperature increasing from 10 K up to 230 K and that the electron mass mc* does not depend on temperature. The integral absorption A (eV cm-1) of the states n=1, 2 and 3 of D2bar(z) excitons depends on the An≈n-3 equality, which it is characteristic for S-type excitonic functions. Temperature dependences of the integral absorption of ground states for D2bar(z) and D2bar(D) excitons differ. The ground states of B and C excitons formed by V3 - C1 and V4 - C1 bands and its parameters had been determined.

  15. Ultracold Gas of Excitons in Traps

    DTIC Science & Technology

    2012-06-08

    Excitons in a GaAs Quantum-Well Structurewith a Diamond-Shaped Electrostatic Trap, Physical Review Letters, (08 2009): 87403. doi: 2012/06/08 14:38:06 19...Kinetics of the inner ring in the exciton emission pattern in coupled GaAs quantum wells, Physical Review B, (10 2009): 155331. doi: 2012/06/08 14:28:30...17 Sen Yang, , L. V. Butov, , L. S. Levitov, , B. D. Simons,, A. C. Gossard. Exciton front propagation in photoexcited GaAs quantum wells, Physical

  16. Excitons in the Fractional Quantum Hall Effect

    DOE R&D Accomplishments Database

    Laughlin, R. B.

    1984-09-01

    Quasiparticles of charge 1/m in the Fractional Quantum Hall Effect form excitons, which are collective excitations physically similar to the transverse magnetoplasma oscillations of a Wigner crystal. A variational exciton wavefunction which shows explicitly that the magnetic length is effectively longer for quasiparticles than for electrons is proposed. This wavefunction is used to estimate the dispersion relation of these excitons and the matrix elements to generate them optically out of the ground state. These quantities are then used to describe a type of nonlinear conductivity which may occur in these systems when they are relatively clean.

  17. Diamagnetic excitons in semiconductors (Review)

    NASA Astrophysics Data System (ADS)

    Seisyan, R. P.

    2016-05-01

    Optical properties of semiconductor crystals in the presence of a high magnetic field have been considered. The field turn-on gives rise to oscillations of the optical-absorption edge or, more specifically, the formation of a complex absorption spectrum with a periodic structure, referred to as the spectrum of "diamagnetic excitons." Such spectra appear a source of the most accurate knowledge about the band structure of semiconductors. Moreover, these spectra can be used for simulating the low-dimensional state in semiconductors and possible interpretation of the emission spectra of neutron stars. The proposed analytical review is based on extensive experimental and theoretical data contained mostly in cited original works of the author with colleagues.

  18. Synthetic CO.sub.2 acceptor

    DOEpatents

    Lancet, Michael S.; Curran, George P.

    1981-08-18

    A synthetic CO.sub.2 acceptor consisting essentially of at least one compound selected from the group consisting of calcium oxide and calcium carbonate supported in a refractory carrier matrix, the carrier having the general formula Ca.sub.5 (SiO.sub.4).sub.2 CO.sub.3. A method for producing the synthetic CO.sub.2 acceptor is also disclosed.

  19. Acoustic-excitonic effects in a two-dimensional gas of dipolar excitons

    NASA Astrophysics Data System (ADS)

    Boev, M. V.; Kovalev, V. M.; Chaplik, A. V.

    2016-08-01

    The theory of the interaction of a two-dimensional gas of indirect dipolar excitons with Rayleigh surface elastic waves has been developed. The absorption and renormalization of the phase velocity of a surface wave, as well as the drag of excitons by the surface acoustic wave and the generation of bulk acoustic waves by a twodimensional gas of dipolar excitons irradiated by external electromagnetic radiation, have been considered. These effects have been studied both in a normal phase at high temperatures and in a condensed phase of the exciton gas. The calculations have been performed in the ballistic and diffusion limits for both phases.

  20. Optical nutation in the exciton range of spectrum

    SciTech Connect

    Khadzhi, P. I.; Vasiliev, V. V.

    2013-08-15

    Optical nutation in the exciton range of spectrum is studied in the mean field approximation taking into account exciton-photon and elastic exciton-exciton interactions. It is shown that the features of nutation development are determined by the initial exciton and photon densities, the resonance detuning, the nonlinearity parameter, and the initial phase difference. For nonzero initial exciton and photon concentrations, three regimes of temporal evolution of excitons and photons exist: periodic conversion of excitons to photons and vice versa, aperiodic conversion of photons to excitons, and the rest regime. In the rest regime, the initial exciton and photon densities are nonzero and do not change with time. The oscillation amplitudes and periods of particle densities determined by the system parameters are found. The exciton self-trapping and photon trapping appearing in the system at threshold values of the nonlinearity parameter were predicted. As this parameter increases, the oscillation amplitudes of the exciton and photon densities sharply change at the critical value of the nonlinearity parameter. These two phenomena are shown to be caused by the elastic exciton-exciton interaction, resulting in the dynamic concentration shift of the exciton level.

  1. Electron acceptors based on alpha-position substituted PDI for OPV solar cells.

    SciTech Connect

    Zhao, Donglin; Wu, Qinghe; Cai, Zhengxu; Zheng, T; Chen, Wei; Lu, Jessica; Yu, L

    2016-02-23

    The ortho-position functionalized perylene diimide derivatives (alphaPPID, alphaPBDT) were synthesized and used as the electron acceptors in nonfullerene organic photovoltaics. Due to the good planarity of ortho-position functionalized PDI, the alphaPPID and alphaPBDT show strong tendency to form aggregate because of their enhanced intermolecular pie-pie interaction. Moreover, they maintain the pure domains and the same packing order as in the pure film if they are blended with PBT7-TH and the SCLC measurement also shows the high electron mobility. The inverted OPVs employing alphaPDI-based compounds as acceptor and PBT7-TH as the donor give the highest PCE of 4.92 % for alphaPBDT based device and 3.61 % for alphaPPID based device, which is 39 % and 4 % higher than that for their counterpart betaPBDT and betaPPID. The charge separation study shows the more efficient exciton dissociation at interfaces between PDI based compounds and PBT7-TH. The results suggest that compared to beta-substituted ones, alpha-substituted PDI derivatives are more promising electron acceptors for OPV.

  2. Radiative lifetime of excitons in carbon nanotubes.

    PubMed

    Perebeinos, Vasili; Tersoff, J; Avouris, Phaedon

    2005-12-01

    We calculate the radiative lifetime and energy bandstructure of excitons in semiconducting carbon nanotubes within a tight-binding approach including the electron-hole correlations via the Bethe-Salpeter equation. In the limit of rapid interband thermalization, the radiative decay rate is maximized at intermediate temperatures and decreases at low temperature because the lowest-energy excitons are optically forbidden. The intrinsic phonons cannot scatter excitons between optically active and forbidden bands, so sample-dependent extrinsic effects that break the symmetries can play a central role. We calculate the diameter-dependent energy splittings between singlet and triplet excitons of different symmetries and the resulting dependence of radiative lifetime on temperature and tube diameter.

  3. Exciton absorption in narrow armchair graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Monozon, B. S.; Schmelcher, P.

    2016-11-01

    We develop an analytical approach to the exciton optical absorption for narrow gap armchair graphene nanoribbons (AGNR). We focus on the regime of dominant size quantization in combination with the attractive electron-hole interaction. An adiabatic separation of slow and fast motions leads via the two-body Dirac equation to the isolated and coupled subband approximations. Discrete and continuous exciton states are in general coupled and form quasi-Rydberg series of purely discrete and resonance type character. The corresponding oscillator strengths and widths are derived. We show that the exciton peaks are blue-shifted, become broader and increase in magnitude upon narrowing the ribbon. At the edge of a subband the singularity related to the 1D density of states is transformed into finite absorption via the presence of the exciton. Our analytical results are in good agreement with those obtained by other methods including numerical approaches. Estimates of the expected experimental values are provided for realistic AGNR.

  4. Excitonic susceptibility in near triangular quantum wells

    NASA Astrophysics Data System (ADS)

    Anitha, A.; Arulmozhi, M.

    2017-03-01

    Diamagnetic susceptibility and binding energy of an exciton in a near triangular quantum well, with potential profile proportional to |z|2/3 composed of GaAs/Ga1- x Al x As and ZnO/Zn1- x Mg x O are calculated as a function of the wellwidth and concentration of Al and Mg respectively varying the magnetic field applied along growth direction (i.e. z-axis). Diamagnetic susceptibility of light hole exciton and heavy hole exciton, shows inverse behaviors in the two materials below 20 nm wellwidth and the binding energy of both excitons increases, as the magnetic field increases. The results obtained, are compared with those of quantum wells with varied potential profiles and the experimental results reported in the literature.

  5. Signatures of Quantum Coherences in Rydberg Excitons

    NASA Astrophysics Data System (ADS)

    Grünwald, P.; Aßmann, M.; Heckötter, J.; Fröhlich, D.; Bayer, M.; Stolz, H.; Scheel, S.

    2016-09-01

    Coherent optical control of individual particles has been demonstrated both for atoms and semiconductor quantum dots. Here we demonstrate the emergence of quantum coherent effects in semiconductor Rydberg excitons in bulk Cu2O . Because of the spectral proximity between two adjacent Rydberg exciton states, a single-frequency laser may pump both resonances with little dissipation from the detuning. As a consequence, additional resonances appear in the absorption spectrum that correspond to dressed states consisting of two Rydberg exciton levels coupled to the excitonic vacuum, forming a V -type three-level system, but driven only by one laser light source. We show that the level of pure dephasing in this system is extremely low. These observations are a crucial step towards coherently controlled quantum technologies in a bulk semiconductor.

  6. Exciton-polariton wakefields in semiconductor microcavities

    NASA Astrophysics Data System (ADS)

    Terças, H.; Mendonça, J. T.

    2016-02-01

    We consider the excitation of polariton wakefields due to a propagating light pulse in a semiconductor microcavity. We show that two kinds of wakes are possible, depending on the constituents fraction (either exciton or photon) of the polariton wavefunction. The nature of the wakefields (pure excitonic or polaritonic) can be controlled by changing the speed of propagation of the external pump. This process could be used as a diagnostic for the internal parameters of the microcavity.

  7. Exciton properties of selected aromatic hydrocarbon systems

    NASA Astrophysics Data System (ADS)

    Roth, Friedrich; Mahns, Benjamin; Hampel, Silke; Nohr, Markus; Berger, Helmuth; Büchner, Bernd; Knupfer, Martin

    2013-02-01

    We have examined the singlet excitons in two representatives of acene-type (tetracene and pentacene) and phenacene-type (chrysene and picene) molecular crystals, respectively, using electron energy-loss spectroscopy at low temperatures. We show that the excitation spectra of the two hydrocarbon families significantly differ. Moreover, close inspection of the data indicates that there is an increasing importance of charge-transfer excitons at lowest excitation energy with increasing length of the molecules.

  8. Quantum and classical solutions for statically screened two-dimensional Wannier-Mott excitons

    SciTech Connect

    Makowski, Adam J.

    2011-08-15

    Quantum solutions and classical orbits are discussed for statically screened Wannier-Mott excitons for two closely related potentials: the Stern-Howard potential and a suggested simple focusing one. Bound states and exact ''quantized'' values of screening are obtained as well. For the suggested potential, the scattering matrix, the Regge poles, and the transmission coefficient are calculated exactly. We argue that the simple potential can be utilized in applications instead of the Stern-Howard potential, which is difficult to handle.

  9. Observation of long-lived interlayer excitons in monolayer MoSe2–WSe2 heterostructures

    DOE PAGES

    Rivera, Pasqual; Schaibley, John R.; Jones, Aaron M.; ...

    2015-02-24

    Van der Waals bound heterostructures constructed with two-dimensional materials, such as graphene, boron nitride and transition metal dichalcogenides, have sparked wide interest in both device physics and technologies at the two-dimensional limit. One highly coveted heterostructure is that of differing monolayer transition metal dichalcogenides with type-II band alignment, with bound electrons and holes localized in individual monolayers, that is, interlayer excitons. Here, we report the observation of interlayer excitons in monolayer MoSe2–WSe2 heterostructures by photoluminescence and photoluminescence excitation spectroscopy. The energy and luminescence intensity are highly tunable by an applied vertical gate voltage. Moreover, we measure an interlayer exciton lifetimemore » of ~1.8 ns, an order of magnitude longer than intralayer excitons in monolayers. Ultimately, our work demonstrates optical pumping of interlayer electric polarization, which may provoke further exploration of interlayer exciton condensation, as well as new applications in two-dimensional lasers, light-emitting diodes and photovoltaic devices.« less

  10. Exciton Resonances in Novel Silicon Carbide Polymers

    NASA Astrophysics Data System (ADS)

    Burggraf, Larry; Duan, Xiaofeng

    2015-05-01

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

  11. Tailored exciton diffusion in organic photovoltaic cells for enhanced power conversion efficiency.

    PubMed

    Menke, S Matthew; Luhman, Wade A; Holmes, Russell J

    2013-02-01

    Photoconversion in planar-heterojunction organic photovoltaic cells (OPVs) is limited by a short exciton diffusion length (L(D)) that restricts migration to the dissociating electron donor/acceptor interface. Consequently, bulk heterojunctions are often used to realize high efficiency as these structures reduce the distance an exciton must travel to be dissociated. Here, we present an alternative approach that seeks to directly engineer L(D) by optimizing the intermolecular separation and consequently, the photophysical parameters responsible for excitonic energy transfer. By diluting the electron donor boron subphthalocyanine chloride into a wide-energy-gap host material, we optimize the degree of interaction between donor molecules and observe a ~50% increase in L(D). Using this approach, we construct planar-heterojunction OPVs with a power conversion efficiency of (4.4 ± 0.3)%, > 30% larger than the case of optimized devices containing an undiluted donor layer. The underlying correlation between L(D) and the degree of molecular interaction has wide implications for the design of both OPV active materials and device architectures.

  12. Upward Bound

    ERIC Educational Resources Information Center

    Journal of Aerospace Education, 1976

    1976-01-01

    Describes an Upward Bound program at Embry-Riddle Aeronautical University designed to assist disadvantaged high school juniors and seniors in overcoming academic deficiencies in order to enter and succeed in college. The Saturday program centered on various aspects of aviation, including career opportunities. (MLH)

  13. Outward Bound.

    ERIC Educational Resources Information Center

    Outward Bound, Inc., Andover, MA.

    The Outward Bound concept was developed in Germany and Great Britain with the saving of human life as the ultimate goal. Courses are designed to help students discover their true physical and mental limits through development of skills including emergency medical aid, firefighting, search and rescue, mountaineering, and sailing. Five Outward Bound…

  14. Relationship between interchain interaction, exciton delocalization, and charge separation in low-bandgap copolymer blends.

    PubMed

    Guo, Zhi; Lee, Doyun; Schaller, Richard D; Zuo, Xiaobing; Lee, Byeongdu; Luo, TengFei; Gao, Haifeng; Huang, Libai

    2014-07-16

    We present a systematic study of the roles of crystallinity, interchain interaction, and exciton delocalization on ultrafast charge separation pathways in donor-acceptor copoloymer blends. We characterize the energy levels, excited state structures, and dynamics of the interchain species by combined ultrafast spectroscopy and computational quantum chemistry approaches. The alkyl side chain of a highly efficient donor-acceptor copolymer for solar cell applications, PBDTTT (poly(4,8-bis-alkyloxybenzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-(alkylthieno[3,4-b]thiophene-2-carboxylate)-2,6-diyl), is varied to tune the molecular packing and interchain interaction of the polymers in order to elucidate the charge separation pathways originating from intrachain and interchain species. Polymers with linear side chains result in more crystalline polymer domain that lead to preferential formation of interchain excitons delocalizing over more than one polymer backbone in the solid state. Our results demonstrate that the higher polymer crystallinity leads to slower charge separation due to coarser phase segregation and formation of the interchain excited states that are energetically unfavorable for charge separation. Such energetics of the interchain excitons in low-bandgap copolymers calls for optimized solar cell morphologies that are fundamentally different from those based on homopolymers such as P3HT (poly-3-hexylthiophene). A long-range crystalline polymer domain is detrimental rather than beneficial to solar cell performance for a low-bandgap copolymer which is in direct contrast to the observed behavior in P3HT based devices.

  15. Coherent Dynamics of Mixed Frenkel and Charge-Transfer Excitons in Dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]-thiophene Thin Films: The Importance of Hole Delocalization.

    PubMed

    Fujita, Takatoshi; Atahan-Evrenk, Sule; Sawaya, Nicolas P D; Aspuru-Guzik, Alán

    2016-04-07

    Charge-transfer states in organic semiconductors play crucial roles in processes such as singlet fission and exciton dissociation at donor/acceptor interfaces. Recently, a time-resolved spectroscopy study of dinaphtho[2,3-b:2'3'-f]thieno[3,2-b]-thiophene (DNTT) thin films provided evidence for the formation of mixed Frenkel and charge-transfer excitons after the photoexcitation. Here, we investigate optical properties and excitation dynamics of the DNTT thin films by combining ab initio calculations and a stochastic Schrödinger equation. Our theory predicts that the low-energy Frenkel exciton band consists of 8-47% CT character. The quantum dynamics simulations show coherent dynamics of Frenkel and CT states in 50 fs after the optical excitation. We demonstrate the role of charge delocalization and localization in the mixing of CT states with Frenkel excitons as well as the role of their decoherence.

  16. Controlled energy transfer between isolated donor-acceptor molecules intercalated in thermally self-ensemble two-dimensional hydrogen bonding cages

    NASA Astrophysics Data System (ADS)

    Al Attar, Hameed A.; Monkman, Andrew P.

    2012-12-01

    Thermally assembled hydrogen bonding cages which are neither size nor guest specific have been developed using a poly (vinyl alcohol) (PVA) host. A water-soluble conjugated polymer poly(2,5-bis(3-sulfonatopropoxy)-1,4-phenylene, disodium salt-alt-1,4-phenylene) (PPP-OPSO3) as a donor and tris(2,2-bipyridyl)- ruthenium(II) [Ru(bpy)32+] as an acceptor have been isolated and trapped in such a PVA matrix network. This is a unique system that shows negligible exciton diffusion and the donor and acceptor predominantly interact by a direct single step excitation transfer process (DSSET). Singlet and triplet exciton quenching have been studied. Time-resolved fluorescence lifetime measurement at different acceptor concentrations has enabled us to determine the dimensionality of the energy-transfer process within the PVA scaffold. Our results reveal that the PVA hydrogen bonding network effectively isolates the donor-acceptor molecules in a two-dimensional layer structure (lamella) leading to the condition where a precise control of the energy and charge transfer is possible.

  17. Interaction of Dirac Fermion excitons and biexciton-exciton cascade in graphene quantum dots

    NASA Astrophysics Data System (ADS)

    Ozfidan, Isil; Korkusinski, Marek; Hawrylak, Pawel

    2015-03-01

    We present a microscopic theory of interacting Dirac quasi-electrons and quasi-holes confined in graphene quantum dots. The single particle states of quantum dots are described using a tight binding model and screened direct, exchange, and scattering Coulomb matrix elements are computed using Slater pz orbitals. The many-body ground and excited states are expanded in a finite number of electron-hole pair excitations from the Hartree-Fock ground state and computed using exact diagonalization techniques. The resulting exciton and bi-exciton spectrum reflects the degeneracy of the top of the valence and bottom of the conduction band characteristic of graphene quantum dots with C3 symmetry. We study the interaction of multi-electron and hole complexes as a function of quantum dot size, shape and strength of Coulomb interactions. We identify two degenerate bright exciton (X) states and a corresponding biexciton (XX) state as XX-X cascade candidates, a source of entangled photon pairs. We next calculate the exciton to bi-exciton transitions detected in transient absorption experiments to extract the strength of exciton-exciton interactions and biexciton binding energies. We further explore the possibility of excitonic instability.

  18. Light-hole exciton in a nanowire quantum dot

    NASA Astrophysics Data System (ADS)

    Jeannin, Mathieu; Artioli, Alberto; Rueda-Fonseca, Pamela; Bellet-Amalric, Edith; Kheng, Kuntheak; André, Régis; Tatarenko, Serge; Cibert, Joël; Ferrand, David; Nogues, Gilles

    2017-01-01

    Quantum dots inserted inside semiconductor nanowires are extremely promising candidates as building blocks for solid-state-based quantum computation and communication. They provide very high crystalline and optical properties and offer a convenient geometry for electrical contacting. Having a complete determination and full control of their emission properties is one of the key goals of nanoscience researchers. Here we use strain as a tool to create in a single magnetic nanowire quantum dot a light-hole exciton, an optically active quasiparticle formed from a single electron bound to a single light hole. In this frame, we provide a general description of the mixing within the hole quadruplet induced by strain or confinement. A multi-instrumental combination of cathodoluminescence, polarization-resolved Fourier imaging, and magneto-optical spectroscopy, allows us to fully characterize the hole ground state, including its valence band mixing with heavy-hole states.

  19. Exciton polarizability in semiconductor nanocrystals.

    PubMed

    Wang, Feng; Shan, Jie; Islam, Mohammad A; Herman, Irving P; Bonn, Mischa; Heinz, Tony F

    2006-11-01

    The response of charge to externally applied electric fields is an important basic property of any material system, as well as one critical for many applications. Here, we examine the behaviour and dynamics of charges fully confined on the nanometre length scale. This is accomplished using CdSe nanocrystals of controlled radius (1-2.5 nm) as prototype quantum systems. Individual electron-hole pairs are created at room temperature within these structures by photoexcitation and are probed by terahertz (THz) electromagnetic pulses. The electronic response is found to be instantaneous even for THz frequencies, in contrast to the behaviour reported in related measurements for larger nanocrystals and nanocrystal assemblies. The measured polarizability of an electron-hole pair (exciton) amounts to approximately 10(4) A(3) and scales approximately as the fourth power of the nanocrystal radius. This size dependence and the instantaneous response reflect the presence of well-separated electronic energy levels induced in the system by strong quantum-confinement effects.

  20. Exciton transport and dissociation at organic interfaces

    NASA Astrophysics Data System (ADS)

    Beljonne, David

    2011-03-01

    This paper focuses on modeling studies of exciton transport and dissociation at organic interfaces and includes three parts: 1) Experiments have shown that the values of exciton diffusion length LD in conjugated polymers (CPs) are rather low, in the range of 5-10 nm, apparently regardless of their chemical structure and solid-state packing. In contrast, larger LD values have been reported in molecular materials that are chemically more well-defined than CPs. Here we demonstrate that energetic disorder alone reduces the exciton diffusion length more than one order of magnitude, from values typically encountered in molecules (> 50nm) to values actually measured in CPs (<10nm). 2) A number of organic crystals show anisotropic excitonic couplings, with weak interlayer interactions between molecules that are more strongly coupled within the layers. The resulting energy carriers are intra-layer 2D excitons that diffuse along the interlayer direction. We model this analytically for infinite layers and using quantum-chemical calculations of the electronic couplings for anthracene clusters. We show that the exciton hopping rates and diffusion lengths depend in a subtle manner on the size and shape of the interacting aggregates, temperature and the presence of energetic disorder. 3) The electronic structure at organic/organic interfaces plays a key role, among others, in defining the quantum efficiency of organic-based photovoltaic cells. Here, we perform quantum-chemical and microelectrostatic calculations on molecular aggregates of various sizes and shapes to characterize the interfacial dipole moment at pentacene/C60 heterojunctions. The results show that the interfacial dipole mostly originates in polarization effects due to the asymmetry in the multipolar expansion of the electronic density distribution between the interacting molecules. We will discuss how the quadrupoles on the pentacene molecules produce direct electrostatic interactions with charge carriers and how

  1. Conduction electrons in acceptor-doped GaAs/GaAlAs heterostructures: a review

    NASA Astrophysics Data System (ADS)

    Zawadzki, Wlodek; Raymond, Andre; Kubisa, Maciej

    2016-05-01

    We review magneto-optical and magneto-transport effects in GaAs/GaAlAs heterostructures doped in GaAlAs barriers with donors, providing two-dimensional (2D) electron gas (2DEG) in GaAs quantum wells (QWS), and additionally doped with smaller amounts of acceptors (mostly Be atoms) in the vicinity of 2DEG. One may also deal with residual acceptors (mostly C atoms). The behavior of such systems in the presence of a magnetic field differs appreciably from those doped in the vicinity of 2DEG with donors. Three subjects related to the acceptor-doped heterostructures are considered. First is the problem of bound states of conduction electrons confined to the vicinity of negatively charged acceptors by the joint effect of a QW and an external magnetic field parallel to the growth direction. A variational theory of such states is presented, demonstrating that an electron turning around a repulsive center has discrete energies above the corresponding Landau levels. Experimental evidence for the discrete electron energies comes from the work on interband photo-magneto-luminescence, intraband cyclotron resonance and quantum magneto-transport (the Quantum Hall and Shubnikov-de Haas effects). An electron rain-down effect at weak electric fields and a boil-off effect at strong electric fields are introduced. It is demonstrated, both theoretically and experimentally, that a negatively charged acceptor can localize more than one electron. The second subject describes experiment and theory of asymmetric quantized Hall and Shubnikov-de Haas plateaus in acceptor-doped GaAs/GaAlAs heterostructures. It is shown that the main features of the plateau asymmetry can be attributed to asymmetric density of Landau states in the presence of acceptors. However, at high magnetic fields, the rain-down effect is also at work. The third subject deals with the so-called disorder modes (DMs) in the cyclotron resonance of conduction electrons. The DMs originate from random distributions of negatively

  2. Optically decomposed near-band-edge structure and excitonic transitions in Ga2S3

    PubMed Central

    Ho, Ching-Hwa; Chen, Hsin-Hung

    2014-01-01

    The band-edge structure and band gap are key parameters for a functional chalcogenide semiconductor to its applications in optoelectronics, nanoelectronics, and photonics devices. Here, we firstly demonstrate the complete study of experimental band-edge structure and excitonic transitions of monoclinic digallium trisulfide (Ga2S3) using photoluminescence (PL), thermoreflectance (TR), and optical absorption measurements at low and room temperatures. According to the experimental results of optical measurements, three band-edge transitions of EA = 3.052 eV, EB = 3.240 eV, and EC = 3.328 eV are respectively determined and they are proven to construct the main band-edge structure of Ga2S3. Distinctly optical-anisotropic behaviors by orientation- and polarization-dependent TR measurements are, respectively, relevant to distinguish the origins of the EA, EB, and EC transitions. The results indicated that the three band-edge transitions are coming from different origins. Low-temperature PL results show defect emissions, bound-exciton and free-exciton luminescences in the radiation spectra of Ga2S3. The below-band-edge transitions are respectively characterized. On the basis of experimental analyses, the optical property of near-band-edge structure and excitonic transitions in the monoclinic Ga2S3 crystal is revealed. PMID:25142550

  3. Excitonic effects in third-harmonic generation: The case of carbon nanotubes and nanoribbons

    NASA Astrophysics Data System (ADS)

    Attaccalite, C.; Cannuccia, E.; Grüning, M.

    2017-03-01

    Linear and nonlinear optical properties of low-dimensional nanostructures have attracted great interest from the scientific community as tools to probe the strong confinement of electrons and for possible applications in optoelectronic devices. In particular it has been shown that the linear optical response of carbon nanotubes [F. Wang et al., Science 308, 838 (2005), 10.1126/science.1110265] and graphene nanoribbons [Nat. Commun. 5 4253 (2014), 10.1038/ncomms5253] is dominated by bounded electron-hole pairs, excitons. The role of excitons in linear response has been widely studied, but still, little is known about their effect on nonlinear susceptibilities. Using a recently developed methodology [Phys. Rev. B 88, 235113 (2013), 10.1103/PhysRevB.88.235113] based on well-established ab initio many-body perturbation theory approaches, we find that quasiparticle shifts and excitonic effects significantly modify the third-harmonic generation in carbon nanotubes and graphene nanoribbons. For both systems the net effect of many-body effects is to reduce the intensity of the main peak in the independent-particle spectrum and redistribute the spectral weight among several excitonic resonances.

  4. Excitons in a quasi-one-dimensional quantum nanorod under a strong electric field

    SciTech Connect

    Lyo, S. K.

    2014-03-21

    The response of an exciton in the ground and first excited states to a strong DC electric field is studied in a quasi-one-dimensional nano quantum well (i.e., nanorod) bounded by high symmetric barriers by studying the energy, the oscillator strength, the root-mean-square (RMS) average of the electron-hole (e-h) separation, and the average positions of the electron and the hole. The interplaying effect between the barrier confinement, e-h attraction, and the field-induced e-h separation for exciton binding is examined. We find that, for a long nanorod, the exciton energy, as well as, the oscillator strength drops abruptly as a function of the field near the exciton-dissociation field while the RMS average of the e-h separation rises rapidly. For shorter rods, the transition is more gradual due to the combined effect of the confinement and the long-range e-h interaction. A strong field is shown to transform the optically-inactive first excited state into an optically-active state in the field range between the dissociation field of the ground state and that of the first excited level. We also find that, in the ground state, the (lighter) electron is dragged by the (heavier) hole below the dissociation field. The dependence of the above mentioned properties on the rod length is also investigated for varying fields. The results are compared with those obtained for the rods with parabolic confinement.

  5. Dissociating excitons photogenerated in semiconducting carbon nanotubes at polymeric photovoltaic heterojunction interfaces.

    PubMed

    Bindl, Dominick J; Safron, Nathaniel S; Arnold, Michael S

    2010-10-26

    Semiconducting single-walled carbon nanotubes (s-SWCNTs) have strong near-infrared and visible absorptivity and exceptional charge transport characteristics, rendering them highly attractive semiconductor absorbers for photovoltaic and photodetector technologies. However, these applications are limited by a poor understanding of how photogenerated charges, which are bound as excitons in s-SWCNTs, can be dissociated in large-area solid-state devices. Here, we measure the dissociation of excitons in s-SWCNT thin films that form planar heterojunction interfaces with polymeric photovoltaic materials using an exciton dissociation-sensitive photocapacitor measurement technique that is advantageously insensitive to optically induced thermal photoconductive effects. We find that fullerene and polythiophene derivatives induce exciton dissociation, resulting in electron and hole transfer, respectively, away from optically excited s-SWCNTs. Significantly weaker or no charge transfer is observed using wider gap polymers due to insufficient energy offsets. These results are expected to critically guide the development of thin film s-SWCNT-based photosensitive devices.

  6. Localised and delocalised excitons in star-like squaraine homo- and heterotrimers.

    PubMed

    Ceymann, Harald; Balkenhohl, Moritz; Schmiedel, Alexander; Holzapfel, Marco; Lambert, Christoph

    2016-01-28

    Exciton coupling of localised chromophore states within covalently bound superchromophores is a viable strategy to modify optical properties such as spectral broadening and red-shifting of absorption bands. These are desirable properties for e.g. organic photovoltaic applications. Attaching three squaraine dyes to a central nitrogen core in a star-shaped manner leads to the formation of superchromophores that may form localised and delocalised excitons upon photoexcitation. In this work we investigated two homotrimers, two heterotrimers and a heterodimer formed by the combination of two different squaraines SQA and SQB. Due to exciton coupling the two homotrimers display a red shift of the main absorption band by about 1000 cm(-1) compared to their monomeric reference compounds. On the other hand, the heterotrimers show a broadening of the absorption spectra with three peak maxima at the exciton manifold band. In fluorescence experiments the homotrimers display signals similar to the emission of the monomeric compounds but red shifted. However, the heterotrimers and the heterodimer show, beside emission from the delocalised lowest energy state, an additional signal that overlaps strongly with the absorption. Excitation and time-dependent emission spectra of the hetero compounds indicate that this emission stems from a localised higher energy state. This interpretation is corroborated by transient absorption measurements with fs-time resolution.

  7. Two-Exciton and Exciton-Magnon Bands in DIMANGANESE(+) Magnets.

    NASA Astrophysics Data System (ADS)

    Darwish, Saqer Mohammed

    The temperature dependence of several exciton -magnon and two-exciton bands in the optical absorption spectra of three antiferromagnets have been studied using a Cary 14 spectrophotometer in conjunction with an Air Product Displex, closed-cycle helium refrigerator. The three antiferromagnets with their T_{ rm N} are: KMnF_3, T_{rm N} = 88.3 K; RbMnF_3, T_{ rm N} = 82.6 K; and MnF_2 , T_{rm N} = 67.3 K. In this work the temperature dependence (10 ^circK to 300^ circK) of the line position E, the oscillator strength f, and the half-width of half maximum delta, for several of these bands were measured. For the two-exciton bands f increases where as for the exciton-magnon and exciton-magnon-phonon bands f decreases as the temperature is lowered through T _{rm N}. The temperature dependence of f for the two-exciton bands in the three antiferromagnets agrees well with the theoretical predictions of Fujiwara et al. For the exciton-magnon bands, f increases with increasing T up to T_{rm N} and then remains essentially constant above T_{rm N}, in reasonable agreement with the theory of Shinagawa and Tanabe. For the exciton-magnon-phonon bands, a slight increase in f above T_{rm N} is believed to be due to the role of a phonon. The temperature dependence of the line positions E(T) is also different for the exciton-magnon and two-exciton bands. The exciton-magnon or exciton-magnon-phonon bands undergo a blue shift in E(T) as the temperature is lowered through T_{rm N}. This is semiquantitatively understood in terms of the exchange field using the molecular field theory of Yen et al. On the other hand, most of the two-exciton bands do not show any anomaly in E(T) below T_{rm N}. Instead their line positions are described well by the Einstein-type relation E(T) = E(O) + A ^{*}/ (exp(T^ {*}/T) - 1), where T^{*} represents an odd symmetry phonon with frequency upsilon * = kT^{*} /h. Above T_{rm N} , the exciton-magnon-phonon bands also follow the same equation. From these fits

  8. Microscopic theory of two-dimensional spatially-indirect-exciton condensates and exciton-polariton condensates

    NASA Astrophysics Data System (ADS)

    Xue, Fei; Wu, Feng Cheng; MacDonald, Allan

    BEC of excitons and polaritons have drawn attention in recent years because of the demonstration of their ability to host macroscopic quantum phenomena and because of their promise for applications. We study the case of a system containing two TMD monolayers that are separated and surrounded by h-BN. Under appropriate conditions this system is expected to support a spatially indirect thermal equilibrium exciton condensate. We combine a microscopic mean-field calculation and a weakly interacting boson model to explore the bilayer exciton condensates phase diagram. By varying the layer separation and exciton density, we find a phase transition occurs between states containing one and two condensate flavors. We also use a microscopic time-dependent mean-field theory to address condensate collective mode spectra and quantum fluctuations. Next we study the case of exciton-polariton formed by strong coupling between quantum well excitons and confined photon modes when the system is placed in a vertical microcavity. We build a microscopic mean-field theory starting from electrons and holes, and account for their coupling to coherent light field. We compare our model with the normal weakly interacting boson model that starts from weakly interacting excitons that are coupled to photons. This work was supported by the SRC and NIST under the Nanoelectronic Research Initiative (NRI) and SWAN, by the Welch Foundation under Grant No. F1473, and by the ARO Grant No. 26-3508-81.

  9. Electron Donor Acceptor Interactions. Final Progress Report

    SciTech Connect

    2002-08-16

    The Gordon Research Conference (GRC) on Electron Donor Acceptor Interactions was held at Salve Regina University, Newport, Rhode Island, 8/11-16/02. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  10. Theoretical characterization on photoelectric properties of benzothiadiazole- and fluorene-based small molecule acceptor materials for the organic photovoltaics.

    PubMed

    Sui, Mingyue; Li, Shuangbao; Pan, Qingqing; Sun, Guangyan; Geng, Yun

    2017-01-01

    The upper efficiency of heterojunction organic photovoltaics depends on the increased open-circuit voltage (V oc) and short-circuit current (J sc). So, a higher lowest unoccupied molecular orbital (LUMO) level is necessary for organic acceptor material to possess higher V oc and more photons absorbsorption in the solar spectrum is needed for larger J sc. In this article, we theoretically designed some small molecule acceptors (2∼5) based on fluorene (F), benzothiadiazole, and cyano group (CN) referring to the reported acceptor material 2-[{7-(9,9-di-n-propyl-9H-fluoren-2-yl)benzo[c][1,2,5]thiadiazol-4-yl}methylene]malononitrile (1), the crucial parameters affecting photoelectrical properties of compounds 2∼5 were evaluated by the density functional theory (DFT) and time dependent density functional theory (TDDFT) methods. The results reveal that compared with 1, 3 and 4 could have the better complementary absorption spectra with P3HT, the increased LUMO level, the improved V oc, and the decreased electronic organization energy (λ e). From the simulation of transition density matrix, it is very clear that the excitons of molecules 3 and 4 are easier to separate in the material surface. Therefore, 3 and 4 may become potential acceptor candidates for organic photovoltaic cells. In addition, with the increased number of CN, the optoelectronic properties of the molecules show a regular change, mainly improve the LUMO level, energy gap, V oc, and absorption intensity. In summary, reasonably adjusting CN can effectively improve the photovoltaic properties of small molecule acceptors. Graphical Abstract Structure-property relationship of small molecule acceptors could be rationally evaluated in the article. The changes of conjugate length and CN are important strategies to alter the photovoltaic properties of small molecule acceptors. Therefore, taking the K12/1 as a reference, we have theoretically designed a series of small molecule acceptors (2-4). The calculated

  11. Excitons in Time-Dependent Density-Functional Theory.

    PubMed

    Ullrich, Carsten A; Yang, Zeng-hui

    2016-01-01

    This chapter gives an overview of the description of the optical and dielectric properties of bulk insulators and semiconductors in time-dependent density-functional theory (TDDFT), with an emphasis on excitons. We review the linear-response formalism for periodic solids, discuss excitonic exchange-correlation kernels, calculate exciton binding energies for various materials, and compare the treatment of excitons with TDDFT and with the Bethe-Salpeter equation.

  12. Probing Bose-Einstein condensation of excitons with electromagnetic radiation.

    PubMed

    Johnsen, K; Kavoulakis, G M

    2001-01-29

    We examine the absorption spectrum of electromagnetic radiation from excitons, where an exciton in the 1s state absorbs a photon and makes a transition to the 2p state. We demonstrate that the absorption spectrum depends strongly on the quantum degeneracy of the exciton gas, and that it will generally manifest many-body effects. Based on our results we propose that absorption of infrared radiation could resolve recent contradictory experimental results on excitons in Cu(2)O.

  13. Influence of excitonic effects on luminescence quantum yield in silicon

    NASA Astrophysics Data System (ADS)

    Sachenko, A. V.; Kostylyov, V. P.; Vlasiuk, V. M.; Sokolovskyi, I. O.; Evstigneev, M.

    2017-03-01

    Nonradiative exciton lifetime in silicon is determined by comparison of the experimental and theoretical curves of bulk minority charge carriers lifetime on doping and excitation levels. This value is used to analyze the influence of excitonic effects on internal luminescence quantum yield at room temperature, taking into account both nonradiative and radiative exciton lifetimes. A range of Shockley-Hall-Reed lifetimes is found, where excitonic effects lead to an increase of internal luminescence quantum yield.

  14. Excitonic interaction in the fluorene dimer

    NASA Astrophysics Data System (ADS)

    Wessel, John; Beck, Steven; Highstrete, Clark

    1994-12-01

    The fluorene van der Waals dimer exhibits a complex origin spectrum. This region has been studied by resonance two-photon ionization and by fluorescence excitation spectroscopies. The spectra can be interpreted on the basis of intermediate strength exciton coupling, in which the electronic interaction is comparable to the van der Waals vibrational energies. The spectra are reasonably well described by two distorted adiabatic potential surfaces, which correspond to the two excitonic components of the origin system. A single Franck-Condon active intermolecular mode provides a reasonable description of the system, however the potentials have significant cubic and quartic contributions. Non-Born-Oppenheimer nuclear momentum coupling is present and intermodal (IVR) interactions are observed, even for intermolecular modes as low as v=1. The results are remarkably different from prior observations of excitonic structure in other systems, providing a detailed picture of coupling between electronic and intermolecular motion in a van der Waals dimer.

  15. Exciton dynamics in perturbed vibronic molecular aggregates

    PubMed Central

    Brüning, C.; Wehner, J.; Hausner, J.; Wenzel, M.; Engel, V.

    2015-01-01

    A site specific perturbation of a photo-excited molecular aggregate can lead to a localization of excitonic energy. We investigate this localization dynamics for laser-prepared excited states. Changing the parameters of the electric field significantly influences the exciton localization which offers the possibility for a selective control of this process. This is demonstrated for aggregates possessing a single vibrational degree of freedom per monomer unit. It is shown that the effects identified for the molecular dimer can be generalized to larger aggregates with a high density of vibronic states. PMID:26798840

  16. Exciton dynamics in conjugated polymer photovoltaics: Steady-state and time-resolved optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Chasteen, Stephanie V.

    The performance of organic photovoltaics is severely limited by poor exciton dissociation and charge transport due in part to high rates of exciton recombination and low charge mobilities in polymers. This challenge can be partially overcome through the use of blended and layered heterojunctions. Such morphologies offer multiple exciton dissociation sites and separate charge pathways, thus limiting exciton recombination, and allowing for thicker, more absorbing, polymer films. I have performed photovoltaic device characterization and time-resolved and steady-state photoluminescence on a variety of donor-acceptor heterojunction. I have used these methods to understand excited state dynamics and how they affect device performance. As hole-transporters I use a derivative of poly-phenylene-vinylene (M3EH-PPV) and poly-3-hexylthiophene (P3HT). As electron-transporters I use the metal oxide titanium dioxide (TiO2), the electron-transporter CN-PPV, and a fullerene derivative (PCBM). These materials are layered and blended together to form donor-acceptor heterojunctions. All heterojunctions result in enhanced device performance, and 1:4 M3EH-PPV:PCBM resulted in the highest efficiencies. M3EH-PPV emission is characterized by single-chain excitations, and the decay is dominated by short components of 0.20 and 0.45 ns. CN-ether-PPV is dominated by interchain excited state species---ie., excimers---with a decay time of 14.0 ns. The broken conjugation imposed by the ether group affect the excited state, resulting in an excited state species that is particularly vulnerable to quenching. This has important ramifications for material design. Hole-transporting polymers blended and layered with CN-ether-PPV have high currents (Jsc up to 3.3 mA/cm2) and good quenching relative to CN-ether-PPV (˜90%) due to charge separation and generation, respectively. Hole-transporters blended with PCBM result in efficient devices (Jsc up to 14 mA/cm2) due to rapid charge transfer and the

  17. Excitons in van der Waals heterostructures: The important role of dielectric screening

    NASA Astrophysics Data System (ADS)

    Latini, S.; Olsen, T.; Thygesen, K. S.

    2015-12-01

    The existence of strongly bound excitons is one of the hallmarks of the newly discovered atomically thin semiconductors. While it is understood that the large binding energy is mainly due to the weak dielectric screening in two dimensions, a systematic investigation of the role of screening on two-dimensional (2D) excitons is still lacking. Here we provide a critical assessment of a widely used 2D hydrogenic exciton model, which assumes a dielectric function of the form ɛ (q )=1 +2 π α q , and we develop a quasi-2D model with a much broader applicability. Within the quasi-2D picture, electrons and holes are described as in-plane point charges with a finite extension in the perpendicular direction, and their interaction is screened by a dielectric function with a nonlinear q dependence which is computed ab initio. The screened interaction is used in a generalized Mott-Wannier model to calculate exciton binding energies in both isolated and supported 2D materials. For isolated 2D materials, the quasi-2D treatment yields results almost identical to those of the strict 2D model, and both are in good agreement with ab initio many-body calculations. On the other hand, for more complex structures such as supported layers or layers embedded in a van der Waals heterostructure, the size of the exciton in reciprocal space extends well beyond the linear regime of the dielectric function, and a quasi-2D description has to replace the 2D one. Our methodology has the merit of providing a seamless connection between the strict 2D limit of isolated monolayer materials and the more bulk-like screening characteristics of supported 2D materials or van der Waals heterostructures.

  18. Bright and dark excitons in semiconductor carbon nanotubes

    SciTech Connect

    Tretiak, Sergei

    2008-01-01

    We report electronic structure calculations of finite-length semiconducting carbon nanotubes using the time dependent density functional theory (TD-DFT) and the time dependent Hartree Fock (TD-HF) approach coupled with semiempirical AM1 and ZINDO Hamiltonians. We specifically focus on the energy splitting, relative ordering, and localization properties of the optically active (bright) and optically forbidden (dark) states from the lowest excitonic band of the nanotubes. These excitonic states are very important in competing radiative and non-radiative processes in these systems. Our analysis of excitonic transition density matrices demonstrates that pure DFT functionals overdelocalize excitons making an electron-hole pair unbound; consequently, excitonic features are not presented in this method. In contrast, the pure HF and A111 calculations overbind excitons inaccurately predicting the lowest energy state as a bright exciton. Changing AM1 with ZINDO Hamiltonian in TD-HF calculations, predicts the bright exciton as the second state after the dark one. However, in contrast to AM1 calculations, the diameter dependence of the excitation energies obtained by ZINDO does not follow the experimental trends. Finally, the TD-DFT approach incorporating hybrid functions with a moderate portion of the long-range HF exchange, such as B3LYP, has the most generality and predictive capacity providing a sufficiently accurate description of excitonic structure in finite-size nanotubes. These methods characterize four important lower exciton bands. The lowest state is dark, the upper band is bright, and the two other dark and nearly degenerate excitons lie in-between. Although the calculated energy splittings between the lowest dark and the bright excitons are relatively large ({approx}0.1 eV), the dense excitonic manifold below the bright exciton allows for fast non-radiative relaxation leasing to the fast population of the lowest dark exciton. This rationalizes the low

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  20. Temperature Evolution of Excitonic Absorptions in Cd(1-x)Zn(x)Te Materials

    NASA Technical Reports Server (NTRS)

    Quijada, Manuel A.; Henry, Ross

    2007-01-01

    The studies consist of measuring the frequency dependent transmittance (T) and reflectance (R) above and below the optical band-gap in the UV/Visible and infrared frequency ranges for Cd(l-x),Zn(x),Te materials for x=0 and x=0.04. Measurements were also done in the temperature range from 5 to 300 K. The results show that the optical gap near 1.49 eV at 300 K increases to 1.62 eV at 5 K. Finally, we observe sharp absorption peaks near this gap energy at low temperatures. The close proximity of these peaks to the optical transition threshold suggests that they originate from the creation of bound electron-hole pairs or excitons. The decay of these excitonic absorptions may contribute to a photoluminescence and transient background response of these back-illuminated HgCdTe CCD detectors.

  1. High-temperature superfluidity with indirect excitons in van der Waals heterostructures.

    PubMed

    Fogler, M M; Butov, L V; Novoselov, K S

    2014-07-28

    All known superfluid and superconducting states of condensed matter are enabled by composite bosons (atoms, molecules and Cooper pairs) made of an even number of fermions. Temperatures where such macroscopic quantum phenomena occur are limited by the lesser of the binding energy and the degeneracy temperature of the bosons. High-critical temperature cuprate superconductors set the present record of ~100 K. Here we propose a design for artificially structured materials to rival this record. The main elements of the structure are two monolayers of a transition metal dichalcogenide separated by an atomically thin spacer. Electrons and holes generated in the system would accumulate in the opposite monolayers and form bosonic bound states--the indirect excitons. The resultant degenerate Bose gas of indirect excitons would exhibit macroscopic occupation of a quantum state and vanishing viscosity at high temperatures.

  2. High-temperature superfluidity with indirect excitons in van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Fogler, M. M.; Butov, L. V.; Novoselov, K. S.

    2014-07-01

    All known superfluid and superconducting states of condensed matter are enabled by composite bosons (atoms, molecules and Cooper pairs) made of an even number of fermions. Temperatures where such macroscopic quantum phenomena occur are limited by the lesser of the binding energy and the degeneracy temperature of the bosons. High-critical temperature cuprate superconductors set the present record of ~100 K. Here we propose a design for artificially structured materials to rival this record. The main elements of the structure are two monolayers of a transition metal dichalcogenide separated by an atomically thin spacer. Electrons and holes generated in the system would accumulate in the opposite monolayers and form bosonic bound states—the indirect excitons. The resultant degenerate Bose gas of indirect excitons would exhibit macroscopic occupation of a quantum state and vanishing viscosity at high temperatures.

  3. Free-exciton states in crystalline GaTe

    NASA Astrophysics Data System (ADS)

    Wan, J. Z.; Brebner, J. L.; Leonelli, R.

    1995-12-01

    Polarized properties of both the singlet and triplet ground exciton states in the photoluminescence and transmission spectra of crystalline GaTe are explained based on the possible symmetry properties of the energy band edge of GaTe. Some experimental results about excited exciton states in GaTe are presented and discussed. The energy positions of exciton series in GaTe follow the three-dimensional direct allowed Wannier exciton formula just as in the the other III-VI layered compounds of GaSe and InSe. The nonthermalized, ``hot'' nature of excitons inside GaTe under higher optical excitation intensities is also discussed.

  4. Exciton dynamics in a single layer MoS2

    NASA Astrophysics Data System (ADS)

    Kim, Jonghwan; Hong, Xiaoping; Shi, Sufei; Jin, Chenhao; Sun, Yinghui; Wang, Feng

    2014-03-01

    In a low dimensional semiconductor, exciton plays a crucial role in the optical property. Recently, a single layer of MoS2 has attracted significant attention due to its unique excitonic features. For example, exciton in MoS2 is predicted to have order of magnitude larger binding energy than conventional direct band gap material. For deeper understanding on such properties, however, it is important to understand how exciton is formed and decays in time domain. Our work on exciton dynamics in MoS2 by pump probe spectroscopy will be presented with control of both power and wavelength.

  5. Identifying electron transfer coordinates in donor-bridge-acceptor systems using mode projection analysis

    PubMed Central

    Yang, Xunmo; Keane, Theo; Delor, Milan; Meijer, Anthony J. H. M.; Weinstein, Julia; Bittner, Eric R.

    2017-01-01

    We report upon an analysis of the vibrational modes that couple and drive the state-to-state electronic transfer branching ratios in a model donor-bridge-acceptor system consisting of a phenothiazine-based donor linked to a naphthalene-monoimide acceptor via a platinum-acetylide bridging unit. Our analysis is based upon an iterative Lanczos search algorithm that finds superpositions of vibronic modes that optimize the electron/nuclear coupling using input from excited-state quantum chemical methods. Our results indicate that the electron transfer reaction coordinates between a triplet charge-transfer state and lower lying charge-separated and localized excitonic states are dominated by asymmetric and symmetric modes of the acetylene groups on either side of the central atom in this system. In particular, we find that while a nearly symmetric mode couples both the charge-separation and charge-recombination transitions more or less equally, the coupling along an asymmetric mode is far greater suggesting that IR excitation of the acetylene modes preferentially enhances charge-recombination transition relative to charge-separation. PMID:28233775

  6. Engineering excitonic dynamics and environmental stability of post-transition metal chalcogenides by pyridine functionalization technique

    NASA Astrophysics Data System (ADS)

    Meng, Xiuqing; Pant, Anupum; Cai, Hui; Kang, Jun; Sahin, Hasan; Chen, Bin; Wu, Kedi; Yang, Sijie; Suslu, Aslihan; Peeters, F. M.; Tongay, Sefaattin

    2015-10-01

    Owing to their strong photon emission, low excitonic binding energies, and nearly-ideal band offset values for water splitting reactions, direct gap quasi-2D gallium chalcogenides are potential candidates for applications in energy harvesting, optoelectronics, and photonics. Unlike other 2D materials systems, chemical functionalization of gallium chalcogenides is still at its seminal stages. Here, we propose vapor phase pyridine intercalation technique to manipulate optical properties of gallium chalcogenides. After functionalization, the excitonic dynamics of quasi-2D GaSe change significantly as evidenced by an increase in integrated PL intensity and emergence of a new emission feature that is below the band edge. Based on our DFT calculations, we attribute these to formation of bound exciton complexes at the trap sites introduced by chemical reaction between pyridine and GaSe. On the contrary, pyridine functionalization does not impact the optical properties of GaTe, instead treats GaTe surface to prevent oxidization of tellurium atoms. Overall, results suggest novel ways to control properties of gallium chalcogenides on demand and unleash their full potential for a range of applications in photonics and optoelectronics.Owing to their strong photon emission, low excitonic binding energies, and nearly-ideal band offset values for water splitting reactions, direct gap quasi-2D gallium chalcogenides are potential candidates for applications in energy harvesting, optoelectronics, and photonics. Unlike other 2D materials systems, chemical functionalization of gallium chalcogenides is still at its seminal stages. Here, we propose vapor phase pyridine intercalation technique to manipulate optical properties of gallium chalcogenides. After functionalization, the excitonic dynamics of quasi-2D GaSe change significantly as evidenced by an increase in integrated PL intensity and emergence of a new emission feature that is below the band edge. Based on our DFT calculations

  7. (Gene sequencing by scanning molecular exciton microscopy)

    SciTech Connect

    Not Available

    1991-01-01

    This report details progress made in setting up a laboratory for optical microscopy of genes. The apparatus including a fluorescence microscope, a scanning optical microscope, various spectrometers, and supporting computers is described. Results in developing photon and exciton tips, and in preparing samples are presented. (GHH)

  8. Multiple exciton generation in colloidal silicon nanocrystals.

    PubMed

    Beard, Matthew C; Knutsen, Kelly P; Yu, Pingrong; Luther, Joseph M; Song, Qing; Metzger, Wyatt K; Ellingson, Randy J; Nozik, Arthur J

    2007-08-01

    Multiple exciton generation (MEG) is a process whereby multiple electron-hole pairs, or excitons, are produced upon absorption of a single photon in semiconductor nanocrystals (NCs) and represents a promising route to increased solar conversion efficiencies in single-junction photovoltaic cells. We report for the first time MEG yields in colloidal Si NCs using ultrafast transient absorption spectroscopy. We find the threshold photon energy for MEG in 9.5 nm diameter Si NCs (effective band gap identical with Eg = 1.20 eV) to be 2.4 +/- 0.1Eg and find an exciton-production quantum yield of 2.6 +/- 0.2 excitons per absorbed photon at 3.4Eg. While MEG has been previously reported in direct-gap semiconductor NCs of PbSe, PbS, PbTe, CdSe, and InAs, this represents the first report of MEG within indirect-gap semiconductor NCs. Furthermore, MEG is found in relatively large Si NCs (diameter equal to about twice the Bohr radius) such that the confinement energy is not large enough to produce a large blue-shift of the band gap (only 80 meV), but the Coulomb interaction is sufficiently enhanced to produce efficient MEG. Our findings are of particular importance because Si dominates the photovoltaic solar cell industry, presents no problems regarding abundance and accessibility within the Earth's crust, and poses no significant environmental problems regarding toxicity.

  9. 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.

  10. Free and trapped hybrid charge transfer excitons at a ZnO/small-molecule heterojunction

    NASA Astrophysics Data System (ADS)

    Panda, Anurag; Ding, Kan; Liu, Xiao; Forrest, Stephen R.

    2016-09-01

    We study the temperature-dependent electrical and optical properties of hybrid charge transfer excitons (HCTEs) at a ZnO/4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) organic/inorganic semiconductor heterojunction (OI-HJ). The electroluminescence spectrum of the HCTE formed by recombination of injected charge undergoes a hypsochromic shift from 1.65 ± 0.01 eV to 2.05 ± 0.01 eV with decreasing temperature from T =300 K to 30 K at a current density of J =100 mA c m-2 , and with increasing voltage from V =1.5 V to 4.5 V. We observe an external quantum efficiency of 6.0 ± 0.2% at a wavelength of 332 nm for excitons generated in CBP, indicating exciton to charge conversion via HCTEs. However, no HCTE photoluminescence is observed at temperatures as low as T =25 K . A quantum mechanical model based on the coexistence of both free and trapped singlet HCTE states at the OI-HJ describes these observations. The free HCTE consists of a hole in CPB Coulombically bound with an energy of 9 meV to a delocalized electron in ZnO, and it is the precursor to photocurrent generation via CBP Frenkel excitons. The observed electroluminescence is due to electron injection into localized defect states at the ZnO surface that are bound to holes in CBP forming a trapped HCTE with binding energies of 60-430 meV and oscillator strength that is four orders of magnitude higher compared to the free HCTE.

  11. Coupled exciton-photon Bose condensate in path integral formalism

    NASA Astrophysics Data System (ADS)

    Elistratov, A. A.; Lozovik, Yu. E.

    2016-03-01

    We study the behavior of exciton polaritons in an optical microcavity with an embedded semiconductor quantum well. We use a two-component exciton-photon approach formulated in terms of path integral formalism. In order to describe spatial distributions of the exciton and photon condensate densities, the two coupled equations of the Gross-Pitaevskii type are derived. For a homogeneous system, we find the noncondensate photon and exciton spectra, calculate the coefficients of transformation from the exciton-photon basis to the lower-upper polariton basis, and obtain the exciton and photon occupation numbers of the lower and upper polariton branches for nonzero temperatures. For an inhomogeneous system, the set of coupled equations of the Bogoliubov-de Gennes type is derived. The equations govern the spectra and spatial distributions of noncondensate photons and excitons.

  12. High Performance Magazine Acceptor Threshold Criteria

    DTIC Science & Technology

    1994-08-01

    detonation transition (DDT). To account for unknown mechanisms the term XDT is also used. Development of a design procedure to prevent SD requires...propagation walls are used to prevent sympathetic detonation between munitions stored in adjacent cells. Design of the walls, and their mitigation...effects, requires sympathetic detonation threshold criteria for acceptor munitions. This paper outlines the procedures being used to develop SD threshold

  13. Characterization of Macroscopic Ordering in Exciton Rings

    NASA Astrophysics Data System (ADS)

    Yang, Sen; Levitov, L. S.; Simons, B. D.; Gossard, A. C.

    2005-03-01

    Recently observed complex PL patterns in 2D QW structures exhibit the inner [1,3] and the outer [1-4] exciton rings, localized bright spots [1,3], and the macroscopically ordered exciton state (MOES) [1,3]. The latter appears at the outer ring via its fragmentation into a periodic array of aggregates. While the gross features have been explained within classical framework, attributing the inner rings to nonradiative exciton transport and cooling [1], and the outermost rings and the bright spots to macroscopic charge separation [3,4], the origin of the MOES remains unidentified [5]. Here, for the first time, we report experiments demonstrating the exciton energy modulation over the MOES as well as the phase diagram of MOES in exciton density and temperature coordinates. The experiments shed new light on the dynamical origin of MOES. Besides, we present the studies of dynamical processes within MOES including the observation of aggregate instabilities and bifurcations that point to the spontaneous character of the instability.[1] L.V. Butov, A.C. Gossard, D.S. Chemla, Nature 418, 751 (2002). [2] D. Snoke, S. Denev, Y. Liu, L. Pfeiffer, K. West, Nature 418, 754 (2002). [3] L.V. Butov, L.S. Levitov, A.V. Mintsev, B.D. Simons, A.C. Gossard, D.S. Chemla PRL 92, 117404 (2004). [4] R. Rapaport, G. Chen, D. Snoke, S.H. Simon, L. Pfeiffer, K. West, Y. Liu, S. Denev PRL 92, 117405 (2004). [5] L.S. Levitov, B.D. Simons, L.V. Butov, cond-mat/0403377.

  14. Molecular design of donor-acceptor dyes for efficient dye-sensitized solar cells I: a DFT study.

    PubMed

    El-Shishtawy, Reda M; Asiri, Abdullah M; Aziz, Saadullah G; Elroby, Shaaban A K

    2014-06-01

    Dye-sensitized solar cells (DSSCs) have drawn great attention as low cost and high performance alternatives to conventional photovoltaic devices. The molecular design presented in this work is based on the use of pyran type dyes as donor based on frontier molecular orbitals (FMO) and theoretical UV-visible spectra in combination with squaraine type dyes as an acceptor. Density functional theory has been used to investigate several derivatives of pyran type dyes for a better dye design based on optimization of absorption, regeneration, and recombination processes in gas phase. The frontier molecular orbital (FMO) of the HOMO and LUMO energy levels plays an important role in the efficiency of DSSCs. These energies contribute to the generation of exciton, charge transfer, dissociation and exciton recombination. The computations of the geometries and electronic structures for the predicted dyes were performed using the B3LYP/6-31+G** level of theory. The FMO energies (EHOMO, ELUMO) of the studied dyes are calculated and analyzed in the terms of the UV-visible absorption spectra, which have been examined using time-dependent density functional theory (TD-DFT) techniques. This study examined absorption properties of pyran based on theoretical UV-visible absorption spectra, with comparisons between TD-DFT using B3LYP, PBE, and TPSSH functionals with 6-31+G (d) and 6-311++G** basis sets. The results provide a valuable guide for the design of donor-acceptor (D-A) dyes with high molar absorptivity and current conversion in DSSCs. The theoretical results indicated 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dye (D2-Me) can be effectively used as a donor dye for DSSCs. This dye has a low energy gap by itself and a high energy gap with squaraine acceptor type dye, the design that reduces the recombination and improves the photocurrent generation in solar cell.

  15. Dynamics of exciton transfer in coupled polymer chains

    NASA Astrophysics Data System (ADS)

    Zhang, Y. L.; Liu, X. J.; Sun, Z.; An, Z.

    2013-05-01

    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.

  16. Solution-Processable Organic Molecule for High-Performance Organic Solar Cells with Low Acceptor Content.

    PubMed

    Wang, Kun; Guo, Bing; Xu, Zhuo; Guo, Xia; Zhang, Maojie; Li, Yongfang

    2015-11-11

    A new planar D2-A-D1-A-D2 structured organic molecule with bithienyl benzodithiophene (BDT) as central donor unit D1 and fluorine-substituted benzothiadiazole (BTF) as acceptor unit and alkyl-dithiophene as end group and donor unit D2, BDT-BTF, was designed and synthesized for the application as donor material in organic solar cells (OSCs). BDT-BTF shows a broad absorption in visible region, suitable highest occupied molecular orbital energy level of -5.20 eV, and high hole mobility of 1.07 × 10(-2) cm(2)/(V s), benefitted from its high coplanarity and strong crystallinity. The OSCs based on BDT-BTF as donor (D) and PC71BM as acceptor (A) at a D/A weight ratio of 3:1 without any extra treatment exhibit high photovoltaic performance with Voc of 0.85 V, Jsc of 10.48 mA/cm(2), FF of 0.66, and PCE of 5.88%. The morphological study by transmission electron microscopy reveals that the blend of BDT-BTF and PC71BM (3:1, w/w) possesses an appropriate interpenetrating D/A network for the exciton separation and charge carrier transport, which agrees well with the good device performance. The optimized D/A weight ratio of 3:1 is the lowest acceptor content in the active layer reported so far for the high-performance OSCs, and the organic molecules with the molecular structure like BDT-BTF could be promising high-performance donor materials in solution-processable OSCs.

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

    PubMed Central

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

    2016-01-01

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

  18. Quantum-confined emission and fluorescence blinking of individual exciton complexes in CdSe nanowires.

    PubMed

    Franz, Dennis; Reich, Aina; Strelow, Christian; Wang, Zhe; Kornowski, Andreas; Kipp, Tobias; Mews, Alf

    2014-11-12

    One-dimensional semiconductor nanostructures combine electron mobility in length direction with the possibility of tailoring the physical properties by confinement effects in radial direction. Here we show that thin CdSe quantum nanowires exhibit low-temperature fluorescence spectra with a specific universal structure of several sharp lines. The structure strongly resembles the pattern of bulk spectra but show a diameter-dependent shift due to confinement effects. Also the fluorescence shows a pronounced complex blinking behavior with very different blinking dynamics of different emission lines in one and the same spectrum. Time- and space-resolved optical spectroscopy are combined with high-resolution transmission electron microscopy of the very same quantum nanowires to establish a detailed structure-property relationship. Extensive numerical simulations strongly suggest that excitonic complexes involving donor and acceptor sites are the origin of the feature-rich spectra.

  19. Ultrafast excitonic and charge transfer dynamics in nanostructured organic polymer materials

    NASA Astrophysics Data System (ADS)

    Polkehn, Matthias; Eisenbrandt, Pierre; Tamura, Hiroyuki; Haacke, Stefan; Méry, Stéphane; Burghardt, Irene

    2016-04-01

    We present theoretical studies of elementary exciton and charge transfer processes in functional organic materials, in view of understanding the key microscopic factors that lead to efficient charge generation in photovoltaics applications. As highlighted by recent experiments, these processes can be guided by quantum coherence, despite the presence of static and dynamic disorder. Our approach combines first-principles parametrized Hamiltonians, based on Time-Dependent Density Functional Theory (TDDFT) and/or high-level electronic structure calculations, with accurate quantum dynamics simulations using the Multi-Configuration Time-Dependent Hartree (MCTDH) method. This contribution specifically addresses charge generation in a novel class of highly ordered oligothiophene-perylene diimide type co-oligomer assemblies, highlighting that chemical design of donor/acceptor combinations needs to be combined with a detailed understanding of the effects of molecular packing.

  20. Evaluation of deoxygenated oligosaccharide acceptor analogs as specific inhibitors of glycosyltransferases.

    PubMed

    Hindsgaul, O; Kaur, K J; Srivastava, G; Blaszczyk-Thurin, M; Crawley, S C; Heerze, L D; Palcic, M M

    1991-09-25

    The glycosyltransferases controlling the biosynthesis of cell-surface complex carbohydrates transfer glycosyl residues from sugar nucleotides to specific hydroxyl groups of acceptor oligosaccharides. These enzymes represent prime targets for the design of glycosylation inhibitors with the potential to specifically alter the structures of cell-surface glycoconjugates. With the aim of producing such inhibitors, synthetic oligosaccharide substrates were prepared for eight different glycosyltransferases. The enzymes investigated were: A, alpha(1----2, porcine submaxillary gland); B, alpha(1----3/4, Lewis); C, alpha(1----4, mung bean); D, alpha(1----3, Lex)-fucosyltransferases; E, beta(1----4)-galactosyltransferase; F, beta(1----6)-N-acetylglucosaminyltransferase V; G, beta(1----6)-mucin-N-acetylglucosaminyltransferase ("core-2" transferase); and H, alpha(2----3)-sialyltransferase from rat liver. These enzymes all transfer sugar residues from their respective sugar nucleotides (GDP-Fuc, UDP-Gal, UDP-GlcNAc, and CMP-sialic acid) with inversion of configuration at their anomeric centers. The Km values for their synthetic oligosaccharide acceptors were in the range of 0.036-1.3 mM. For each of these eight enzymes, acceptor analogs were next prepared where the hydroxyl group undergoing glycosylation was chemically removed and replaced by hydrogen. The resulting deoxygenated acceptor analogs can no longer be substrates for the corresponding glycosyltransferases and, if still bound by the enzymes, should act as competitive inhibitors. In only four of the eight cases examined (enzymes A, C, F, and G) did the deoxygenated acceptor analogs inhibit their target enzymes, and their Ki values (all competitive) remained in the general range of the corresponding acceptor Km values. No inhibition was observed for the remaining four enzymes even at high concentrations of deoxygenated acceptor analog. For these latter enzymes it is suggested that the reactive acceptor hydroxyl groups are

  1. Photoionization in micelles: Addition of charged electron acceptors

    NASA Astrophysics Data System (ADS)

    Stenland, Chris; Kevan, Larry

    The relative photoyield of the electron donor N, N, N', N'-tetramethylbenzidine (TMB), solubilized in sodium and lithium dodecyl sulfate micelles with added charged electron acceptors was investigated. It was attempted to control the acceptor distance from a charged micellar interface by differently charged acceptors, cationic dimethyl viologen and anionic ferricyanide. However, back electron transfer from both cationic and anionic acceptors was found to be efficient. Thus simple electrostatic arguments for control of the photoyield do not seem applicable. Salt effects associated with the added ionic acceptors which partially neutralize the ionic micellar interface are suggested to be an important factor.

  2. Evidence of Delocalization in Charge-Transfer State Manifold for Donor:Acceptor Organic Photovoltaics.

    PubMed

    Guan, Zhiqiang; Li, Ho-Wa; Zhang, Jinfeng; Cheng, Yuanhang; Yang, Qingdan; Lo, Ming-Fai; Ng, Tsz-Wai; Tsang, Sai-Wing; Lee, Chun-Sing

    2016-08-24

    How charge-transfer states (CTSs) assist charge separation of a Coulombically bound exciton in organic photovoltaics has been a hot topic. It is believed that the delocalization feature of a CTS plays a crucial role in the charge separation process. However, the delocalization of the "hot" and the "relaxed" CTSs is still under debate. Here, with a novel frequency dependent charge-modulated electroabsorption spectroscopy (CMEAS) technique, we elucidate clearly that both "hot" and "relaxed" CTSs are loosely bound and delocalized states. This is confirmed by comparing the CMEAS results of CTSs with those of localized polaron states. Our results reveal the role of CTS delocalization on charge separation and indicate that no substantial delocalization gradient exists in CTSs.

  3. Anomalous excitons and screenings unveiling strong electronic correlations in SrTi1 -xNbxO3 (0 ≤x ≤0.005 )

    NASA Astrophysics Data System (ADS)

    Gogoi, Pranjal Kumar; Sponza, Lorenzo; Schmidt, Daniel; Asmara, Teguh Citra; Diao, Caozheng; Lim, Jason C. W.; Poh, Sock Mui; Kimura, Shin-ichi; Trevisanutto, Paolo E.; Olevano, Valerio; Rusydi, Andrivo

    2015-07-01

    Electron-electron (e-e) and electron-hole (e-h) interactions are often associated with many exotic phenomena in correlated electron systems. Here, we report an observation of anomalous excitons at 3.75, 4.67, and 6.11 eV at 4.2 K in bulk SrTiO3. Fully supported by ab initio G W Bethe-Salpeter equation calculations, these excitons are due to strong e-h and e-e interactions with different characters: 4.67 and 6.11 eV are resonant excitons and 3.75 eV is a bound Wannier-like exciton with an unexpectedly higher level of delocalization. Measurements and calculations on SrTi1 -xNbxO3 for 0.0001 ≤x ≤0.005 further show that the energy and spectral-weight of the excitonic peaks vary as a function of electron doping (x ) and temperature, which are attributed to screening effects. Our results show the importance of e-h and e-e interactions yielding to anomalous excitons and thus bring out a new fundamental perspective in SrTiO3.

  4. Exciton polaritons in two-dimensional dichalcogenide layers placed in a planar microcavity: Tunable interaction between two Bose-Einstein condensates

    NASA Astrophysics Data System (ADS)

    Vasilevskiy, Mikhail I.; Santiago-Pérez, Darío G.; Trallero-Giner, Carlos; Peres, Nuno M. R.; Kavokin, Alexey

    2015-12-01

    Exciton-polariton modes arising from interaction between bound excitons in monolayer thin semiconductor sheets and photons in a Fabry-Perot microcavity are considered theoretically. We calculate the dispersion curves, mode lifetimes, Rabi splitting, and Hopfield coefficients of these structures for two nearly 2D semiconductor materials, MoS2 and WS2, and suggest that they are interesting for studying the rich physics associated with the Bose-Einstein condensation of exciton polaritons. The large exciton binding energy and dipole allowed exciton transitions, in addition to the relatively easily controllable distance between the semiconductor sheets, are the advantages of this system in comparison with traditional GaAs or CdTe based semiconductor microcavities. In particular, in order to mimic the rich physical properties of the quantum degenerate mixture of two bosonic species of dilute atomic gases with tunable interspecies interaction, we put forward a structure containing two semiconductor sheets separated by some atomic-scale distance (l ) using a nearly 2D dielectric (e.g., h-BN), which offers the possibility of tuning the interaction between two exciton-polariton Bose-Enstein condensates. We show that the dynamics of this structure are ruled by two coupled Gross-Pitaevskii equations with the coupling parameter ˜l-1 .

  5. Exciton radiative lifetime in transition metal dichalcogenide monolayers

    NASA Astrophysics Data System (ADS)

    Robert, C.; Lagarde, D.; Cadiz, F.; Wang, G.; Lassagne, B.; Amand, T.; Balocchi, A.; Renucci, P.; Tongay, S.; Urbaszek, B.; Marie, X.

    2016-05-01

    We have investigated the exciton dynamics in transition metal dichalcogenide monolayers using time-resolved photoluminescence experiments performed with optimized time resolution. For MoS e2 monolayer, we measure τrad0=1.8 ±0.2 ps at T =7 K that we interpret as the intrinsic radiative recombination time. Similar values are found for WS e2 monolayers. Our detailed analysis suggests the following scenario: at low temperature (T ≲50 K ), the exciton oscillator strength is so large that the entire light can be emitted before the time required for the establishment of a thermalized exciton distribution. For higher lattice temperatures, the photoluminescence dynamics is characterized by two regimes with very different characteristic times. First the photoluminescence intensity drops drastically with a decay time in the range of the picosecond driven by the escape of excitons from the radiative window due to exciton-phonon interactions. Following this first nonthermal regime, a thermalized exciton population is established gradually yielding longer photoluminescence decay times in the nanosecond range. Both the exciton effective radiative recombination and nonradiative recombination channels including exciton-exciton annihilation control the latter. Finally the temperature dependence of the measured exciton and trion dynamics indicates that the two populations are not in thermodynamical equilibrium.

  6. Fine structure of the exciton electroabsorption in semiconductor superlattices

    NASA Astrophysics Data System (ADS)

    Monozon, B. S.; Schmelcher, P.

    2017-02-01

    Wannier-Mott excitons in a semiconductor layered superlattice (SL) are investigated analytically for the case that the period of the superlattice is much smaller than the 2D exciton Bohr radius. Additionally we assume the presence of a longitudinal external static electric field directed parallel to the SL axis. The exciton states and the optical absorption coefficient are derived in the tight-binding and adiabatic approximations. Strong and weak electric fields providing spatially localized and extended electron and hole states, respectively, are studied. The dependencies of the exciton states and the exciton absorption spectrum on the SL parameters and the electric field strength are presented in an explicit form. We focus on the fine structure of the ground quasi-2D exciton level formed by the series of closely spaced energy levels adjacent from the high frequencies. These levels are related to the adiabatically slow relative exciton longitudinal motion governed by the potential formed by the in-plane exciton state. It is shown that the external electric fields compress the fine structure energy levels, decrease the intensities of the corresponding optical peaks and increase the exciton binding energy. A possible experimental study of the fine structure of the exciton electroabsorption is discussed.

  7. Taming excitons in II-VI semiconductor nanowires and nanobelts

    NASA Astrophysics Data System (ADS)

    Xu, Xinlong; Zhang, Qing; Zhang, Jun; Zhou, Yixuan; Xiong, Qihua

    2014-10-01

    Excitons are one of the most important fundamental quasi-particles, and are involved in a variety of processes forming the basis of a wide range of opto-electronic and photonic devices based on II-VI semiconductor nanowires and nanobelts, such as light-emitting diodes, photovoltaic cells, photodetectors and nanolasers. A clear understanding of their properties and unveiling the potential engineering for excitons is of particular importance for the design and optimization of nanoscale opto-electronic and photonic devices. Herein, we present a comprehensive review on discussing the fundamental behaviours of the excitons in one-dimensional (1D) II-VI semiconductor nanomaterials (nanowires and nanobelts). We will start with a focus on the unique properties (origin, generation, etc) and dynamics of excitons and exciton complexes in the II-VI semiconductor nanowires and nanobelts. Then we move to the recent progress on the excitonic response in 1D nanomaterials and focus on the tailoring and engineering of excitonic properties through rational controlling of the physical parameters and conditions, intrinsically and extrinsically. These include (1) exciton-exciton interaction, which is important for 1D nanomaterial nanolasing; (2) exciton-phonon interaction, which has interesting applications for laser cooling; and (3) exciton-plasmon interaction, which is the cornerstone towards the realization of plasmonic lasers. The potential of electric field, morphology and size control for excitonic properties is also discussed. Unveiling and controlling excitonic properties in II-VI semiconductor nanowires and nanobelts would promote the development of 1D nanoscience and nanotechnology.

  8. Observation of long-lived interlayer excitons in monolayer MoSe2–WSe2 heterostructures

    SciTech Connect

    Rivera, Pasqual; Schaibley, John R.; Jones, Aaron M.; Ross, Jason S.; Wu, Sanfeng; Aivazian, Grant; Klement, Philip; Seyler, Kyle; Clark, Genevieve; Ghimire, Nirmal J.; Yan, Jiaqiang; Mandrus, D. G.; Yao, Wang; Xu, Xiaodong

    2015-02-24

    Van der Waals bound heterostructures constructed with two-dimensional materials, such as graphene, boron nitride and transition metal dichalcogenides, have sparked wide interest in both device physics and technologies at the two-dimensional limit. One highly coveted heterostructure is that of differing monolayer transition metal dichalcogenides with type-II band alignment, with bound electrons and holes localized in individual monolayers, that is, interlayer excitons. Here, we report the observation of interlayer excitons in monolayer MoSe2–WSe2 heterostructures by photoluminescence and photoluminescence excitation spectroscopy. The energy and luminescence intensity are highly tunable by an applied vertical gate voltage. Moreover, we measure an interlayer exciton lifetime of ~1.8 ns, an order of magnitude longer than intralayer excitons in monolayers. Ultimately, our work demonstrates optical pumping of interlayer electric polarization, which may provoke further exploration of interlayer exciton condensation, as well as new applications in two-dimensional lasers, light-emitting diodes and photovoltaic devices.

  9. Binomial distribution-based quantitative measurement of multiple-acceptors fluorescence resonance energy transfer by partially photobleaching acceptor

    NASA Astrophysics Data System (ADS)

    Zhang, Lili; Yu, Huaina; Zhang, Jianwei; Chen, Tongsheng

    2014-06-01

    We report that binomial distribution depending on acceptor photobleaching degree can be used to characterize the proportions of various kinds of FRET (Fluorescence Resonance Energy Transfer) constructs resulted from partial acceptor photobleaching of multiple-acceptors FRET system. On this basis, we set up a rigorous quantitation theory for multiple-acceptors FRET construct named as Mb-PbFRET which is not affected by the imaging conditions and fluorophore properties. We experimentally validate Mb-PbFRET with FRET constructs consisted of one donor and two or three acceptors inside living cells on confocal and wide-field microscopes.

  10. Two-dimensional coherent spectroscopy of excitons, biexcitons, and exciton-polaritons

    NASA Astrophysics Data System (ADS)

    Bristow, Alan D.

    2016-10-01

    Semiconductors systems exhibiting excitonic properties are discussed in terms of their coherent response, which is extracted using two-dimensional coherent spectroscopy. This control method allows for separation of quantum pathways that comprise the optical response, such as interactions between excitons, their dephasing rates, the effects of many-body interactions and the role of structure on the microscopic electronic environment. Additional controls, such as polarization can be used to further distinguish biexcitons and suppress many-body interactions. These result are compared and contrasted with those from a semiconductor microcavity where the excitons form polaritonic modes due to normal-mode splitting. Rephrasing spectra map the detuning dependence of the exciton-polariton branches. Increasing the detuning shifts all features to higher energy and the expected anti-crossing is observed. An isolated biexciton is seen only at negative detuning, separated by a binding energy. For positive detuning, the spectral weight of the off-diagonal features swap, as the lower polariton branch and biexciton come into resonance. This indicates that the off-diagonal features are sensitive to the interactions of the exciton-polaritons and other resonances in the system.

  11. Optical properties of MgZnO alloys: Excitons and exciton-phonon complexes

    SciTech Connect

    Neumann, M. D.; Cobet, C.; Esser, N.; Laumer, B.; Wassner, T. A.; Eickhoff, M.; Feneberg, M.; Goldhahn, R.

    2011-07-01

    The characteristics of the excitonic absorption and emission around the fundamental bandgap of wurtzite Mg{sub x}Zn{sub 1-x}O grown on c-plane sapphire substrates by plasma assisted molecular beam epitaxy with Mg contents between x = 0 and x = 0.23 are studied using spectroscopic ellipsometry and photoluminescence (PL) measurements. The ellipsometric data were analyzed using a multilayer model yielding the dielectric function (DF). The imaginary part of the DF for the alloys exhibits a pronounced feature which is attributed to exciton-phonon coupling (EPC) similar to the previously reported results for ZnO. Thus, in order to determine reliable transition energies, the spectral dependence is analyzed by a model which includes free excitonic lines, the exciton continuum, and the enhanced absorption due to EPC. A line shape analysis of the temperature-dependent PL spectra yielded in particular the emission-related free excitonic transition energies, which are compared to the results from the DF line-shape analysis. The PL linewidth is discussed within the framework of an alloy disorder model.

  12. Proposal for dark exciton based chemical sensors

    NASA Astrophysics Data System (ADS)

    Feierabend, Maja; Berghäuser, Gunnar; Knorr, Andreas; Malic, Ermin

    2017-03-01

    The rapidly increasing use of sensors throughout different research disciplines and the demand for more efficient devices with less power consumption depends critically on the emergence of new sensor materials and novel sensor concepts. Atomically thin transition metal dichalcogenides have a huge potential for sensor development within a wide range of applications. Their optimal surface-to-volume ratio combined with strong light-matter interaction results in a high sensitivity to changes in their surroundings. Here, we present a highly efficient sensing mechanism to detect molecules based on dark excitons in these materials. We show that the presence of molecules with a dipole moment transforms dark states into bright excitons, resulting in an additional pronounced peak in easy accessible optical spectra. This effect exhibits a huge potential for sensor applications, since it offers an unambiguous optical fingerprint for the detection of molecules--in contrast to common sensing schemes relying on small peak shifts and intensity changes.

  13. 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.

  14. Emission of Tamm plasmon/exciton polaritons

    NASA Astrophysics Data System (ADS)

    Symonds, C.; Lemaître, A.; Homeyer, E.; Plenet, J. C.; Bellessa, J.

    2009-10-01

    We report on the observation of the strong coupling regime occurring between a Tamm plasmon (TP) mode and an exciton from inorganic quantum wells (QWs). The sample is formed by a silver thin film deposited onto an AlAs/GaAlAs Bragg reflector containing InGaAs QWs located in the high refractive index layers. Angular resolved reflectometry experiments evidence a clear anticrossing in the dispersion relations, a signature of the strong coupling regime. The Rabi splitting energy is 11.5 meV. The experimental data are in very good agreement with simple transfer matrix calculations. The emission from low and high energy TP/exciton polaritons is also demonstrated.

  15. Alkyl Chlorides as Hydrogen Bond Acceptors

    SciTech Connect

    Nadas, Janos I; Vukovic, Sinisa; Hay, Benjamin

    2012-01-01

    To gain an understanding of the role of an alkyl chloride as a hydrogen bond acceptor, geometries and interaction energies were calculated at the MP2/aug-cc-pVDZ level of theory for complexes between ethyl chloride and representative hydrogen donor groups. The results establish that these donors, which include hydrogen cyanide, methanol, nitrobenzene, pyrrole, acetamide, and N-methylurea, form X-H {hor_ellipsis} Cl hydrogen bonds (X = C, N, O) of weak to moderate strength, with {Delta}E values ranging from -2.8 to -5.3 kcal/mol.

  16. A method to quantify FRET stoichiometry with phasor plot analysis and acceptor lifetime ingrowth.

    PubMed

    Chen, WeiYue; Avezov, Edward; Schlachter, Simon C; Gielen, Fabrice; Laine, Romain F; Harding, Heather P; Hollfelder, Florian; Ron, David; Kaminski, Clemens F

    2015-03-10

    FRET is widely used for the study of protein-protein interactions in biological samples. However, it is difficult to quantify both the FRET efficiency (E) and the affinity (Kd) of the molecular interaction from intermolecular FRET signals in samples of unknown stoichiometry. Here, we present a method for the simultaneous quantification of the complete set of interaction parameters, including fractions of bound donors and acceptors, local protein concentrations, and dissociation constants, in each image pixel. The method makes use of fluorescence lifetime information from both donor and acceptor molecules and takes advantage of the linear properties of the phasor plot approach. We demonstrate the capability of our method in vitro in a microfluidic device and also in cells, via the determination of the binding affinity between tagged versions of glutathione and glutathione S-transferase, and via the determination of competitor concentration. The potential of the method is explored with simulations.

  17. Resonant pairing of excitons in semiconductor heterostructures

    NASA Astrophysics Data System (ADS)

    Andreev, S. V.

    2016-10-01

    We suggest indirect excitons in two-dimensional semiconductor heterostructures as a platform for the realization of a bosonic analog of the Bardeen-Cooper-Schrieffer superconductor. The quantum phase transition to a biexcitonic gapped state can be controlled in situ by tuning the electric field applied to the structure in the growth direction. The proposed playground should allow one to go to strongly correlated and high-temperature regimes, unattainable with Feshbach resonant atomic gases.

  18. Highly luminescent two dimensional excitons in atomically thin CdSe nanosheets

    NASA Astrophysics Data System (ADS)

    Halder, O.; Pradhani, A.; Sahoo, P. K.; Satpati, B.; Rath, S.

    2014-05-01

    Atomically thin Cadmium Selenide (CdSe) nanosheets have been synthesized using a surfactant mediated growth technique. The transmission electron microscopy studies confirm the presence of single layered nanosheets with thickness 1.31 nm and their stacking structures which are complemented by the small angle x-ray scattering measurements. The strongly bound and polarized character of two dimensional excitonic states with enhanced oscillator strength yielding distinct narrow blue luminescence has been observed from the CdSe nanosheets using room temperature based optical studies.

  19. Highly luminescent two dimensional excitons in atomically thin CdSe nanosheets

    SciTech Connect

    Halder, O.; Pradhani, A.; Rath, S.; Sahoo, P. K.; Satpati, B.

    2014-05-05

    Atomically thin Cadmium Selenide (CdSe) nanosheets have been synthesized using a surfactant mediated growth technique. The transmission electron microscopy studies confirm the presence of single layered nanosheets with thickness 1.31 nm and their stacking structures which are complemented by the small angle x-ray scattering measurements. The strongly bound and polarized character of two dimensional excitonic states with enhanced oscillator strength yielding distinct narrow blue luminescence has been observed from the CdSe nanosheets using room temperature based optical studies.

  20. Excitonic effects in oxyhalide scintillating host compounds

    SciTech Connect

    Shwetha, G.; Kanchana, V.; Valsakumar, M. C.

    2014-10-07

    Ab-initio calculations based on density functional theory have been performed to study the electronic, optical, mechanical, and vibrational properties of scintillator host compounds YOX (X = F, Cl, Br, and I). Semiempirical dispersion correction schemes are used to find the effect of van der Waals forces on these layered compounds and we found this effect to be negligible except for YOBr. Calculations of phonons and elastic constants showed that all the compounds studied here are both dynamically and mechanically stable. YOF and YOI are found to be indirect band gap insulators while YOCl and YOBr are direct band gap insulators. The band gap is found to decrease as we move from fluorine to iodine, while the calculated refractive index shows the opposite trend. As the band gap decreases on going down the periodic table from YOF to YOI, the luminescence increases. The excitonic binding energy calculated, within the effective mass approximation, is found to be more for YOF than the remaining compounds, suggesting that the excitonic effect to be more in YOF than the other compounds. The optical properties are calculated within the Time-Dependent Density Functional Theory (TDDFT) and compared with results obtained within the random phase approximation. The TDDFT calculations, using the newly developed bootstrap exchange-correlation kernel, showed significant excitonic effects in all the compounds studied here.

  1. Microcavity controlled coupling of excitonic qubits.

    PubMed

    Albert, F; Sivalertporn, K; Kasprzak, J; Strauß, M; Schneider, C; Höfling, S; Kamp, M; Forchel, A; Reitzenstein, S; Muljarov, E A; Langbein, W

    2013-01-01

    Controlled non-local energy and coherence transfer enables light harvesting in photosynthesis and non-local logical operations in quantum computing. This process is intuitively pictured by a pair of mechanical oscillators, coupled by a spring, allowing for a reversible exchange of excitation. On a microscopic level, the most relevant mechanism of coherent coupling of distant quantum bits--like trapped ions, superconducting qubits or excitons confined in semiconductor quantum dots--is coupling via the electromagnetic field. Here we demonstrate the controlled coherent coupling of spatially separated quantum dots via the photon mode of a solid state microresonator using the strong exciton-photon coupling regime. This is enabled by two-dimensional spectroscopy of the sample's coherent response, a sensitive probe of the coherent coupling. The results are quantitatively understood in a rigorous description of the cavity-mediated coupling of the quantum dot excitons. This mechanism can be used, for instance in photonic crystal cavity networks, to enable a long-range, non-local coherent coupling.

  2. Chiral topological excitons in the monolayer transition metal dichalcogenides.

    PubMed

    Gong, Z R; Luo, W Z; Jiang, Z F; Fu, H C

    2017-02-10

    We theoretically investigate the chiral topological excitons emerging in the monolayer transition metal dichalcogenides, where a bulk energy gap of valley excitons is opened up by a position dependent external magnetic field. We find two emerging chiral topological nontrivial excitons states, which exactly connects to the bulk topological properties, i.e., Chern number = 2. The dependence of the spectrum of the chiral topological excitons on the width of the magnetic field domain wall as well as the magnetic filed strength is numerically revealed. The chiral topological valley excitons are not only important to the excitonic transport due to prevention of the backscattering, but also give rise to the quantum coherent control in the optoelectronic applications.

  3. Chiral topological excitons in the monolayer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Gong, Z. R.; Luo, W. Z.; Jiang, Z. F.; Fu, H. C.

    2017-02-01

    We theoretically investigate the chiral topological excitons emerging in the monolayer transition metal dichalcogenides, where a bulk energy gap of valley excitons is opened up by a position dependent external magnetic field. We find two emerging chiral topological nontrivial excitons states, which exactly connects to the bulk topological properties, i.e., Chern number = 2. The dependence of the spectrum of the chiral topological excitons on the width of the magnetic field domain wall as well as the magnetic filed strength is numerically revealed. The chiral topological valley excitons are not only important to the excitonic transport due to prevention of the backscattering, but also give rise to the quantum coherent control in the optoelectronic applications.

  4. Chiral topological excitons in the monolayer transition metal dichalcogenides

    PubMed Central

    Gong, Z. R.; Luo, W. Z.; Jiang, Z. F.; Fu, H. C.

    2017-01-01

    We theoretically investigate the chiral topological excitons emerging in the monolayer transition metal dichalcogenides, where a bulk energy gap of valley excitons is opened up by a position dependent external magnetic field. We find two emerging chiral topological nontrivial excitons states, which exactly connects to the bulk topological properties, i.e., Chern number = 2. The dependence of the spectrum of the chiral topological excitons on the width of the magnetic field domain wall as well as the magnetic filed strength is numerically revealed. The chiral topological valley excitons are not only important to the excitonic transport due to prevention of the backscattering, but also give rise to the quantum coherent control in the optoelectronic applications. PMID:28186154

  5. Singlet exciton fission in nanostructured organic solar cells.

    PubMed

    Jadhav, Priya J; Mohanty, Aseema; Sussman, Jason; Lee, Jiye; Baldo, Marc A

    2011-04-13

    Singlet exciton fission is an efficient multiexciton generation process in organic molecules. But two concerns must be satisfied before it can be exploited in low-cost solution-processed organic solar cells. Fission must be combined with longer wavelength absorption in a structure that can potentially surpass the single junction limit, and its efficiency must be demonstrated in nanoscale domains within blended devices. Here, we report organic solar cells comprised of tetracene, copper phthalocyanine, and the buckyball C(60). Short wavelength light generates singlet excitons in tetracene. These are subsequently split into two triplet excitons and transported through the phthalocyanine. In addition, the phthalocyanine absorbs photons below the singlet exciton energy of tetracene. To test tetracene in nanostructured blends, we fabricate coevaporated bulk heterojunctions and multilayer heterojunctions of tetracene and C(60). We measure a singlet fission efficiency of (71 ± 18)%, demonstrating that exciton fission can efficiently compete with exciton dissociation on the nanoscale.

  6. Bose-Einstein condensation of dipolar excitons in quantum wells

    NASA Astrophysics Data System (ADS)

    Timofeev, V. B.; Gorbunov, A. V.

    2009-02-01

    The experiments on Bose-Einstein condensation (BEC) of dipolar (spatially-indirect) excitons in the lateral traps in GaAs/AlGaAs Schottky-diode heterostructures with double and single quantum wells are presented. The condensed part of dipolar excitons under detection in the far zone is placed in k-space in the range which is almost two orders of magnitude less than thermal exciton wave vector. BEC occurs spontaneously in a reservoir of thermalized excitons. Luminescence images of Bose-condensate of dipolar excitons exhibit along perimeter of circular trap axially symmetrical spatial structures of equidistant bright spots which strongly depend on excitation power and temperature. By means of two-beam interference experiments with the use of cw and pulsed photoexcitation it was found that the state of dipolar exciton Bose-condensate is spatially coherent and the whole patterned luminescence configuration in real space is described by a common wave function.

  7. Excitonic Stark effect in MoS2 monolayers

    NASA Astrophysics Data System (ADS)

    Scharf, Benedikt; Frank, Tobias; Gmitra, Martin; Fabian, Jaroslav; Žutić, Igor; Perebeinos, Vasili

    2016-12-01

    We theoretically investigate excitons in MoS2 monolayers in an applied in-plane electric field. Tight-binding and Bethe-Salpeter equation calculations predict a quadratic Stark shift, of the order of a few meV for fields of 10 V/μ m , in the linear absorption spectra. The spectral weight of the main exciton peaks decreases by a few percent with an increasing electric field due to the exciton field ionization into free carriers as reflected in the exciton wave functions. Subpicosecond exciton decay lifetimes at fields of a few tens of V/μ m could be utilized in solar energy harvesting and photodetection. We find simple scaling relations of the exciton binding, radius, and oscillator strength with the dielectric environment and an electric field, which provides a path to engineering the MoS2 electro-optical response.

  8. Hybrid states of Tamm plasmons and exciton-polaritons

    NASA Astrophysics Data System (ADS)

    Kaliteevski, M.; Brand, S.; Abram, R. A.; Iorsh, I.; Kavokin, A. V.; Liew, T. C. H.; Shelykh, I. A.

    2011-03-01

    We have demonstrated theoretically that it is possible to use the resonant coupling of exciton-polaritons in a planar microcavity and Tamm plasmons at a metal film on the surface of the structure to provide lateral spatial control of the exciton-polaritons within the cavity. The resonant coupling of the Tamm plasmons to cavity exciton-polaritons results in a triplet of hybrid plasmon-exciton-polariton modes with the lowest at a significantly lower energy than that of the unperturbed exciton-polaritons. Further, a patterned metal film on the structure surface can provide a sufficiently large lateral modulation of the excitation energy that localization of the exciton-polaritons within chosen regions of the cavity is possible. We show how the approach opens the way to a practical demonstration of polariton channels, traps, and devices, including logic gates.

  9. Excitonic gap formation and condensation in the bilayer graphene structure

    NASA Astrophysics Data System (ADS)

    Apinyan, V.; Kopeć, T. K.

    2016-09-01

    We have studied the excitonic gap formation in the Bernal Stacked, bilayer graphene (BLG) structures at half-filling. Considering the local Coulomb interaction between the layers, we calculate the excitonic gap parameter and we discuss the role of the interlayer and intralayer Coulomb interactions and the interlayer hopping on the excitonic pair formation in the BLG. Particularly, we predict the origin of excitonic gap formation and condensation, in relation to the furthermost interband optical transition spectrum. The general diagram of excitonic phase transition is given, explaining different interlayer correlation regimes. The temperature dependence of the excitonic gap parameter is shown and the role of the chemical potential, in the BLG, is discussed in details.

  10. Phonon-Induced Dephasing of Excitons in Semiconductor Quantum Dots: Multiple Exciton Generation, Fission, and Luminescence

    NASA Astrophysics Data System (ADS)

    Madrid, Angeline; Kim, Hyeon-Deuk; Habenicht, Bradley; Prezhdo, Oleg

    2010-03-01

    Phonon-induced dephasing processes that govern optical line widths, multiple exciton (ME) generation (MEG), and ME fission (MEF) in semiconductor quantum dots (QDs) are investigated by ab initio molecular dynamics simulation. Using Si QDs as an example, we propose that MEF occurs by phonon-induced dephasing and, for the first time, estimate its time scale to be 100 fs. In contrast, luminescence and MEG dephasing times are all sub-10 fs. Generally, dephasing is faster for higher-energy and higher-order excitons and increased temperatures. MEF is slow because it is facilitated only by low-frequency acoustic modes. Luminescence and MEG couple to both acoustic and optical modes of the QD, as well as ligand vibrations. The detailed atomistic simulation of the dephasing processes advances understanding of exciton dynamics in QDs and other nanoscale materials.

  11. Plasmon-Frenkel-exciton in a clustered solid

    NASA Astrophysics Data System (ADS)

    Rotkin, Slava V.; Suris, Robert A.

    1998-08-01

    The standard theory of the Frenkel exciton (a small radius exciton) is applied to a fullerene 2D solid. It is the dipole collective electron excitation of a single cluster which forms the delocalized plasmon-Frenkel-exciton (PFE) in a crystal. The PFE retarded interaction is taken into account. We present transverse PFE-polariton dispersion curves along with the Coulomb problem solution for longitudinal excitation in the 2D plane.

  12. Spatially indirect exciton condensate phases in double bilayer graphene

    NASA Astrophysics Data System (ADS)

    Su, Jung-Jung; MacDonald, Allan H.

    2017-01-01

    We present a theory of spatially indirect exciton condensate states in systems composed of a pair of electrically isolated Bernal graphene bilayers. The ground-state phase diagram in a two-dimensional displacement-field/inter-bilayer-bias space includes layer-polarized semiconductors, spin-density-wave states, exciton condensates, and states with mixed excitonic and spin order. We find that two different condensate states, distinguished by a chirality index, are stable under different electrical control conditions.

  13. Photogenerated exciton dissociation in highly coupled lead salt nanocrystal assemblies.

    PubMed

    Choi, Joshua J; Luria, Justin; Hyun, Byung-Ryool; Bartnik, Adam C; Sun, Liangfeng; Lim, Yee-Fun; Marohn, John A; Wise, Frank W; Hanrath, Tobias

    2010-05-12

    Internanocrystal coupling induced excitons dissociation in lead salt nanocrystal assemblies is investigated. By combining transient photoluminescence spectroscopy, grazing incidence small-angle X-ray scattering, and time-resolved electric force microscopy, we show that excitons can dissociate, without the aid of an external bias or chemical potential gradient, via tunneling through a potential barrier when the coupling energy is comparable to the exciton binding energy. Our results have important implications for the design of nanocrystal-based optoelectronic devices.

  14. Phase diagram for the trapping kinetics of partially coherent excitons

    NASA Astrophysics Data System (ADS)

    Pearlstein, Robert M.

    1998-06-01

    The kinetics of exciton trapping within molecular assemblies similar to those of recently reported structural models of photosynthetic light-harvesting antennas have been described theoretically for any degree of exciton coherence. It is shown here that in the space of two of the kinetic parameters - the local exciton scattering rate constant and the nearest-neighbor separation distance of the exciton-generating transition dipoles - the trapping kinetics segregate into coherent and incoherent phases delineated by universal curves. Consequences of these findings are discussed, particularly as they may apply to purple photosynthetic bacteria.

  15. 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.

  16. Simulations of singlet exciton diffusion in organic semiconductors: a review

    SciTech Connect

    Bjorgaard, Josiah A.; Kose, Muhammet Erkan

    2014-12-22

    Our review describes the various aspects of simulation strategies for exciton diffusion in condensed phase thin films of organic semiconductors. Several methods for calculating energy transfer rate constants are discussed along with procedures for how to account for energetic disorder. Exciton diffusion can be modelled by using kinetic Monte-Carlo methods or master equations. Recent literature on simulation efforts for estimating exciton diffusion lengths of various conjugated polymers and small molecules are introduced. Moreover, these studies are discussed in the context of the effects of morphology on exciton diffusion and the necessity of accurate treatment of disorder for comparison of simulation results with those of experiment.

  17. 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

  18. Analysis of wavelength-dependent photoisomerization quantum yields in bilirubins by fitting two exciton absorption bands

    NASA Astrophysics Data System (ADS)

    Mazzoni, M.; Agati, G.; Troup, G. J.; Pratesi, R.

    2003-09-01

    The absorption spectra of bilirubins were deconvoluted by two Gaussian curves of equal width representing the exciton bands of the non-degenerate molecular system. The two bands were used to study the wavelength dependence of the (4Z, 15Z) rightarrow (4Z, 15E) configurational photoisomerization quantum yield of the bichromophoric bilirubin-IXalpha (BR-IX), the intrinsically asymmetric bile pigment associated with jaundice and the symmetrically substituted bilirubins (bilirubin-IIIalpha and mesobilirubin-XIIIalpha), when they are irradiated in aqueous solution bound to human serum albumin (HSA). The same study was performed for BR-IX in ammoniacal methanol solution (NH4OH/MeOH). The quantum yields of the configurational photoprocesses were fitted with a combination function of the two Gaussian bands normalized to the total absorption, using the proportionality coefficients and a scaling factor as parameters. The decrease of the (4Z, 15Z) rightarrow (4Z, 15E) quantum yield with increasing wavelength, which occurs for wavelengths longer than the most probable Franck-Condon transition of the molecule, did not result in a unique function of the exciton absorptions. In particular we found two ranges corresponding to different exciton interactions with different proportionality coefficients and scaling factors. The wavelength-dependent photoisomerization of bilirubins was described as an abrupt change in quantum yield as soon as the resulting excitation was strongly localized in each chromophore. The change was correlated to a variation of the interaction between the two chromophores when the short-wavelength exciton absorption became vanishingly small. With the help of the circular dichroism (CD) spectrum of BR-IX in HSA, a small band was resolved in the bilirubin absorption spectrum, delivering part of the energy required for the (4Z, 15Z) rightarrow (4Z, 15E) photoisomerization of the molecule.

  19. Exciton dissociation at donor-acceptor heterojunctions: Dynamics using the collective effective mode representation of the spin-boson model

    SciTech Connect

    Chenel, Aurélie; Mangaud, Etienne; Burghardt, Irene E-mail: chris@irsamc.ups-tlse.fr; Meier, Christoph E-mail: chris@irsamc.ups-tlse.fr; Desouter-Lecomte, Michèle E-mail: chris@irsamc.ups-tlse.fr

    2014-01-28

    Following the recent quantum dynamics investigation of the charge transfer at an oligothiophene-fullerene heterojunction by the multi-configuration time dependent Hartree method [H. Tamura, R. Martinazzo, M. Ruckenbauer and I. Burghardt, J. Chem. Phys. 137, 22A540 (2012)], we revisit the transfer process by a perturbative non-Markovian master equation treated by the time local auxiliary density matrix approach. We compare the efficiency of the spin-boson model calibrated by quantum chemistry with the effective mode representation. A collective mode is extracted from the spin-boson spectral density. It is weakly coupled to a residual bath of vibrational modes, allowing second-order dynamics. The electron transfer is analyzed for a sampling of inter-fragment distances showing the fine interplay of the electronic coupling and energy gap on the relaxation. The electronic coherence, expected to play a role in the process, is preserved during about 200 fs.

  20. A spectroscopic study of the wavelength-dependent photoisomerizations of bilirubins bound to human serum albumin

    NASA Astrophysics Data System (ADS)

    Mazzoni, Marina; Agati, Giovanni; Pratesi, Riccardo; Persico, Maurizio

    2005-12-01

    The wavelength-dependent photoisomerizations of the asymmetric bilirubin BR-IXα and of the symmetric bilirubin-IIIα (BR-III) and mesobilirubin-XIIIα (MBR-XIII) bound to human serum albumin (HSA) in aqueous solution were analysed with the help of an exciton coupling model. The modelling was based on the absorption and circular dichroism (CD) spectra (bisignate Cotton effect). Time-dependent density functional theory (TD-DFT) of the free BR-IX molecule suggested the presence of two main bands of exciton coupling character in the blue region of the spectrum, and other weaker bands of charge transfer character at longer wavelengths. These peculiarities were taken into account to fit the photoisomerization quantum yields in the blue-green region as functions of the wavelength, obtaining the bandshape of the exciton coupling bands from the experimental CD spectra. The other excitons were extracted from the decomposition of the band resulting from the difference between the absorption spectrum and the sum (normalized-to-absorption) of the two CD excitons. We expressed photoisomerization quantum yields in terms of the sum of the contributions to photon absorption deriving from all the exciton states normalized to total absorption. For all the reversible photoprocesses of bilirubins and for the irreversible one of BR-IXα in HSA (i.e. lumirubin formation), we give reliable mean values of the individual state excitation probabilities and photoisomerization efficiencies in the pigment protein complex.

  1. [Relations between the retinoic acid acceptor and teratogenesis of retinoids].

    PubMed

    Li, Zeng-Gang; Sun, Kai-Lai

    2004-09-01

    Retinoic acid can induce teratogenesis of the fetus of many animals including human, and its biological activities are induced by a serious of different retinoic acid accepters and their ligands. The retinoic acid acceptor RAR plays key roles in the teratogenesis, and the ligands of RAR are strong teratogens. The intensity sequence of the relative teratogenesis is ligandalpha, ligandbeta and ligandgamma. The ligands of the retinoic acid acceptor RXR cannot induce teratogenesis, but they can enhance the teratogenesis of the RAR stimulus. The retinoic acid acceptors can also affect the development of the fetus by adjusting the expression of the other genes. The relations between the gene mutation of the retinoic acid acceptor, various retinoic acid acceptors and their ligands and teratogenesis of retinoic acid are summarized in this article. In addition, the regulations of the retinoic acid acceptors to the other genes are also discussed.

  2. The reaction of choline dehydrogenase with some electron acceptors.

    PubMed Central

    Barrett, M C; Dawson, A P

    1975-01-01

    1. The choline dehydrogenase (EC 1.1.99.1) WAS SOLUBILIZED FROM ACETONE-DRIED POWDERS OF RAT LIVER MITOCHONDRIA BY TREATMENT WITH Naja naja venom. 2. The kinetics of the reaction of enzyme with phenazine methosulphate and ubiquinone-2 as electron acceptors were investigated. 3. With both electron acceptors the reaction mechanism appears to involve a free, modified-enzyme intermediate. 4. With some electron acceptors the maximum velocity of the reaction is independent of the nature of the acceptor. With phenazine methosulphate and ubiquinone-2 as acceptors the Km value for choline is also independent of the nature of the acceptor molecule. 5. The mechanism of the Triton X-100-solubilized enzyme is apparently the smae as that for the snake venom solubilized enzyme. PMID:1218095

  3. The reaction of choline dehydrogenase with some electron acceptors.

    PubMed

    Barrett, M C; Dawson, A P

    1975-12-01

    1. The choline dehydrogenase (EC 1.1.99.1) WAS SOLUBILIZED FROM ACETONE-DRIED POWDERS OF RAT LIVER MITOCHONDRIA BY TREATMENT WITH Naja naja venom. 2. The kinetics of the reaction of enzyme with phenazine methosulphate and ubiquinone-2 as electron acceptors were investigated. 3. With both electron acceptors the reaction mechanism appears to involve a free, modified-enzyme intermediate. 4. With some electron acceptors the maximum velocity of the reaction is independent of the nature of the acceptor. With phenazine methosulphate and ubiquinone-2 as acceptors the Km value for choline is also independent of the nature of the acceptor molecule. 5. The mechanism of the Triton X-100-solubilized enzyme is apparently the smae as that for the snake venom solubilized enzyme.

  4. Improvement of both efficiency and working lifetime in organic photovoltaic devices by using bathophenanthroline/tin(IV) phthalocyanine dichloride as bilayer exciton blocking layers

    NASA Astrophysics Data System (ADS)

    Zhuang, Taojun; Su, Zisheng; Liu, Yadong; Chu, Bei; Li, Wenlian; Wang, Junbo; Jin, Fangming; Yan, Xingwu; Zhao, Bo; Zhang, Feng; Fan, Di

    2012-06-01

    We demonstrate that the improvement of both efficiency and lifetime of organic photovoltaic (OPV) devices by employing thinner bathophenanthroline (Bphen) and thicker tin(IV) phthalocyanine dichloride (SnCl2Pc) as the bilayer exciton blocking layers (EBLs), where Bphen and SnCl2Pc acts as the photogenerated exciton blocking layer and optical spacer, respectively. The thicker SnCl2Pc layer can be adopted due to its high electron mobility and aligned lowest unoccupied molecular orbital with the acceptor. The OPV device with such a bilayer EBL leads to an increase by 27% in power conversion efficiency compared to the device with a traditional bathocuproine EBL. Moreover, the lifetime is also improved due to the superior oxygen and moisture diffusion blocking effect of the thick SnCl2Pc layer. The operation mechanism for the improvement in PCE and lifetime was also discussed.

  5. On the effect of nuclear bridge modes on donor-acceptor electronic coupling in donor-bridge-acceptor molecules

    NASA Astrophysics Data System (ADS)

    Davis, Daly; Toroker, Maytal Caspary; Speiser, Shammai; Peskin, Uri

    2009-03-01

    We report a theoretical study of intra-molecular electronic coupling in a symmetric DBA (donor-bridge-acceptor) complex, in which a donor electronic site is coupled to an acceptor site by way of intervening orbitals of a molecular bridge unit. In the off-resonant (deep tunneling) regime of electronic transport, the lowest unoccupied molecular orbitals (MO's) of the DBA system are split into distinguishable donor/acceptor and bridge orbitals. The effect of geometrical changes at the bridge on the donor/acceptor electronic energy manifold is studied for local stretching and bending modes. It is demonstrated that the energy splitting in the manifold of donor/acceptor unoccupied MOs changes in response to such changes, as assumed in simple McConnell-type models. Limitations of the simple models are revealed where the electronic charging of the bridge orbitals correlates with increasing donor/acceptor orbital energy splitting only for stretching but not for bending bridge modes.

  6. Quantum computing with acceptor spins in silicon

    NASA Astrophysics Data System (ADS)

    Salfi, Joe; Tong, Mengyang; Rogge, Sven; Culcer, Dimitrie

    2016-06-01

    The states of a boron acceptor near a Si/SiO2 interface, which bind two low-energy Kramers pairs, have exceptional properties for encoding quantum information and, with the aid of strain, both heavy hole and light hole-based spin qubits can be designed. Whereas a light-hole spin qubit was introduced recently (arXiv:1508.04259), here we present analytical and numerical results proving that a heavy-hole spin qubit can be reliably initialised, rotated and entangled by electrical means alone. This is due to strong Rashba-like spin-orbit interaction terms enabled by the interface inversion asymmetry. Single qubit rotations rely on electric-dipole spin resonance (EDSR), which is strongly enhanced by interface-induced spin-orbit terms. Entanglement can be accomplished by Coulomb exchange, coupling to a resonator, or spin-orbit induced dipole-dipole interactions. By analysing the qubit sensitivity to charge noise, we demonstrate that interface-induced spin-orbit terms are responsible for sweet spots in the dephasing time {T}2* as a function of the top gate electric field, which are close to maxima in the EDSR strength, where the EDSR gate has high fidelity. We show that both qubits can be described using the same starting Hamiltonian, and by comparing their properties we show that the complex interplay of bulk and interface-induced spin-orbit terms allows a high degree of electrical control and makes acceptors potential candidates for scalable quantum computation in Si.

  7. Quantum computing with acceptor spins in silicon.

    PubMed

    Salfi, Joe; Tong, Mengyang; Rogge, Sven; Culcer, Dimitrie

    2016-06-17

    The states of a boron acceptor near a Si/SiO2 interface, which bind two low-energy Kramers pairs, have exceptional properties for encoding quantum information and, with the aid of strain, both heavy hole and light hole-based spin qubits can be designed. Whereas a light-hole spin qubit was introduced recently (arXiv:1508.04259), here we present analytical and numerical results proving that a heavy-hole spin qubit can be reliably initialised, rotated and entangled by electrical means alone. This is due to strong Rashba-like spin-orbit interaction terms enabled by the interface inversion asymmetry. Single qubit rotations rely on electric-dipole spin resonance (EDSR), which is strongly enhanced by interface-induced spin-orbit terms. Entanglement can be accomplished by Coulomb exchange, coupling to a resonator, or spin-orbit induced dipole-dipole interactions. By analysing the qubit sensitivity to charge noise, we demonstrate that interface-induced spin-orbit terms are responsible for sweet spots in the dephasing time [Formula: see text] as a function of the top gate electric field, which are close to maxima in the EDSR strength, where the EDSR gate has high fidelity. We show that both qubits can be described using the same starting Hamiltonian, and by comparing their properties we show that the complex interplay of bulk and interface-induced spin-orbit terms allows a high degree of electrical control and makes acceptors potential candidates for scalable quantum computation in Si.

  8. Effects of Be acceptors on the spin polarization of carriers in p-i-n resonant tunneling diodes

    SciTech Connect

    Awan, I. T.; Galvão Gobato, Y.; Galeti, H. V. A.; Brasil, M. J. S. P.; Taylor, D.; Henini, M.

    2014-08-07

    In this paper, we have investigated the effect of Be acceptors on the electroluminescence and the spin polarization in GaAs/AlAs p-i-n resonant tunneling diodes. The quantum well emission comprise two main lines separated by ∼20 meV attributed to excitonic and Be-related transitions, which intensities show remarkably abrupt variations at critical voltages, particularly at the electron resonant peak where it shows a high-frequency bistability. The circular-polarization degree of the quantum-well electroluminescence also shows strong and abrupt variations at the critical bias voltages and it attains relatively large values (of ∼−75% at 15 T). These effects may be explored to design novel devices for spintronic applications such as a high-frequency spin-oscillators.

  9. Time-dependent transition density matrix for visualizing charge-transfer excitations in photoexcited organic donor-acceptor systems

    NASA Astrophysics Data System (ADS)

    Li, Yonghui; Ullrich, Carsten

    2013-03-01

    The time-dependent transition density matrix (TDM) is a useful tool to visualize and interpret the induced charges and electron-hole coherences of excitonic processes in large molecules. Combined with time-dependent density functional theory on a real-space grid (as implemented in the octopus code), the TDM is a computationally viable visualization tool for optical excitation processes in molecules. It provides real-time maps of particles and holes which gives information on excitations, in particular those that have charge-transfer character, that cannot be obtained from the density alone. Some illustration of the TDM and comparison with standard density difference plots will be shown for photoexcited organic donor-acceptor molecules. This work is supported by NSF Grant DMR-1005651

  10. Exciton-vibrational coupling in the dynamics and spectroscopy of Frenkel excitons in molecular aggregates

    NASA Astrophysics Data System (ADS)

    Schröter, M.; Ivanov, S. D.; Schulze, J.; Polyutov, S. P.; Yan, Y.; Pullerits, T.; Kühn, O.

    2015-03-01

    The influence of exciton-vibrational coupling on the optical and transport properties of molecular aggregates is an old problem that gained renewed interest in recent years. On the experimental side, various nonlinear spectroscopic techniques gave insight into the dynamics of systems as complex as photosynthetic antennae. Striking evidence was gathered that in these protein-pigment complexes quantum coherence is operative even at room temperature conditions. Investigations were triggered to understand the role of vibrational degrees of freedom, beyond that of a heat bath characterized by thermal fluctuations. This development was paralleled by theory, where efficient methods emerged, which could provide the proper frame to perform non-Markovian and non-perturbative simulations of exciton-vibrational dynamics and spectroscopy. This review summarizes the state of affairs of the theory of exciton-vibrational interaction in molecular aggregates and photosynthetic antenna complexes. The focus is put on the discussion of basic effects of exciton-vibrational interaction from the stationary and dynamics points of view. Here, the molecular dimer plays a prominent role as it permits a systematic investigation of absorption and emission spectra by numerical diagonalization of the exciton-vibrational Hamiltonian in a truncated Hilbert space. An extension to larger aggregates, having many coupled nuclear degrees of freedom, becomes possible with the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method for wave packet propagation. In fact it will be shown that this method allows one to approach the limit of almost continuous spectral densities, which is usually the realm of density matrix theory. Real system-bath situations are introduced for two models, which differ in the way strongly coupled nuclear coordinates are treated, as a part of the relevant system or the bath. A rather detailed exposition of the Hierarchy Equations Of Motion (HEOM) method will be

  11. Excitons and Optical Properties of {alpha} -Quartz

    SciTech Connect

    Chang, Eric K.; Rohlfing, Michael; Louie, Steven G. [Department of Physics, University of California at Berkeley, Berkeley, California 94720

    2000-09-18

    We present an ab initio study of the optical properties of {alpha} -quartz. The absorption spectrum is calculated by solving the Bethe-Salpeter equation for the interacting electron-hole system and found to be in excellent agreement with the measured spectrum up to 10 eV above the absorption threshold. We find that excitonic effects are crucial in understanding the sharp features in the absorption spectrum in this energy range. They are also crucial in the ab initio computation of the static dielectric constant, significantly enhancing its value. (c) 2000 The American Physical Society.

  12. Dynamical excitonic effects in metals and semiconductors.

    PubMed

    Marini, Andrea; Del Sole, Rodolfo

    2003-10-24

    The dynamics of an electron-hole pair induced by the time-dependent screened Coulomb interaction is discussed. In contrast to the case where the static electron-hole interaction is considered we demonstrate the occurrence of important dynamical excitonic effects in the solution of the Bethe-Salpeter equation. This is illustrated in the calculated absorption spectra of noble metals (copper and silver) and silicon. Dynamical corrections strongly affect the spectra, partially canceling dynamical self-energy effects and leading to good agreement with experiment.

  13. Electro-optical properties of Rydberg excitons

    NASA Astrophysics Data System (ADS)

    Zielińska-Raczyńska, Sylwia; Ziemkiewicz, David; Czajkowski, Gerard

    2016-07-01

    We show how to compute the electro-optical functions (absorption, reflection, and transmission) when Rydberg exciton-polaritons appear, including the effect of the coherence between the electron-hole pair and the electromagnetic field. With the use of the real density matrix approach, numerical calculations applied for the Cu2O crystal are performed. We also examine in detail and explain the dependence of the resonance displacement on the state number and applied electric field strength. We report a fairly good agreement with recently published experimental data.

  14. 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

  15. Excitonic luminescence upconversion in a two-dimensional semiconductor

    SciTech Connect

    Jones, Aaron M.; Yu, Hongyi; Schaibley, John R.; Yan, Jiaqiang; Mandrus, David G.; Taniguchi, Takashi; Watanabe, Kenji; Dery, Hanan; Yao, Wang; Xu, Xiaodong

    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) closely 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.

  16. New acceptor-donor-acceptor (A-D-A) type copolymers for efficient organic photovoltaic devices

    NASA Astrophysics Data System (ADS)

    Ghomrasni, S.; Ayachi, S.; Alimi, K.

    2015-01-01

    Three new conjugated systems alternating acceptor-donor-acceptor (A-D-A) type copolymers have been investigated by means of Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) at the 6-31g (d) level of theory. 4,4‧-Dimethoxy-chalcone, also called the 1,3-bis(4-methoxyphenyl)prop-2-en-1-one (BMP), has been used as a common acceptor moiety. It forced intra-molecular S⋯O interactions through alternating oligo-thiophene derivatives: 4-AlkylThiophenes (4-ATP), 4-AlkylBithiophenes (4-ABTP) and 4-Thienylene Vinylene (4-TEV) as donor moieties. The band gap, HOMO and LUMO electron distributions as well as optical properties were analyzed for each molecule. The fully optimized resulting copolymers showed low band gaps (2.2-2.8 eV) and deep HOMO energy levels ranging from -4.66 to -4.86 eV. A broad absorption [300-900 nm] covering the solar spectrum and absorption maxima ranges from 486 to 604 nm. In addition, organic photovoltaic cells (OPCs) based on alternating copolymers in bulk heterojunction (BHJ) composites with the 1-(3-methoxycarbonyl) propyl-1-phenyl-[6,6]-C61 (PCBM), as an acceptor, have been optimized. Thus, the band gap decreased to 1.62 eV, the power conversion efficiencies (PCEs) were about 3-5% and the open circuit voltage Voc of the resulting molecules decreased from 1.50 to 1.27 eV.

  17. Surface-coupled proton exchange of a membrane-bound proton acceptor.

    PubMed

    Sandén, Tor; Salomonsson, Lina; Brzezinski, Peter; Widengren, Jerker

    2010-03-02

    Proton-transfer reactions across and at the surface of biological membranes are central for maintaining the transmembrane proton electrochemical gradients involved in cellular energy conversion. In this study, fluorescence correlation spectroscopy was used to measure the local protonation and deprotonation rates of single pH-sensitive fluorophores conjugated to liposome membranes, and the dependence of these rates on lipid composition and ion concentration. Measurements of proton exchange rates over a wide proton concentration range, using two different pH-sensitive fluorophores with different pK(a)s, revealed two distinct proton exchange regimes. At high pH (> 8), proton association increases rapidly with increasing proton concentrations, presumably because the whole membrane acts as a proton-collecting antenna for the fluorophore. In contrast, at low pH (< 7), the increase in the proton association rate is slower and comparable to that of direct protonation of the fluorophore from the bulk solution. In the latter case, the proton exchange rates of the two fluorophores are indistinguishable, indicating that their protonation rates are determined by the local membrane environment. Measurements on membranes of different surface charge and at different ion concentrations made it possible to determine surface potentials, as well as the distance between the surface and the fluorophore. The results from this study define the conditions under which biological membranes can act as proton-collecting antennae and provide fundamental information on the relation between the membrane surface charge density and the local proton exchange kinetics.

  18. Efficient organic dye-sensitized solar cells: molecular engineering of donor-acceptor-acceptor cationic dyes.

    PubMed

    Cheng, Ming; Yang, Xichuan; Zhao, Jianghua; Chen, Cheng; Tan, Qin; Zhang, Fuguo; Sun, Licheng

    2013-12-01

    Three metal-free donor-acceptor-acceptor sensitizers with ionized pyridine and a reference dye were synthesized, and a detailed investigation of the relationship between the dye structure and the photophysical and photoelectrochemical properties and the performance of dye-sensitized solar cells (DSSCs) is described. The ionization of pyridine results in a red shift of the absorption spectrum in comparison to that of the reference dye. This is mainly attributable to the ionization of pyridine increasing the electron-withdrawing ability of the total acceptor part. Incorporation of the strong electron-withdrawing units of pyridinium and cyano acrylic acid gives rise to optimized energy levels, resulting in a large response range of wavelengths. When attached to TiO2 film, the conduction band of TiO2 is negatively shifted to a different extent depending on the dye. This is attributed to the electron recombination rate between the TiO2 film and the electrolyte being efficiently suppressed by the introduction of long alkyl chains and thiophene units. DSSCs assembled using these dyes show efficiencies as high as 8.8 %.

  19. How to Draw Energy Level Diagrams in Excitonic Solar Cells.

    PubMed

    Zhu, X-Y

    2014-07-03

    Emerging photovoltaic devices based on molecular and nanomaterials are mostly excitonic in nature. The initial absorption of a photon in these materials creates an exciton that can subsequently dissociate in each material or at their interfaces to give charge carriers. Any attempt at mechanistic understanding of excitonic solar cells must start with drawing energy level diagrams. This seemingly elementary exercise, which is described in textbooks for inorganic solar cells, has turned out to be a difficult subject in the literature. The problem stems from conceptual confusion of single-particle energy with quasi-particle energy and the misleading practice of mixing the two on the same energy level diagram. Here, I discuss how to draw physically accurate energy diagrams in excitonic solar cells using only single-particle energies (ionization potentials and electron affinities) of both ground and optically excited states. I will briefly discuss current understanding on the electronic energy landscape responsible for efficient charge separation in excitonic solar cells.

  20. High-Absorption-Efficiency Superlattice Solar Cells by Excitons

    NASA Astrophysics Data System (ADS)

    Nishinaga, Jiro; Kawaharazuka, Atsushi; Onomitsu, Koji; Horikoshi, Yoshiji

    2013-11-01

    The effect of excitonic absorption on solar cell efficiency has been investigated using solar cells with AlGaAs/GaAs superlattice structures. Numerical calculations reveal that excitonic absorption considerably enhances the overall absorption of bulk GaAs. Excitonic absorption shows strong and sharp peaks at the absorption edge and in the energy region above the band gap. Absorption enhancement is also achieved in the AlGaAs/GaAs superlattice. The measured quantum efficiency spectra of the superlattice solar cells are quite similar to the calculated absorption spectra considering the excitonic effect. The superlattice solar cells are confirmed to have high absorption coefficient compared with the GaAs and AlGaAs bulk solar cells. These results suggest that the enhanced absorption by excitons can increase the quantum efficiency of solar cells. This effect is more prominent for the solar cells with small absorption layer thicknesses.

  1. Exciton band structure in two-dimensional materials

    NASA Astrophysics Data System (ADS)

    Cudazzo, Pier Luigi; Sponza, Lorenzo; Giorgetti, Christine; Reining, Lucia; Sottile, Francesco; Gatti, Matteo

    In low-dimensional materials the screening of the Coulomb interaction is strongly reduced. As a consequence, the binding energy of both Wannier and Frenkel excitons in the optical spectra is large and comparable in size. Therefore, contrarily to bulk materials, it cannot serve as a criterion to distinguish different kinds of excitons. Here we demonstrate that the exciton band structure, which can be accessed experimentally, instead provides a powerful way to identify the exciton character. By comparing the ab initio solution of the many-body Bethe-Salpeter equation for graphane and single-layer hexagonal BN, we draw a general picture of the exciton dispersion in two-dimensional materials, highlighting the different role played by the exchange electron-hole interaction and by the hopping terms related to the electronic band structure.

  2. Excitons in conjugated polymers: wavefunctions, symmetries, and quantum numbers.

    PubMed

    Barford, William; Paiboonvorachat, Nattapong

    2008-10-28

    We introduce a mapping from configuration interaction singles wavefunctions, expressed as linear combinations of particle-hole excitations between Hartree-Fock molecular orbitals, to real-space exciton wavefunctions, expressed as linear combinations of particle-hole excitations between localized Wannier functions. The exciton wavefunction is a two-dimensional amplitude for the exciton center-of-mass coordinate, R, and the electron-hole separation (or relative coordinate), r, having an exact analogy to one-dimensional hydrogenlike wavefunctions. We describe the excitons by their appropriate quantum numbers, namely, the principle quantum number, n, associated with r and the center-of-mass pseudomomentum quantum number, j, associated with R. In addition, for models with particle-hole symmetry, such as the Pariser-Parr-Pople model, we emphasize the connection between particle-hole symmetry and particle-hole parity. The method is applied to the study of excitons in trans-polyacetylene and poly(para-phenylene).

  3. Photoinduced charge transfer in donor-acceptor (DA) copolymer: fullerene bis-adduct polymer solar cells.

    PubMed

    Kang, Tae Eui; Cho, Han-Hee; Cho, Chul-Hee; Kim, Ki-Hyun; Kang, Hyunbum; Lee, Myounghee; Lee, Sunae; Kim, Bongsoo; Im, Chan; Kim, Bumjoon J

    2013-02-01

    terms of fullerene acceptor. The low EQE and J(SC) in PBDTTPD and PBDTTT-C blended with ICBA and ICTA were attributed to an insufficient ΔG(CT) due to the higher LUMO levels of the fullerene multiadducts. Quantitative information on the efficiency of the charge transfer was obtained by comparing the polaron yield, lifetime, and exciton dissociation probability in the DA copolymer:fullerene acceptor films.

  4. Magnetic field enhanced electroluminescence in organic light emitting diodes based on electron donor-acceptor exciplex blends

    NASA Astrophysics Data System (ADS)

    Baniya, Sangita; Basel, Tek; Sun, Dali; McLaughlin, Ryan; Vardeny, Zeev Valy

    2016-03-01

    A useful process for light harvesting from injected electron-hole pairs in organic light emitting diodes (OLED) is the transfer from triplet excitons (T) to singlet excitons (S) via reverse intersystem crossing (RISC). This process adds a delayed electro-luminescence (EL) emission component that is known as thermally activated delayed fluorescence (TADF). We have studied electron donor (D)/acceptor(A) blends that form an exciplex manifold in which the energy difference, ΔEST between the lowest singlet (S1) and triplet (T1) levels is relatively small (<100 meV), and thus allows RISC at ambient temperature. We found that the EL emission in OLED based on the exciplex blend is enhanced up to 40% by applying a relatively weak magnetic field of 50 mT at ambient. Moreover the MEL response is activated with activation energy similar that of the EL emission. This suggests that the large magneto-EL originates from an additional spin-mixing channel between singlet and triplet states of the generated exciplexes, which is due to TADF. We will report on the MEL dependencies on the temperature, bias voltage, and D-A materials for optimum OLED performance. Supported by SAMSUNG Global Research Outreach (GRO) program, and also by the NSF-Material Science & Engineering Center (MRSEC) program at the University of Utah (DMR-1121252).

  5. Roles of Energy/Charge Cascades and Intermixed Layers at Donor/Acceptor Interfaces in Organic Solar Cells

    PubMed Central

    Nakano, Kyohei; Suzuki, Kaori; Chen, Yujiao; Tajima, Keisuke

    2016-01-01

    The secret to the success of mixed bulk heterojunctions (BHJs) in yielding highly efficient organic solar cells (OSCs) could reside in the molecular structures at their donor/acceptor (D/A) interfaces. In this study, we aimed to determine the effects of energy and charge cascade structures at the interfaces by using well-defined planar heterojunctions (PHJs) as a model system. The results showed that (1) the charge cascade structure enhanced VOC because it shuts down the recombination pathway through charge transfer (CT) state with a low energy, (2) the charge cascade layer having a wider energy gap than the bulk material decreased JSC because the diffusion of the excitons from the bulk to D/A interface was blocked; the energy of the cascade layers must be appropriately arranged for both the charges and the excitons, and (3) molecular intermixing in the cascade layer opened the recombination path through the low-energy CT state and decreased VOC. Based on these findings, we propose improved structures for D/A interfaces in BHJs. PMID:27404948

  6. Roles of Energy/Charge Cascades and Intermixed Layers at Donor/Acceptor Interfaces in Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    Nakano, Kyohei; Suzuki, Kaori; Chen, Yujiao; Tajima, Keisuke

    2016-07-01

    The secret to the success of mixed bulk heterojunctions (BHJs) in yielding highly efficient organic solar cells (OSCs) could reside in the molecular structures at their donor/acceptor (D/A) interfaces. In this study, we aimed to determine the effects of energy and charge cascade structures at the interfaces by using well-defined planar heterojunctions (PHJs) as a model system. The results showed that (1) the charge cascade structure enhanced VOC because it shuts down the recombination pathway through charge transfer (CT) state with a low energy, (2) the charge cascade layer having a wider energy gap than the bulk material decreased JSC because the diffusion of the excitons from the bulk to D/A interface was blocked; the energy of the cascade layers must be appropriately arranged for both the charges and the excitons, and (3) molecular intermixing in the cascade layer opened the recombination path through the low-energy CT state and decreased VOC. Based on these findings, we propose improved structures for D/A interfaces in BHJs.

  7. π-Extended rigid triptycene-trisaroylenimidazoles as electron acceptors.

    PubMed

    Menke, Elisabeth H; Lami, Vincent; Vaynzof, Yana; Mastalerz, Michael

    2016-01-18

    Two soluble isomeric acceptor molecules based on a triptycene core, which is connected to three aroylenimidazole units are described. Due to the inherent threefold axis, the molecules are soluble and thus could be fully photophysically characterized in solution and film. Additionally, the preliminary results of these acceptors in organic photovoltaic devices with two different donor materials are reported.

  8. Exciton Correlations in Intramolecular Singlet Fission

    DOE PAGES

    Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.; ...

    2016-05-16

    We have synthesized a series of asymmetric pentacene-tetracene heterodimers with a variable-length conjugated bridge that undergo fast and efficient intramolecular singlet fission (iSF). These compounds have distinct singlet and triplet energies, which allow us to study the spatial dynamics of excitons during the iSF process, including the significant role of exciton correlations in promoting triplet pair generation and recombination. We demonstrate that the primary photoexcitations in conjugated dimers are delocalized singlets that enable fast and efficient iSF. However, in these asymmetric dimers, the singlet becomes more localized on the lower energy unit as the length of the bridge is increased,more » slowing down iSF relative to analogous symmetric dimers. We resolve the recombination kinetics of the inequivalent triplets produced via iSF, and find that they primarily decay via concerted processes. By identifying different decay channels, including delayed fluorescence via triplet-triplet annihilation, we can separate transient species corresponding to both correlated triplet pairs and uncorrelated triplets. Recombination of the triplet pair proceeds rapidly despite our experimental and theoretical demonstration that individual triplets are highly localized and unable to be transported across the conjugated linker. In this class of compounds, the rate of formation and yield of uncorrelated triplets increases with bridge length. Overall, these constrained, asymmetric systems provide a unique platform to isolate and study transient species essential for singlet fission, which are otherwise difficult to observe in symmetric dimers or condensed phases.« less

  9. Exciton Correlations in Intramolecular Singlet Fission

    SciTech Connect

    Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B.; Appavoo, Kannatassen; Steigerwald, Michael L.; Campos, Luis M.; Sfeir, Matthew Y.

    2016-05-16

    We have synthesized a series of asymmetric pentacene-tetracene heterodimers with a variable-length conjugated bridge that undergo fast and efficient intramolecular singlet fission (iSF). These compounds have distinct singlet and triplet energies, which allow us to study the spatial dynamics of excitons during the iSF process, including the significant role of exciton correlations in promoting triplet pair generation and recombination. We demonstrate that the primary photoexcitations in conjugated dimers are delocalized singlets that enable fast and efficient iSF. However, in these asymmetric dimers, the singlet becomes more localized on the lower energy unit as the length of the bridge is increased, slowing down iSF relative to analogous symmetric dimers. We resolve the recombination kinetics of the inequivalent triplets produced via iSF, and find that they primarily decay via concerted processes. By identifying different decay channels, including delayed fluorescence via triplet-triplet annihilation, we can separate transient species corresponding to both correlated triplet pairs and uncorrelated triplets. Recombination of the triplet pair proceeds rapidly despite our experimental and theoretical demonstration that individual triplets are highly localized and unable to be transported across the conjugated linker. In this class of compounds, the rate of formation and yield of uncorrelated triplets increases with bridge length. Overall, these constrained, asymmetric systems provide a unique platform to isolate and study transient species essential for singlet fission, which are otherwise difficult to observe in symmetric dimers or condensed phases.

  10. Exciton Dynamics in Semiconducting Carbon Nanotubes

    SciTech Connect

    Graham, Matt; Chmeliov, Javgenij; Ma, Yingzhong; Shinohara, Nori; Green, Alexander A.; Hersam, Mark C.; Valkunas, Leonas; Fleming, Graham

    2010-01-01

    We report femtosecond transient absorption spectroscopic study on the (6, 5) single-walled carbon nanotubes and the (7, 5) inner tubes of a dominant double-walled carbon nanotube species. We found that the dynamics of exciton relaxation probed at the first transition-allowed state (E11) of a given tube type exhibits a markedly slower decay when the second transition-allowed state (E22) is excited than that measured by exciting its first transition-allowed state (E11). A linear intensity dependence of the maximal amplitude of the transient absorption signal is found for the E22 excitation, whereas the corresponding amplitude scales linearly with the square root of the E11 excitation intensity. Theoretical modeling of these experimental findings was performed by developing a continuum model and a stochastic model with explicit consideration of the annihilation of coherent excitons. Our detailed numerical simulations show that both models can reproduce reasonably well the initial portion of decay kinetics measured upon the E22 and E11 excitation of the chosen tube species, but the stochastic model gives qualitatively better agreement with the intensity dependence observed experimentally than those obtained with the continuum model.

  11. Acceptor impurity activation in III-nitride light emitting diodes

    SciTech Connect

    Römer, Friedhard Witzigmann, Bernd

    2015-01-12

    In this work, the role of the acceptor doping and the acceptor activation and its impact on the internal quantum efficiency (IQE) of a Gallium Nitride (GaN) based multi-quantum well light emitting diode is studied by microscopic simulation. Acceptor impurities in GaN are subject to a high activation energy which depends on the presence of proximate dopant atoms and the electric field. A combined model for the dopant ionization and activation barrier reduction has been developed and implemented in a semiconductor carrier transport simulator. By model calculations, we demonstrate the impact of the acceptor activation mechanisms on the decay of the IQE at high current densities, which is known as the efficiency droop. A major contributor to the droop is the electron leakage which is largely affected by the acceptor doping.

  12. Theoretical Studies of the Interaction of Excitons with Charged Impurities in Single-Walled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Tayo, Benjamin O.

    A fundamental theory of the electronic and optical properties of semiconductors shows the importance of impurities, which are often unavoidable and can alter intrinsic properties of semiconductor materials substantially. While the subject of impurity doping is well understood in bulk semiconductors, the role and impact of doping in low dimensional materials like carbon nanotubes is still under investigation and there exists significant debate on the exact nature of electronic impurity levels in single-walled carbon nanotubes associated with adatoms. In this work, we address the role of impurities in single-walled carbon nanotubes. A simple model is developed for studying the interaction of bright (singlet) excitons in semiconducting single-wall nanotubes with charged impurities. The model reveals a red shift in the energy of excitonic states in the presence of an impurity, thus indicating binding of excitons in the impurity potential well. Signatures of several bound states were found in the absorption spectrum below the onset of excitonic optical transitions in the bare nanotube. The dependence of the binding energy on the model parameters, such as impurity charge and position, was determined and analytical fits were derived for a number of tubes of different diameter. The nanotube family splitting is seen in the diameter dependence, gradually decreasing with the diameter. By calculating the partial absorption coefficient for a small segment of nanotube the local nature of the wave function of the bound states was derived. Our studies provide useful insights into the role of the physical environment (here, a charged impurity atom) in the manipulation of the excited states of carbon nanotubes. We performed very detailed calculations of the electronic and optical properties of carbon nanotubes in the presence of an immobile impurity atom, thus going beyond previous many-body perturbation theory (MBPT) studies in which the carbon nanotubes were considered in vacuum

  13. Structural basis for acceptor-substrate recognition of UDP-glucose: anthocyanidin 3-O-glucosyltransferase from Clitoria ternatea.

    PubMed

    Hiromoto, Takeshi; Honjo, Eijiro; Noda, Naonobu; Tamada, Taro; Kazuma, Kohei; Suzuki, Masahiko; Blaber, Michael; Kuroki, Ryota

    2015-03-01

    UDP-glucose: anthocyanidin 3-O-glucosyltransferase (UGT78K6) from Clitoria ternatea catalyzes the transfer of glucose from UDP-glucose to anthocyanidins such as delphinidin. After the acylation of the 3-O-glucosyl residue, the 3'- and 5'-hydroxyl groups of the product are further glucosylated by a glucosyltransferase in the biosynthesis of ternatins, which are anthocyanin pigments. To understand the acceptor-recognition scheme of UGT78K6, the crystal structure of UGT78K6 and its complex forms with anthocyanidin delphinidin and petunidin, and flavonol kaempferol were determined to resolutions of 1.85 Å, 2.55 Å, 2.70 Å, and 1.75 Å, respectively. The enzyme recognition of unstable anthocyanidin aglycones was initially observed in this structural determination. The anthocyanidin- and flavonol-acceptor binding details are almost identical in each complex structure, although the glucosylation activities against each acceptor were significantly different. The 3-hydroxyl groups of the acceptor substrates were located at hydrogen-bonding distances to the Nε2 atom of the His17 catalytic residue, supporting a role for glucosyl transfer to the 3-hydroxyl groups of anthocyanidins and flavonols. However, the molecular orientations of these three acceptors are different from those of the known flavonoid glycosyltransferases, VvGT1 and UGT78G1. The acceptor substrates in UGT78K6 are reversely bound to its binding site by a 180° rotation about the O1-O3 axis of the flavonoid backbones observed in VvGT1 and UGT78G1; consequently, the 5- and 7-hydroxyl groups are protected from glucosylation. These substrate recognition schemes are useful to understand the unique reaction mechanism of UGT78K6 for the ternatin biosynthesis, and suggest the potential for controlled synthesis of natural pigments.

  14. Structural basis for acceptor-substrate recognition of UDP-glucose: anthocyanidin 3-O-glucosyltransferase from Clitoria ternatea

    PubMed Central

    Hiromoto, Takeshi; Honjo, Eijiro; Noda, Naonobu; Tamada, Taro; Kazuma, Kohei; Suzuki, Masahiko; Blaber, Michael; Kuroki, Ryota

    2015-01-01

    UDP-glucose: anthocyanidin 3-O-glucosyltransferase (UGT78K6) from Clitoria ternatea catalyzes the transfer of glucose from UDP-glucose to anthocyanidins such as delphinidin. After the acylation of the 3-O-glucosyl residue, the 3′- and 5′-hydroxyl groups of the product are further glucosylated by a glucosyltransferase in the biosynthesis of ternatins, which are anthocyanin pigments. To understand the acceptor-recognition scheme of UGT78K6, the crystal structure of UGT78K6 and its complex forms with anthocyanidin delphinidin and petunidin, and flavonol kaempferol were determined to resolutions of 1.85 Å, 2.55 Å, 2.70 Å, and 1.75 Å, respectively. The enzyme recognition of unstable anthocyanidin aglycones was initially observed in this structural determination. The anthocyanidin- and flavonol-acceptor binding details are almost identical in each complex structure, although the glucosylation activities against each acceptor were significantly different. The 3-hydroxyl groups of the acceptor substrates were located at hydrogen-bonding distances to the Nε2 atom of the His17 catalytic residue, supporting a role for glucosyl transfer to the 3-hydroxyl groups of anthocyanidins and flavonols. However, the molecular orientations of these three acceptors are different from those of the known flavonoid glycosyltransferases, VvGT1 and UGT78G1. The acceptor substrates in UGT78K6 are reversely bound to its binding site by a 180° rotation about the O1–O3 axis of the flavonoid backbones observed in VvGT1 and UGT78G1; consequently, the 5- and 7-hydroxyl groups are protected from glucosylation. These substrate recognition schemes are useful to understand the unique reaction mechanism of UGT78K6 for the ternatin biosynthesis, and suggest the potential for controlled synthesis of natural pigments. PMID:25556637

  15. 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.

  16. Hot exciton cooling and multiple exciton generation in PbSe quantum dots.

    PubMed

    Kumar, Manoj; Vezzoli, Stefano; Wang, Zilong; Chaudhary, Varun; Ramanujan, Raju V; Gurzadyan, Gagik G; Bruno, Annalisa; Soci, Cesare

    2016-11-16

    Multiple exciton generation (MEG) is a promising process to improve the power conversion efficiency of solar cells. PbSe quantum dots (QDs) have shown reasonably high MEG quantum yield (QY), although the photon energy threshold for this process is still under debate. One of the reasons for this inconsistency is the complicated competition of MEG and hot exciton cooling, especially at higher excited states. Here, we investigate MEG QY and the origin of the photon energy threshold for MEG in PbSe QDs of three different sizes by studying the transient absorption (TA) spectra, both at the band gap (near infrared, NIR) and far from the band gap energy (visible range). The comparison of visible TA spectra and dynamics for different pump wavelengths, below, around and above the MEG threshold, provides evidence of the role of the Σ transition in slowing down the exciton cooling process that can help MEG to take over the phonon relaxation process. The universality of this behavior is confirmed by studying QDs of three different sizes. Moreover, our results suggest that MEG QY can be determined by pump-probe experiments probed above the band gap.

  17. Ubiquity of Exciton Localization in Cryogenic Carbon Nanotubes

    PubMed Central

    2016-01-01

    We present photoluminescence studies of individual semiconducting single-wall carbon nanotubes at room and cryogenic temperatures. From the analysis of spatial and spectral features of nanotube photoluminescence, we identify characteristic signatures of unintentional exciton localization. Moreover, we quantify the energy scale of exciton localization potentials as ranging from a few to a few tens of millielectronvolts and stemming from both environmental disorder and shallow covalent side-wall defects. Our results establish disorder-induced crossover from the diffusive to the localized regime of nanotube excitons at cryogenic temperatures as a ubiquitous phenomenon in micelle-encapsulated and as-grown carbon nanotubes. PMID:27105355

  18. Transport of indirect excitons in high magnetic fields

    NASA Astrophysics Data System (ADS)

    Kuznetsova, Y. Y.; Dorow, C. J.; Calman, E. V.; Butov, L. V.; Wilkes, J.; Muljarov, E. A.; Campman, K. L.; Gossard, A. C.

    2017-03-01

    We present spatially and spectrally resolved photoluminescence measurements of indirect excitons in high magnetic fields. Long indirect exciton lifetimes give the opportunity to measure magnetoexciton transport by optical imaging. Indirect excitons formed from electrons and holes at zeroth Landau levels (0e-0h indirect magnetoexcitons) travel over large distances and form a ring emission pattern around the excitation spot. In contrast, the spatial profiles of 1e-1h and 2e-2h indirect magnetoexciton emission closely follow the laser excitation profile. The 0e-0h indirect magnetoexciton transport distance reduces with increasing magnetic field. These effects are explained in terms of magnetoexciton energy relaxation and effective mass enhancement.

  19. Compensation of dipolar-exciton spin splitting in magnetic field

    NASA Astrophysics Data System (ADS)

    Gorbunov, A. V.; Timofeev, V. B.

    2013-03-01

    Magnetoluminescence of spatially indirect dipolar excitons in 25 nm GaAs/AlGaAs single quantum well collected within a lateral potential trap has been studied in Faraday geometry. The paramagnetic spin splitting of the luminescence line of the heavy-hole excitons in the trap centre is completely compensated at magnetic field below critical value ≈2 Т. The effect of spin splitting compensation is caused by the exchange interaction in dense exciton Bose gas which is in qualitative agreement with the existing theoretical concepts.

  20. Quantized Vortices and Four-Component Superfluidity of Semiconductor Excitons

    NASA Astrophysics Data System (ADS)

    Anankine, Romain; Beian, Mussie; Dang, Suzanne; Alloing, Mathieu; Cambril, Edmond; Merghem, Kamel; Carbonell, Carmen Gomez; Lemaître, Aristide; Dubin, François

    2017-03-01

    We study spatially indirect excitons of GaAs quantum wells, confined in a 10 μ m electrostatic trap. Below a critical temperature of about 1 K, we detect macroscopic spatial coherence and quantized vortices in the weak photoluminescence emitted from the trap. These quantum signatures are restricted to a narrow range of density, in a dilute regime. They manifest the formation of a four-component superfluid, made by a low population of optically bright excitons coherently coupled to a dominant fraction of optically dark excitons.

  1. Excitonic AND Logic Gates on DNA Brick Nanobreadboards

    PubMed Central

    2015-01-01

    A promising application of DNA self-assembly is the fabrication of chromophore-based excitonic devices. DNA brick assembly is a compelling method for creating programmable nanobreadboards on which chromophores may be rapidly and easily repositioned to prototype new excitonic devices, optimize device operation, and induce reversible switching. Using DNA nanobreadboards, we have demonstrated each of these functions through the construction and operation of two different excitonic AND logic gates. The modularity and high chromophore density achievable via this brick-based approach provide a viable path toward developing information processing and storage systems. PMID:25839049

  2. Excitons and the lifetime of organic semiconductor devices

    PubMed Central

    Forrest, Stephen R.

    2015-01-01

    While excitons are responsible for the many beneficial optical properties of organic semiconductors, their non-radiative recombination within the material can result in material degradation due to the dumping of energy onto localized molecular bonds. This presents a challenge in developing strategies to exploit the benefits of excitons without negatively impacting the device operational stability. Here, we will briefly review the fundamental mechanisms leading to excitonic energy-driven device ageing in two example devices: blue emitting electrophosphorescent organic light emitting devices (PHOLEDs) and organic photovoltaic (OPV) cells. We describe strategies used to minimize or even eliminate this fundamental device degradation pathway. PMID:25987572

  3. Excitons and the lifetime of organic semiconductor devices.

    PubMed

    Forrest, Stephen R

    2015-06-28

    While excitons are responsible for the many beneficial optical properties of organic semiconductors, their non-radiative recombination within the material can result in material degradation due to the dumping of energy onto localized molecular bonds. This presents a challenge in developing strategies to exploit the benefits of excitons without negatively impacting the device operational stability. Here, we will briefly review the fundamental mechanisms leading to excitonic energy-driven device ageing in two example devices: blue emitting electrophosphorescent organic light emitting devices (PHOLEDs) and organic photovoltaic (OPV) cells. We describe strategies used to minimize or even eliminate this fundamental device degradation pathway.

  4. Ubiquity of Exciton Localization in Cryogenic Carbon Nanotubes.

    PubMed

    Hofmann, Matthias S; Noé, Jonathan; Kneer, Alexander; Crochet, Jared J; Högele, Alexander

    2016-05-11

    We present photoluminescence studies of individual semiconducting single-wall carbon nanotubes at room and cryogenic temperatures. From the analysis of spatial and spectral features of nanotube photoluminescence, we identify characteristic signatures of unintentional exciton localization. Moreover, we quantify the energy scale of exciton localization potentials as ranging from a few to a few tens of millielectronvolts and stemming from both environmental disorder and shallow covalent side-wall defects. Our results establish disorder-induced crossover from the diffusive to the localized regime of nanotube excitons at cryogenic temperatures as a ubiquitous phenomenon in micelle-encapsulated and as-grown carbon nanotubes.

  5. Ultrafast excitonic room temperature nonlinearity in neutron irradiated quantum wells

    SciTech Connect

    Ten, S.; Williams, J.G.; Guerreiro, P.T.; Khitrova, G.; Peyghambarian, N.

    1997-01-01

    Sharp room temperature exciton features and complete recovery of the excitonic absorption with 21 ps time constant are demonstrated in neutron irradiated (Ga,Al)As/GaAs multiple quantum wells. Carrier lifetime reduction is consistent with the EL2 midgap defect which is efficiently generated by fast neutrons. Influence of gamma rays accompanying neutron irradiation is discussed. Neutron irradiation provides a straightforward way to control carrier lifetime in semiconductor heterostructures with minor deterioration of their excitonic properties. {copyright} {ital 1997 American Institute of Physics.}

  6. Excitonic AND Logic Gates on DNA Brick Nanobreadboards.

    PubMed

    Cannon, Brittany L; Kellis, Donald L; Davis, Paul H; Lee, Jeunghoon; Kuang, Wan; Hughes, William L; Graugnard, Elton; Yurke, Bernard; Knowlton, William B

    2015-03-18

    A promising application of DNA self-assembly is the fabrication of chromophore-based excitonic devices. DNA brick assembly is a compelling method for creating programmable nanobreadboards on which chromophores may be rapidly and easily repositioned to prototype new excitonic devices, optimize device operation, and induce reversible switching. Using DNA nanobreadboards, we have demonstrated each of these functions through the construction and operation of two different excitonic AND logic gates. The modularity and high chromophore density achievable via this brick-based approach provide a viable path toward developing information processing and storage systems.

  7. Exciton coupling of surface complexes on a nanocrystal surface.

    PubMed

    Xu, Xiangxing; Ji, Jianwei; Wang, Guan; You, Xiaozeng

    2014-08-25

    Exciton coupling may arise when chromophores are brought into close spatial proximity. Herein the intra-nanocrystal exciton coupling of the surface complexes formed by coordination of 8-hydroxyquinoline to ZnS nanocrystals (NCs) is reported. It is studied by absorption, photoluminescence (PL), PL excitation (PLE), and PL lifetime measurements. The exciton coupling of the surface complexes tunes the PL color and broadens the absorption and PLE windows of the NCs, and thus is a potential strategy for improving the light-harvesting efficiency of NC solar cells and photocatalysts.

  8. Donor–Acceptor Oligorotaxanes Made to Order

    SciTech Connect

    Basu, Subhadeep; Coskun, Ali; Friedman, Douglas C.; Olson, Mark A.; Benitez, Diego; Tkatchouk, Ekaterina; Barin, Gokhan; Yang, Jeffrey; Fahrenbach, Albert C.; Goddard, William A.; Stoddart, J. Fraser

    2011-01-01

    Five donor–acceptor oligorotaxanes made up of dumbbells composed of tetraethylene glycol chains, interspersed with three and five 1,5-dioxynaphthalene units, and terminated by 2,6-diisopropylphenoxy stoppers, have been prepared by the threading of discrete numbers of cyclobis(paraquat-p-phenylene) rings, followed by a kinetically controlled stoppering protocol that relies on click chemistry. The well-known copper(I)-catalyzed alkyne–azide cycloaddition between azide functions placed at the ends of the polyether chains and alkyne-bearing stopper precursors was employed during the final kinetically controlled template-directed synthesis of the five oligorotaxanes, which were characterized subsequently by ¹H NMR spectroscopy at low temperature (233 K) in deuterated acetonitrile. The secondary structures, as well as the conformations, of the five oligorotaxanes were unraveled by spectroscopic comparison with the dumbbell and ring components. By focusing attention on the changes in chemical shifts of some key probe protons, obtained from a wide range of low-temperature spectra, a picture emerges of a high degree of folding within the thread protons of the dumbbells of four of the five oligorotaxanes—the fifth oligorotaxane represents a control compound in effect—brought about by a combination of C[BOND]H···O and π–π stacking interactions between the π-electron-deficient bipyridinium units in the rings and the π-electron-rich 1,5-dioxynaphthalene units and polyether chains in the dumbbells. The secondary structures of a foldamer-like nature have received further support from a solid-state superstructure of a related [3]pseudorotaxane and density functional calculations performed thereon.

  9. Role of phonons in Josephson oscillations of excitonic and polaritonic condensates

    SciTech Connect

    Magnusson, E. B.; Flayac, H.; Malpuech, G.; Shelykh, I. A.

    2010-11-15

    We analyze theoretically the role of the exciton-phonon interactions in phenomena related to the Josephson effect between two spatially separated exciton and exciton-polariton condensates. We consider the role of the dephasing introduced by phonons in such phenomena as Josephson tunneling, self-trapping and spontaneous polarization separation. In the regime of cw pumping we find a remarkable bistability effect arising from exciton-exciton interactions as well as regimes of self-sustained regular and chaotic oscillations.

  10. Dopant-Catalyzed Singlet Exciton Fission.

    PubMed

    Snamina, Mateusz; Petelenz, Piotr

    2017-01-04

    In acene-based molecular crystals, singlet exciton fission occurs through superexchange mediated by two virtual charge-transfer states. Hence, it is sensitive to their energies, which depend on the local environment. The crucial point is the balance between the charge-quadrupole interactions within the pair of molecules directly involved in the process and those with the surrounding crystal matrix, which are governed by local symmetry and may be influenced by breaking this symmetry. This happens, for example, in the vicinity of a vacancy or an impurity and in the latter case is complemented by polarization energy and potentially by dipolar contributions. Our model calculations indicate that the superexchange coupling is sensitive enough to these factors to enable fission to be catalyzed by judiciously designed dopant molecules. In favorable cases, dipolar dopants are expected to increase the fission rate by an order of magnitude.

  11. 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.

  12. The role of exciton ionization processes in bulk heterojunction organic photovoltaic cells

    NASA Astrophysics Data System (ADS)

    Zou, Yunlong; Holmes, Russell

    2015-03-01

    Dissociating photogenerated excitons into their constituent charges is essential for efficient photoconversion in organic semiconductors. Organic photovoltaics cells (OPV) widely adopt a heterojunction architecture where dissociation is facilitated by charge transfer at a donor-acceptor (D-A) interface. Interestingly, recent work on MoOx/C60 Schottky OPVs has demonstrated that excitons in C60 may also undergo bulk-ionization to generate photocurrent, driven by the built-in field at the MoOx/C60 interface. Here, we show that bulk-ionization processes also contribute to the photocurrent in bulk heterojunction (BHJ) OPVs with fullerene-rich compositions. The short-circuit current density (JSC) in a MoOx/C60 Schottky OPVs shows almost no dependence on temperature down to 80 K. This characteristic of bulk-ionization allows the use of temperature-dependent measurements of JSC to distinguish dissociation by bulk-ionization from charge transfer at a D-A interface. For BHJ OPVs constructed using the D-A pairing of boron subphthalocyanine chloride (SubPc)-C60, bulk-ionization is found to contribute >10% of the total photocurrent and >30% of the photocurrent from C60. We further find that fullerene-rich SubPc-C60 BHJ OPVs show a larger open-circuit voltage (VOC) than evenly mixed BHJs due to the presence of bulk-ionization. This talk will examine the dependence of JSC and VOC on the relative fraction of dissociation by charge transfer and bulk-ionization processes.

  13. Intramolecular charge transfer in donor-acceptor molecules

    SciTech Connect

    Slama-Schwok, A.; Blanchard-Desce, M.; Lehn, J.M. )

    1990-05-17

    The photophysical properties of donor-acceptor molecules, push-pull polyenes and carotenoids, have been studied by absorption and fluorescence spectroscopy. The compounds bear various acceptor and donor groups, linked together by chains of different length and structure. The position of the absorption and fluorescence maxima and their variation in solvents of increasing polarity are in agreement with long-distance intramolecular charge-transfer processes, the linker acting as a molecular wire. The effects of the linker length and structure and of the nature of acceptor and donor are presented.

  14. Alteration of cartilage glycosaminoglycan protein acceptor by somatomedin and cortisol.

    PubMed

    Kilgore, B S; McNatt, M L; Meador, S; Lee, J A; Hughes, E R; Elders, M J

    1979-02-01

    The effect of somatomedin and cortisol on embryonic chick cartilage in vitro indicates that somatomedin stimulates 35SO4 uptake while cortisol decreases it with no effect on glycosaminoglycan turnover. Xylosyltransferase activity is increased in crude fractions of somatomedin-treated cartilage but decreased in cortisol-treated cartilage. By using a Smith-degraded proteoglycan as an exogenous acceptor, xylosyltransferase activities from both treatments were equivalent, suggesting that the enzyme was not rate limiting. The results of xylosyltransferase assays conducted by mixing enzyme and endogenous acceptor from control, cortisol-treated and somatomedin-treated cartilage, suggest both effects to be at the level of the acceptor protein.

  15. Bound states and the Bekenstein bound

    SciTech Connect

    Bousso, Raphael

    2003-10-16

    We explore the validity of the generalized Bekenstein bound, S<= pi M a. We define the entropy S as the logarithm of the number of states which have energy eigenvalue below M and are localized to a flat space region of width alpha. If boundary conditions that localize field modes are imposed by fiat, then the bound encounters well-known difficulties with negative Casimir energy and large species number, as well as novel problems arising only in the generalized form. In realistic systems, however, finite-size effects contribute additional energy. We study two different models for estimating such contributions. Our analysis suggests that the bound is both valid and nontrivial if interactions are properly included, so that the entropy S counts the bound states of interacting fields.

  16. Exciton-exciton interactions in CdWO{sub 4} irradiated by intense femtosecond vacuum ultraviolet pulses

    SciTech Connect

    Kirm, M.; Nagirnyi, V.; Feldbach, E.; De Grazia, M.; Carre, B.; Merdji, H.; Guizard, S.; Geoffroy, G.; Gaudin, J.; Fedorov, N.; Martin, P.; Vasil'ev, A.; Belsky, A.

    2009-06-15

    Exciton-exciton interaction is experimentally revealed and quantitatively analyzed in a wide band-gap scintillator material CdWO{sub 4}. Under high-intensity femtosecond vacuum ultraviolet excitation, the CdWO{sub 4} luminescence is quenched, while its decay becomes essentially nonexponential. We propose an analytical model, which successfully reproduces the decay kinetics recorded in a wide range of excitation densities. The dipole-dipole interaction between excitons leading to their nonradiative decay is shown to be the main cause of a nonproportional response common for many scintillators.

  17. Hole-Burning Spectroscopy on Excitonically Coupled Pigments in Proteins: Theory Meets Experiment

    PubMed Central

    2016-01-01

    A theory for the calculation of resonant and nonresonant hole-burning (HB) spectra of pigment–protein complexes is presented and applied to the water-soluble chlorophyll-binding protein (WSCP) from cauliflower. The theory is based on a non-Markovian line shape theory (Renger and MarcusJ. Chem. Phys.2002, 116, 9997) and includes exciton delocalization, vibrational sidebands, and lifetime broadening. An earlier approach by Reppert (J. Phys. Chem. Lett.2011, 2, 2716) is found to describe nonresonant HB spectra only. Here we present a theory that can be used for a quantitative description of HB data for both nonresonant and resonant burning conditions. We find that it is important to take into account the excess energy of the excitation in the HB process. Whereas excitation of the zero-phonon transition of the lowest exciton state, that is, resonant burning allows the protein to access only its conformational substates in the neighborhood of the preburn state, any higher excitation gives the protein full access to all conformations present in the original inhomogeneous ensemble. Application of the theory to recombinant WSCP from cauliflower, reconstituted with chlorophyll a or chlorophyll b, gives excellent agreement with experimental data by Pieper et al. (J. Phys. Chem. B2011, 115, 405321417356) and allows us to obtain an upper bound of the lifetime of the upper exciton state directly from the HB experiments in agreement with lifetimes measured recently in time domain 2D experiments by Alster et al. (J. Phys. Chem. B2014, 118, 352424627983). PMID:26811003

  18. First-principles simulation of light propagation and exciton dynamics in metal cluster nanostructures

    NASA Astrophysics Data System (ADS)

    Lisinetskaya, Polina G.; Röhr, Merle I. S.; Mitrić, Roland

    2016-06-01

    We present a theoretical approach for the simulation of the electric field and exciton propagation in ordered arrays constructed of molecular-sized noble metal clusters bound to organic polymer templates. In order to describe the electronic coupling between individual constituents of the nanostructure we use the ab initio parameterized transition charge method which is more accurate than the usual dipole-dipole coupling. The electronic population dynamics in the nanostructure under an external laser pulse excitation is simulated by numerical integration of the time-dependent Schrödinger equation employing the fully coupled Hamiltonian. The solution of the TDSE gives rise to time-dependent partial point charges for each subunit of the nanostructure, and the spatio-temporal electric field distribution is evaluated by means of classical electrodynamics methods. The time-dependent partial charges are determined based on the stationary partial and transition charges obtained in the framework of the TDDFT. In order to treat large plasmonic nanostructures constructed of many constituents, the approximate self-consistent iterative approach presented in (Lisinetskaya and Mitrić in Phys Rev B 89:035433, 2014) is modified to include the transition-charge-based interaction. The developed methods are used to study the optical response and exciton dynamics of Ag3+ and porphyrin-Ag4 dimers. Subsequently, the spatio-temporal electric field distribution in a ring constructed of ten porphyrin-Ag4 subunits under the action of circularly polarized laser pulse is simulated. The presented methodology provides a theoretical basis for the investigation of coupled light-exciton propagation in nanoarchitectures built from molecular size metal nanoclusters in which quantum confinement effects are important.

  19. Enhanced multiple exciton generation in quasi-one-dimensional semiconductors.

    PubMed

    Cunningham, Paul D; Boercker, Janice E; Foos, Edward E; Lumb, Matthew P; Smith, Anthony R; Tischler, Joseph G; Melinger, Joseph S

    2011-08-10

    The creation of a single electron-hole pair (i.e., exciton) per incident photon is a fundamental limitation for current optoelectronic devices including photodetectors and photovoltaic cells. The prospect of multiple exciton generation per incident photon is of great interest to fundamental science and the improvement of solar cell technology. Multiple exciton generation is known to occur in semiconductor nanostructures with increased efficiency and reduced threshold energy compared to their bulk counterparts. Here we report a significant enhancement of multiple exciton generation in PbSe quasi-one-dimensional semiconductors (nanorods) over zero-dimensional nanostructures (nanocrystals), characterized by a 2-fold increase in efficiency and reduction of the threshold energy to (2.23 ± 0.03)E(g), which approaches the theoretical limit of 2E(g). Photovoltaic cells based on PbSe nanorods are capable of improved power conversion efficiencies, in particular when operated in conjunction with solar concentrators.

  20. Electrical Activation of Dark Excitonic States in Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

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

    Electrical activation of optical transitions to parity-forbidden dark excitonic states in individual carbon nanotubes is reported. We examine electric field effects on various excitonic states by simultaneously measuring both photocurrent and photoluminescence. As the applied field increases, we observe an emergence of new absorption peaks in the excitation spectra. From the diameter dependence of the energy separation between the new peaks and the ground state of E11 excitons, we attribute the peaks to the dark excited states which became optically active due to the applied field. A simple field-induced exciton dissociation model is introduced to explain the photocurrent threshold fields, and the edge of the E11 continuum states have been identified using this model. Work supported by JSPS (KAKENHI 24340066, 26610080), MEXT (Photon Frontier Network Program, Nanotechnology Platform), Canon Foundation, and Asahi Glass Foundation.

  1. Singlet exciton fission-sensitized infrared quantum dot solar cells.

    PubMed

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

    2012-02-08

    We demonstrate an organic/inorganic hybrid photovoltaic device architecture that uses singlet exciton fission to permit the collection of two electrons per absorbed high-energy photon while simultaneously harvesting low-energy photons. In this solar cell, infrared photons are absorbed using lead sulfide (PbS) nanocrystals. Visible photons are absorbed in pentacene to create singlet excitons, which undergo rapid exciton fission to produce pairs of triplets. Crucially, we identify that these triplet excitons can be ionized at an organic/inorganic heterointerface. We report internal quantum efficiencies exceeding 50% and power conversion efficiencies approaching 1%. These findings suggest an alternative route to circumvent the Shockley-Queisser limit on the power conversion efficiency of single-junction solar cells.

  2. Excitonic condensation in systems of strongly correlated electrons

    NASA Astrophysics Data System (ADS)

    Kuneš, Jan

    2015-08-01

    The idea of exciton condensation in solids was introduced in the 1960s with the analogy of superconductivity in mind. While exciton supercurrents have been realised only in artificial quantum-well structures so far, the application of the concept of excitonic condensation to bulk solids leads to a rich spectrum of thermodynamic phases with diverse physical properties. In this review we discuss recent developments in the theory of exciton condensation in systems described by Hubbard-type models. In particular, we focus on the connections to their various strong-coupling limits that have been studied in other contexts, e.g. cold atoms physics. One of our goals is to provide a ‘dictionary’ that would allow the reader to efficiently combine results obtained in these different fields.

  3. Simulations of singlet exciton diffusion in organic semiconductors: a review

    DOE PAGES

    Bjorgaard, Josiah A.; Kose, Muhammet Erkan

    2014-12-22

    Our review describes the various aspects of simulation strategies for exciton diffusion in condensed phase thin films of organic semiconductors. Several methods for calculating energy transfer rate constants are discussed along with procedures for how to account for energetic disorder. Exciton diffusion can be modelled by using kinetic Monte-Carlo methods or master equations. Recent literature on simulation efforts for estimating exciton diffusion lengths of various conjugated polymers and small molecules are introduced. Moreover, these studies are discussed in the context of the effects of morphology on exciton diffusion and the necessity of accurate treatment of disorder for comparison of simulationmore » results with those of experiment.« less

  4. Exciton-stimulated modulation of recombination in solar cells

    SciTech Connect

    Karazhanov, S.Z.

    1997-12-01

    This work reports an investigation of the effect of excitons on carrier recombination and solar energy conversion processes. The probabilities of exciton-stimulated modulation of the occupancy of r centers in CdS as well as the binding coefficient of free electrons and holes into excitons are estimated. Carrier recombination and transport theories are presented. The theories are applied to Cu{sub 2}S/CdS solar cells for AM1 illumination at a temperature of 300 K. It has been shown by numerical estimation that exciton-stimulated modulation of the occupancy of deep impurities does give a significant reduction of carrier recombination losses and efficiency improvements for Cu{sub 2}S/CdS solar cells. {copyright} {ital 1997 American Institute of Physics.}

  5. Anomalous magnetization of a carbon nanotube as an excitonic insulator

    NASA Astrophysics Data System (ADS)

    Rontani, Massimo

    2014-11-01

    We show theoretically that an undoped carbon nanotube might be an excitonic insulator—the long-sought phase of matter proposed by Keldysh, Kohn, and others fifty years ago. We predict that the condensation of triplet excitons, driven by intervalley exchange interaction, spontaneously occurs at equilibrium if the tube radius is sufficiently small. The signatures of exciton condensation are its sizable contributions to both the energy gap and the magnetic moment per electron. The increase of the gap might have already been measured, albeit with a different explanation [V. V. Deshpande, B. Chandra, R. Caldwell, D. S. Novikov, J. Hone, and M. Bockrath, Science 323, 106 (2009), 10.1126/science.1165799]. The enhancement of the quasiparticle magnetic moment is a pair-breaking effect that counteracts the weak paramagnetism of the ground-state condensate of excitons. This property could rationalize the anomalous magnitude of magnetic moments recently observed in different devices close to charge neutrality.

  6. Nitrogen is a deep acceptor in ZnO

    SciTech Connect

    Tarun, M. C.; Iqbal, M. Zafar; McCluskey, M. D.

    2011-04-14

    Zinc oxide is a promising material for blue and UV solid-state lighting devices, among other applications. Nitrogen has been regarded as a potential p-type dopant for ZnO. However, recent calculations indicate that nitrogen is a deep acceptor. This paper presents experimental evidence that nitrogen is, in fact, a deep acceptor and therefore cannot produce p-type ZnO. A broad photoluminescence (PL) emission band near 1.7 eV, with an excitation onset of ~2.2 eV, was observed, in agreement with the deep-acceptor model of the nitrogen defect. Thus the deep-acceptor behavior can be explained by the low energy of the ZnO valence band relative to the vacuum level.

  7. Nitrogen is a deep acceptor in ZnO

    DOE PAGES

    Tarun, M. C.; Iqbal, M. Zafar; McCluskey, M. D.

    2011-04-14

    Zinc oxide is a promising material for blue and UV solid-state lighting devices, among other applications. Nitrogen has been regarded as a potential p-type dopant for ZnO. However, recent calculations indicate that nitrogen is a deep acceptor. This paper presents experimental evidence that nitrogen is, in fact, a deep acceptor and therefore cannot produce p-type ZnO. A broad photoluminescence (PL) emission band near 1.7 eV, with an excitation onset of ~2.2 eV, was observed, in agreement with the deep-acceptor model of the nitrogen defect. Thus the deep-acceptor behavior can be explained by the low energy of the ZnO valence bandmore » relative to the vacuum level.« less

  8. 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.

  9. Exciton dynamics of CdS thin films produced by chemical bath deposition and DC pulse sputtering.

    PubMed

    Cooper, Jason K; Cao, Jinbo; Zhang, Jin Z

    2013-08-14

    Exciton dynamics of CdS films have been investigated using ultrafast laser spectroscopy with an emphasis on understanding defect-related recombination. Two types of CdS films were deposited on glass substrates via direct current pulse sputtering (DCPS) and chemical bath deposition (CBD) techniques. The films displayed distinct morphological, optical, and structural properties. Their exciton and charge carrier dynamics within the first 1 ns following photoexcitation were characterized by femotosecond pump probe spectroscopy. A singular value decomposition (SVD) global fitting technique was employed to extract the lifetime and wavelength dependence of transient species. The excited electrons of the DCPS sample decays through 1.8, 8, 65, and 450 ps time constants which were attributed to donor level electron trapping, valence band (VB) → conduction band (CB) recombination, shallow donor recombination, and deep donor recombination, respectively. The CBD sample shows time constants of 6, 65, and 450 ps which were attributed to CB → VB recombination, sulfur vacancy (VS) recombination, and VS → oxygen interstitial (Oi) donor-acceptor pair (DAP) recombination, respectively. It was found that the DCPS deposition technique produces films with lower defect density and improved carrier dynamics, which are important for high performance solar cell applications.

  10. Impact of intramolecular twisting and exciton migration on emission efficiency of multifunctional fluorene-benzothiadiazole-carbazole compounds

    NASA Astrophysics Data System (ADS)

    Karpicz, R.; Puzinas, S.; Krotkus, S.; Kazlauskas, K.; Jursenas, S.; Grazulevicius, J. V.; Grigalevicius, S.; Gulbinas, V.

    2011-05-01

    Novel donor-acceptor compounds consisting of singly bonded fluorene (Fl), benzothiadiazole (BT), and carbazole (Cz) functional units in the same molecule were investigated. Analysis of the optical spectra and fluorescence transients of the compounds revealed the domination of intramolecular charge transfer (ICT) states with high fluorescence quantum yield (72%-85%). A similar Cz-Fl-Cz compound exhibiting 100% fluorescence quantum yield and no ICT character was also studied as a reference to reveal the impact of electron-accepting BT groups. Thorough examination of the optical properties of the compounds in different media, i.e., dilute solution and polymer matrix, indicated their twisted conformations due to steric hindrance in the ground state and flattened geometry in the excited state for both reference and ICT compounds. Remarkable fluorescence efficiency losses (amounting to 70%) observed upon casting the molecular solutions into neat films were determined to originate from the low-fluorescent twisted conformers and migration-facilitated exciton quenching. The majority of emission efficiency losses (over 70%) were caused by the twisted conformers, whereas only less than 30% by exciton-migration-induced nonradiative deactivation.

  11. Fullerene-bisadduct acceptors for polymer solar cells.

    PubMed

    Li, Yongfang

    2013-10-01

    Polymer solar cells (PSCs) have drawn great attention in recent years for their simple device structure, light weight, and low-cost fabrication in comparison with inorganic semiconductor solar cells. However, the power-conversion efficiency (PCE) of PSCs needs to be increased for their future application. The key issue for improving the PCE of PSCs is the design and synthesis of high-efficiency conjugated polymer donors and fullerene acceptors for the photovoltaic materials. For the acceptor materials, several fullerene-bisadduct acceptors with high LUMO energy levels have demonstrated excellent photovoltaic performance in PSCs with P3HT as a donor. In this Focus Review, recent progress in high-efficiency fullerene-bisadduct acceptors is discussed, including the bisadduct of PCBM, indene-C60 bisadduct (ICBA), indene-C70 bisadduct (IC70BA), DMPCBA, NCBA, and bisTOQC. The LUMO levels and photovoltaic performance of these bisadduct acceptors with P3HT as a donor are summarized and compared. In addition, the applications of an ICBA acceptor in new device structures and with other conjugated polymer donors than P3HT are also introduced and discussed.

  12. Luminescence dynamics of bound exciton of hydrogen doped ZnO nanowires

    SciTech Connect

    Yoo, Jinkyoung; Yi, Gyu -Chul; Chon, Bonghwan; Joo, Taiha; Wang, Zhehui

    2016-04-11

    In this study, all-optical camera, converting X-rays into visible photons, is a promising strategy for high-performance X-ray imaging detector requiring high detection efficiency and ultrafast detector response time. Zinc oxide is a suitable material for all-optical camera due to its fast radiative recombination lifetime in sub-nanosecond regime and its radiation hardness. ZnO nanostructures have been considered as proper building blocks for ultrafast detectors with spatial resolution in sub-micrometer scale. To achieve remarkable enhancement of luminescence efficiency n-type doping in ZnO has been employed. However, luminescence dynamics of doped ZnO nanostructures have not been thoroughly investigated whereas undoped ZnO nanostructures have been employed to study their luminescence dynamics. Here we report a study of luminescence dynamics of hydrogen doped ZnO nanowires obtained by hydrogen plasma treatment. Hydrogen doping in ZnO nanowires gives rise to significant increase in the near-band-edge emission of ZnO and decrease in averaged photoluminescence lifetime from 300 to 140 ps at 10 K. The effects of hydrogen doping on the luminescent characteristics of ZnO nanowires were changed by hydrogen doping process variables.

  13. Luminescence dynamics of bound exciton of hydrogen doped ZnO nanowires

    DOE PAGES

    Yoo, Jinkyoung; Yi, Gyu -Chul; Chon, Bonghwan; ...

    2016-04-11

    In this study, all-optical camera, converting X-rays into visible photons, is a promising strategy for high-performance X-ray imaging detector requiring high detection efficiency and ultrafast detector response time. Zinc oxide is a suitable material for all-optical camera due to its fast radiative recombination lifetime in sub-nanosecond regime and its radiation hardness. ZnO nanostructures have been considered as proper building blocks for ultrafast detectors with spatial resolution in sub-micrometer scale. To achieve remarkable enhancement of luminescence efficiency n-type doping in ZnO has been employed. However, luminescence dynamics of doped ZnO nanostructures have not been thoroughly investigated whereas undoped ZnO nanostructures havemore » been employed to study their luminescence dynamics. Here we report a study of luminescence dynamics of hydrogen doped ZnO nanowires obtained by hydrogen plasma treatment. Hydrogen doping in ZnO nanowires gives rise to significant increase in the near-band-edge emission of ZnO and decrease in averaged photoluminescence lifetime from 300 to 140 ps at 10 K. The effects of hydrogen doping on the luminescent characteristics of ZnO nanowires were changed by hydrogen doping process variables.« less

  14. Exciton energy-momentum map of hexagonal boron nitride

    NASA Astrophysics Data System (ADS)

    Fugallo, Giorgia; Aramini, Matteo; Koskelo, Jaakko; Watanabe, Kenji; Taniguchi, Takashi; Hakala, Mikko; Huotari, Simo; Gatti, Matteo; Sottile, Francesco

    2015-10-01

    Understanding and controlling the way excitons propagate in solids is a key for tailoring materials with improved optoelectronic properties. A fundamental step in this direction is the determination of the exciton energy-momentum dispersion. Here, thanks to the solution of the parameter-free Bethe-Salpeter equation (BSE), we draw and explain the exciton energy-momentum map of hexagonal boron nitride (h-BN) in the first three Brillouin zones. We show that h-BN displays strong excitonic effects not only in the optical spectra at vanishing momentum q , as previously reported, but also at large q . We validate our theoretical predictions by assessing the calculated exciton map by means of an inelastic x-ray scattering (IXS) experiment. Moreover, we solve the discrepancies between previous experimental data and calculations, proving then that the BSE is highly accurate through the whole momentum range. Therefore, these results put forward the combination BSE and IXS as the tool of choice for addressing the exciton dynamics in complex materials.

  15. Exciton Band Structure in Two-Dimensional Materials

    NASA Astrophysics Data System (ADS)

    Cudazzo, Pierluigi; Sponza, Lorenzo; Giorgetti, Christine; Reining, Lucia; Sottile, Francesco; Gatti, Matteo

    2016-02-01

    Low-dimensional materials differ from their bulk counterparts in many respects. In particular, the screening of the Coulomb interaction is strongly reduced, which can have important consequences such as the significant increase of exciton binding energies. In bulk materials the binding energy is used as an indicator in optical spectra to distinguish different kinds of excitons, but this is not possible in low-dimensional materials, where the binding energy is large and comparable in size for excitons of very different localization. Here we demonstrate that the exciton band structure, which can be accessed experimentally, instead provides a powerful way to identify the exciton character. By comparing the ab initio solution of the many-body Bethe-Salpeter equation for graphane and single-layer hexagonal boron nitride, we draw a general picture of the exciton dispersion in two-dimensional materials, highlighting the different role played by the exchange electron-hole interaction and by the electronic band structure. Our interpretation is substantiated by a prediction for phosphorene.

  16. Magnetic brightening of dark excitons in transitional metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-Xiao; Lu, Zhengguang; Cao, Ting; Zhang, Fan; Hone, James; Louie, Steven G.; Li, Zhiqiang; Smirnov, Dmitry; Heinz, Tony

    Transitional metal dichalcogenides (TMDC) in the MX2 (M = Mo, W, X = S, Se) family represent an excellent platform to study of excitonic effects. At monolayer thickness, these materials exhibit both direct band-gap character and enhanced excitonic interactions. Theoretical studies suggest that both the valence and conduction bands are split and exhibit spin polarized character at the K/K' valleys. The lowest energy band-edge excitons are predicted to have different spin configurations for different materials in this family. When the lowest lying exciton has parallel electron and hole spin, radiative decay is forbidden and the state is dark. Here we demonstrate that by applying an in-plane magnetic field we can perturb the exciton spin configuration and brighten this state, allowing it to undergo radiative decay. We identify such a brightened dark state by the emergence of a new emission peak lying below the absorption peak, with a strength growing with applied in-plane magnetic field. On the other hand, for monolayer MoSe2, where no low-lying dark state is expected, we do not see the growth of a new emission feature under application of an in-plane magnetic field. Our experimental findings are in agreement with the calculated properties of dark excitons based on GW plus Bethe-Salpeter equation approach

  17. Exciton Band Structure in Two-Dimensional Materials.

    PubMed

    Cudazzo, Pierluigi; Sponza, Lorenzo; Giorgetti, Christine; Reining, Lucia; Sottile, Francesco; Gatti, Matteo

    2016-02-12

    Low-dimensional materials differ from their bulk counterparts in many respects. In particular, the screening of the Coulomb interaction is strongly reduced, which can have important consequences such as the significant increase of exciton binding energies. In bulk materials the binding energy is used as an indicator in optical spectra to distinguish different kinds of excitons, but this is not possible in low-dimensional materials, where the binding energy is large and comparable in size for excitons of very different localization. Here we demonstrate that the exciton band structure, which can be accessed experimentally, instead provides a powerful way to identify the exciton character. By comparing the ab initio solution of the many-body Bethe-Salpeter equation for graphane and single-layer hexagonal boron nitride, we draw a general picture of the exciton dispersion in two-dimensional materials, highlighting the different role played by the exchange electron-hole interaction and by the electronic band structure. Our interpretation is substantiated by a prediction for phosphorene.

  18. Two-dminensional exciton states in monolayer semiconducting phosphorus alotropes

    NASA Astrophysics Data System (ADS)

    Rocha, Alexandre R.; Villegas, Cesar E. P.

    During the last decade, novel two-dimensional (2D) semiconducting materials have been synthesized and characterised. As a result, there have been several theoretical and experimental proposals to incorporate 2D materials for designing next generation electronic and optoelectronics devices. In particular, it has been demonstrated that light absorption in phosphorus-based monolayers can span the whole visible spectrum, suggesting they could be used for optolectronic applications. A key ingredient for optolectronic applications is the presence of excitons and their subsequent diffusion along a donor material. This is influenced by the character of the different excitations taking place, as well as, the exciton binding energy. Therefore, In this work we use accurate many-body corrected density functional theory by means of GW-BSE methodology to elucidate the most important optical transitions, exciton energy spectrum as well as exciton extension in different types of phosphorene materials. In addition, we solve the Schrodinger equation for different 2D screened potentials and estimate the 2D exciton energy levels and radius extension. Finally, in order to assess further studies based on these systems, we provide a simple analityc expression for estimating 2D exciton energy levels. Research funded by FAPESP-Brazil.

  19. Cooperative effects of solvent and polymer acceptor co-additives in P3HT:PDI solar cells: simultaneous optimization in lateral and vertical phase separation.

    PubMed

    Li, Mingguang; Wang, Lei; Liu, Jiangang; Zhou, Ke; Yu, Xinhong; Xing, Rubo; Geng, Yanhou; Han, Yanchun

    2014-03-14

    In this work, solvent chloronaphthalene (CN) and polymer acceptor an alternating copolymer of perylene diimide and carbazole (PCPDI) were utilized as co-additives to optimize the nanoscale phase-separated morphology and photovoltaic properties of bulk-heterojunction (BHJ) polymer solar cells based on the poly(3-hexyl thiophene) (P3HT)/N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) system. The domain size of EP-PDI molecules together with that of P3HT distinctly decreased by adding a 0.75 vol% CN additive. The optimized lateral phase separation increased the donor-acceptor interfacial area and facilitated the exciton dissociation process, leading to 5-fold enhancement of short-circuit current (JSC). Furthermore, when PCPDI was employed as a co-additive, acceptor materials (including PCPDI and EP-PDI) were prone to aggregation towards the top surface of blend films, improving vertical phase separation of active layers. PCPDI incorporation, which improved the percolation pathways for electron carriers, suppressed the crystallinity of P3HT distinctly. Thus, much more balanced charge transport was achieved by PCPDI addition, which resulted in almost 1-fold enhancement of open-circuit voltage (VOC) by reducing nongeminate recombination. As a consequence, cooperative effects of CN and PCPDI additives improved the nanoscale phase-separated morphology in lateral and vertical directions simultaneously, achieving the enhancement in both VOC and JSC.

  20. Acousto-exciton interaction in a gas of 2D indirect dipolar excitons in the presence of disorder

    NASA Astrophysics Data System (ADS)

    Kovalev, V. M.; Chaplik, A. V.

    2016-03-01

    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 drag 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.

  1. Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures

    SciTech Connect

    Boulesbaa, Abdelaziz; Wang, Kai; Mahjouri-Samani, Masoud; Tian, Mengkun; Puretzky, Alexander A.; Ivanov, Ilia; Rouleau, Christopher M.; Xiao, Kai; Sumpter, Bobby G.; Geohegan, David B.

    2016-10-18

    We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure for optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.

  2. Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures

    DOE PAGES

    Boulesbaa, Abdelaziz; Wang, Kai; Mahjouri-Samani, Masoud; ...

    2016-10-18

    We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure formore » optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.« less

  3. Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures.

    PubMed

    Boulesbaa, Abdelaziz; Wang, Kai; Mahjouri-Samani, Masoud; Tian, Mengkun; Puretzky, Alexander A; Ivanov, Ilia; Rouleau, Christopher M; Xiao, Kai; Sumpter, Bobby G; Geohegan, David B

    2016-11-09

    Photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors, i.e., monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions has attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge-transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure for optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS2) and a single layer of cadmium selenide/zinc sulfide core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that, following electron transfer from the 2D to the 0D, hybrid excitons, wherein the electron resides in the 0D and the hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ∼140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.

  4. Electronic and optical properties of single excitons and biexcitons in type-II quantum dot nanocrystals

    NASA Astrophysics Data System (ADS)

    Koc, Fatih; Sahin, Mehmet

    2014-05-01

    In this study, a detailed investigation of the electronic and optical properties (i.e., binding energies, absorption wavelength, overlap of the electron-hole wave functions, recombination oscillator strength, etc.) of an exciton and a biexciton in CdTe/CdSe core/shell type-II quantum dot heterostructures has been carried out in the frame of the single band effective mass approximation. In order to determine the electronic properties, we have self-consistently solved the Poisson-Schrödinger equations in the Hartree approximation. We have considered all probable Coulomb interaction effects on both energy levels and also on the corresponding wave functions for both single exciton and biexciton. In addition, we have taken into account the quantum mechanical exchange-correlation effects in the local density approximation between same kinds of particles for biexciton. Also, we have examined the effect of the ligands and dielectric mismatch on the electronic and optical properties. We have used a different approximation proposed by Sahin and Koc [Appl. Phys. Lett. 102, 183103 (2013)] for the recombination oscillator strength of the biexciton for bound and unbound cases. The results obtained have been presented comparatively as a function of the shell thicknesses and probable physical reasons in behind of the results have been discussed in a detail.

  5. Electronic and optical properties of single excitons and biexcitons in type-II quantum dot nanocrystals

    SciTech Connect

    Koc, Fatih; Sahin, Mehmet E-mail: mehsahin@gmail.com

    2014-05-21

    In this study, a detailed investigation of the electronic and optical properties (i.e., binding energies, absorption wavelength, overlap of the electron-hole wave functions, recombination oscillator strength, etc.) of an exciton and a biexciton in CdTe/CdSe core/shell type-II quantum dot heterostructures has been carried out in the frame of the single band effective mass approximation. In order to determine the electronic properties, we have self-consistently solved the Poisson-Schrödinger equations in the Hartree approximation. We have considered all probable Coulomb interaction effects on both energy levels and also on the corresponding wave functions for both single exciton and biexciton. In addition, we have taken into account the quantum mechanical exchange-correlation effects in the local density approximation between same kinds of particles for biexciton. Also, we have examined the effect of the ligands and dielectric mismatch on the electronic and optical properties. We have used a different approximation proposed by Sahin and Koc [Appl. Phys. Lett. 102, 183103 (2013)] for the recombination oscillator strength of the biexciton for bound and unbound cases. The results obtained have been presented comparatively as a function of the shell thicknesses and probable physical reasons in behind of the results have been discussed in a detail.

  6. Temperature Evolution in Excitonic Absorptions of Cd(0.96)Zn(0.04) Materials

    NASA Technical Reports Server (NTRS)

    Quijada, Manuel A.; Henry, Ross

    2007-01-01

    We report cryogenic optical properties of Cd(0.96)Zn(0.04)Te wafers that are used as substrate seed layers in HgCdTe focal-plane array detectors. These studies are motivated by the fact that the substrate optical properties influence the overall detector performance. The studies consist of measuring the sample frequency dependent transmittance (T) and reflectance (R) above and below the optical band-gap in the UV/Visible and infrared frequency ranges, and with temperature variation of the sample from 5 to 300 K. These measurements show that the optical gap near 1.49 eV at 300 K increases to 1.62 eV at 5 K. Finally, we observe sharp absorption peaks near this gap energy at low temperatures. The close proximity of these peaks to the optical transition threshold suggests that they originate from the creation of bound electron-hole pairs or excitons. The decay of these excitonic absorptions may contribute to a photoluminescence and transient background response of these back-illuminated HgCdTe CCD detectors.

  7. Cooperative Singlet and Triplet Exciton Transport in Tetracene Crystals Visualized by Ultrafast Microscopys

    SciTech Connect

    Wan, Yan; Guo, Zhi; Zhu, Tong; Yan, Suxia; Johnson, Justin; Huang, Libai

    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 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.

  8. 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.

  9. Combined effects of local and nonlocal hybridization on formation and condensation of excitons in the extended Falicov-Kimball model

    NASA Astrophysics Data System (ADS)

    Farkašovský, Pavol

    2017-04-01

    We study the combined effects of local and nonlocal hybridization on the formation and condensation of the excitonic bound states in the extended Falicov-Kimball model by the density-matrix-renormalization-group (DMRG) method. Analysing the resultant behaviours of the excitonic momentum distribution N(q) we found, that unlike the local hybridization V, which supports the formation of the q=0 momentum condensate, the nonlocal hybridization Vn supports the formation of the q = π momentum condensate. The combined effect of local and nonlocal hybridization further enhances the excitonic correlations in q=0 as well as q = π state, especially for V and Vn values from the charge-density-wave (CDW) region. Strong effects of local and nonlocal hybridization are observed also for other ground-state quantities of the model such as the f-electron density, or the density of unbound d-electrons, which are generally enhanced with increasing V and Vn. The same calculations performed for nonzero values of f-level energy Ef revealed that this model can yield a reasonable explanation for the pressure-induced resistivity anomaly observed experimentally in TmSe0.45Te0.55 compound.

  10. Optical Absorption Spectra and Excitons of Dye-Substrate Interfaces: Catechol on TiO2(110).

    PubMed

    Mowbray, Duncan John; Migani, Annapaola

    2016-06-14

    Optimizing the photovoltaic efficiency of dye-sensitized solar cells (DSSC) based on staggered gap heterojunctions requires a detailed understanding of sub-band gap transitions in the visible from the dye directly to the substrate's conduction band (CB) (type-II DSSCs). Here, we calculate the optical absorption spectra and spatial distribution of bright excitons in the visible region for a prototypical DSSC, catechol on rutile TiO2(110), as a function of coverage and deprotonation of the OH anchoring groups. This is accomplished by solving the Bethe-Salpeter equation (BSE) based on hybrid range-separated exchange and correlation functional (HSE06) density functional theory (DFT) calculations. Such a treatment is necessary to accurately describe the interfacial level alignment and the weakly bound charge transfer transitions that are the dominant absorption mechanism in type-II DSSCs. Our HSE06 BSE spectra agree semiquantitatively with spectra measured for catechol on anatase TiO2 nanoparticles. Our results suggest deprotonation of catechol's OH anchoring groups, while being nearly isoenergetic at high coverages, shifts the onset of the absorption spectra to lower energies, with a concomitant increase in photovoltaic efficiency. Further, the most relevant bright excitons in the visible region are rather intense charge transfer transitions with the electron and hole spatially separated in both the [110] and [001] directions. Such detailed information on the absorption spectra and excitons is only accessible via periodic models of the combined dye-substrate interface.

  11. Strong excitonic effects in the optical properties of graphitic carbon nitride g-C3N4 from first principles

    NASA Astrophysics Data System (ADS)

    Wei, Wei; Jacob, Timo

    2013-02-01

    Graphitic carbon nitride (g-C3N4) has recently triggered extensive investigations due to its potential applications, such as in direct photochemical water splitting, CO2 activation, and transition-metal-free spintronics. However, electronic, and particularly the optical properties of g-C3N4 still have not been well established. Based on one of the state-of-the-art approaches—many-body Green's function theory (i.e., GW + BSE)—absorption of ultraviolet light by g-C3N4 is found to be determined by strong excitonic effects with a significantly large binding energy assigned to the bound excitons. Dark states have also been found in g-C3N4, which can affect the photoluminescence yield of g-C3N4. We find that the band gap of g-C3N4 probably can be tuned by adjusting the condensation (dimensionality) to initiate excitonic absorption in the visible light region, which might help improve the solar energy conversion efficiency.

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

    PubMed

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

    2014-06-11

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

  13. The Impact of Heterogeneity and Dark Acceptor States on FRET: Implications for Using Fluorescent Protein Donors and Acceptors

    PubMed Central

    Vogel, Steven S.; Nguyen, Tuan A.; van der Meer, B. Wieb; Blank, Paul S.

    2012-01-01

    Förster resonance energy transfer (FRET) microscopy is widely used to study protein interactions in living cells. Typically, spectral variants of the Green Fluorescent Protein (FPs) are incorporated into proteins expressed in cells, and FRET between donor and acceptor FPs is assayed. As appreciable FRET occurs only when donors and acceptors are within 10 nm of each other, the presence of FRET can be indicative of aggregation that may denote association of interacting species. By monitoring the excited-state (fluorescence) decay of the donor in the presence and absence of acceptors, dual-component decay analysis has been used to reveal the fraction of donors that are FRET positive (i.e., in aggregates)._However, control experiments using constructs containing both a donor and an acceptor FP on the same protein repeatedly indicate that a large fraction of these donors are FRET negative, thus rendering the interpretation of dual-component analysis for aggregates between separately donor-containing and acceptor-containing proteins problematic. Using Monte-Carlo simulations and analytical expressions, two possible sources for such anomalous behavior are explored: 1) conformational heterogeneity of the proteins, such that variations in the distance separating donor and acceptor FPs and/or their relative orientations persist on time-scales long in comparison with the excited-state lifetime, and 2) FP dark states. PMID:23152925

  14. Negative activation energy and dielectric signatures of excitons and excitonic Mott transitions in quantum confined laser structures

    NASA Astrophysics Data System (ADS)

    Bhunia, Amit; Bansal, Kanika; Henini, Mohamed; Alshammari, Marzook S.; Datta, Shouvik

    2016-10-01

    Mostly, optical spectroscopies are used to investigate the physics of excitons, whereas their electrical evidences are hardly explored. Here, we examined a forward bias activated differential capacitance response of GaInP/AlGaInP based multi-quantum well laser diodes to trace the presence of excitons using electrical measurements. Occurrence of "negative activation energy" after light emission is understood as thermodynamical signature of steady state excitonic population under intermediate range of carrier injections. Similar corroborative results are also observed in an InGaAs/GaAs quantum dot laser structure grown by molecular beam epitaxy. With increasing biases, the measured differential capacitance response slowly vanishes. This represents gradual Mott transition of an excitonic phase into an electron-hole plasma in a GaInP/AlGaInP laser diode. This is further substantiated by more and more exponentially looking shapes of high energy tails in electroluminescence spectra with increasing forward bias, which originates from a growing non-degenerate population of free electrons and holes. Such an experimental correlation between electrical and optical properties of excitons can be used to advance the next generation excitonic devices.

  15. Physical Uncertainty Bounds (PUB)

    SciTech Connect

    Vaughan, Diane Elizabeth; Preston, Dean L.

    2015-03-19

    This paper introduces and motivates the need for a new methodology for determining upper bounds on the uncertainties in simulations of engineered systems due to limited fidelity in the composite continuum-level physics models needed to simulate the systems. We show that traditional uncertainty quantification methods provide, at best, a lower bound on this uncertainty. We propose to obtain bounds on the simulation uncertainties by first determining bounds on the physical quantities or processes relevant to system performance. By bounding these physics processes, as opposed to carrying out statistical analyses of the parameter sets of specific physics models or simply switching out the available physics models, one can obtain upper bounds on the uncertainties in simulated quantities of interest.

  16. 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

  17. Simple screened exact-exchange approach for excitonic properties in solids

    NASA Astrophysics Data System (ADS)

    Yang, Zeng-hui; Sottile, Francesco; Ullrich, Carsten A.

    2015-07-01

    We present a screened exact-exchange (SXX) method for the efficient and accurate calculation of the optical properties of solids, where the screening is achieved through the zero-wave-vector limit of the inverse dielectric function. The SXX approach can be viewed as a simplification of the Bethe-Salpeter equation (BSE) or, in the context of time-dependent density-functional theory, as a first step towards a new class of hybrid functionals for the optical properties of solids. SXX performs well for bound excitons and continuum spectra in both small-gap semiconductors and large-gap insulators, with a computational cost much lower than that of the BSE.

  18. Strongly confined excitons in self-assembled InGaAs quantum dot clusters

    NASA Astrophysics Data System (ADS)

    Creasey, Megan; Li, Xiaoqin; Lee, Jihoon; Wang, Zhiming; Salamo, Gregory

    2011-03-01

    Quantum dot clusters (QDCs) consisting of regular geometric patterns of six InGaAs quantum dots (QD) are grown on a GaAs substrate using a hybrid growth method that combines droplet homoepitaxy and Stranski-Krastonov growth. These novel structures have potential applications as tunable single photon sources, entangled photon sources, or error corrected qubits - devices critical to the fields of secure optical communications and quantum computing We study the photoluminescence arising from a single cluster using both continuous wave and ultrafast spectroscopic techniques with variations in the sample temperature and excitation power. Our results suggest excitons (bound electron-hole pairs) are strongly confined within the individual QDs rather than loosely confined throughout the entire QDC. The work at Texas is supported financially by NSF, ARO, AFOSR, ONR, the Welch Foundation, and the Alfred Sloan Foundation. The work at Arkansas is supported by the NSF.

  19. Electrons, Phonons and Excitons at Semiconductor Surfaces

    NASA Astrophysics Data System (ADS)

    Pollmann, Johannes; Krueger, Peter; Mazur, Albert; Rohlfing, Michael

    We briefly address 'state-of-the-art' ab-initio calculations of basic properties of semiconductor surfaces such as their atomic configuration, electronic structure and surface vibrations, as well as, their optical properties and compare exemplary results with experimental data. The surface structure and the electronic ground state are described within the local density approximation (LDA) of density functional theory (DFT). The description of excited electronic states requires to take dynamical correlations in the many electron system into account, which is achieved to a considerable extent within the GW approximation (GWA) leading to the concept of the quasiparticle bandstructure. Surface phonons are treated from first principles within density functional perturbation theory (DFPT). The theory of optical surface properties and surface excitons, in particular, requires to account for the electron-hole Coulomb correlation which is done in the framework of the Bethe-Salpeter equation (BSE). These methods yield results which are in good agreement with experiment and can significantly contribute to an interpretation of experimental data from high-resolution surface microscopy and spectroscopy thus enhancing our current understanding of semiconductor surfaces.

  20. Plasmon transmission through excitonic subwavelength gaps.

    PubMed

    Sukharev, Maxim; Nitzan, Abraham

    2016-04-14

    We study the transfer of electromagnetic energy across a subwavelength gap separating two co-axial metal nanorods. In the absence of spacer in the gap separating the rods, the system exhibits strong coupling behavior between longitudinal plasmons in the two rods. The nature and magnitude of this coupling are studied by varying various geometrical parameters. As a function of frequency, the transmission is dominated by a split longitudinal plasmon peak. The two hybrid modes are the dipole-like "bonding" mode characterized by a peak intensity in the gap and a quadrupole-like "antibonding" mode whose amplitude vanishes at the gap center. When the length of one rod is varied, this mode spectrum exhibits the familiar anti-crossing behavior that depends on the coupling strength determined by the gap width. When off-resonant 2-level emitters are placed in the gap, almost no effect on the frequency dependent transmission is observed. In contrast, when the molecular system is resonant with the plasmonic line shape, the transmission is strongly modified, showing characteristics of strong exciton-plasmon coupling. Most strongly modified is the transmission near the lower frequency "bonding" plasmon mode. The presence of resonant molecules in the gap affects not only the molecule-field interaction but also the spatial distribution of the field intensity and the electromagnetic energy flux across the junction.

  1. Plasmon transmission through excitonic subwavelength gaps

    NASA Astrophysics Data System (ADS)

    Sukharev, Maxim; Nitzan, Abraham

    2016-04-01

    We study the transfer of electromagnetic energy across a subwavelength gap separating two co-axial metal nanorods. In the absence of spacer in the gap separating the rods, the system exhibits strong coupling behavior between longitudinal plasmons in the two rods. The nature and magnitude of this coupling are studied by varying various geometrical parameters. As a function of frequency, the transmission is dominated by a split longitudinal plasmon peak. The two hybrid modes are the dipole-like "bonding" mode characterized by a peak intensity in the gap and a quadrupole-like "antibonding" mode whose amplitude vanishes at the gap center. When the length of one rod is varied, this mode spectrum exhibits the familiar anti-crossing behavior that depends on the coupling strength determined by the gap width. When off-resonant 2-level emitters are placed in the gap, almost no effect on the frequency dependent transmission is observed. In contrast, when the molecular system is resonant with the plasmonic line shape, the transmission is strongly modified, showing characteristics of strong exciton-plasmon coupling. Most strongly modified is the transmission near the lower frequency "bonding" plasmon mode. The presence of resonant molecules in the gap affects not only the molecule-field interaction but also the spatial distribution of the field intensity and the electromagnetic energy flux across the junction.

  2. Benchmarking Calculations of Excitonic Couplings between Bacteriochlorophylls.

    PubMed

    Kenny, Elise P; Kassal, Ivan

    2016-01-14

    Excitonic couplings between (bacterio)chlorophyll molecules are necessary for simulating energy transport in photosynthetic complexes. Many techniques for calculating the couplings are in use, from the simple (but inaccurate) point-dipole approximation to fully quantum-chemical methods. We compared several approximations to determine their range of applicability, noting that the propagation of experimental uncertainties poses a fundamental limit on the achievable accuracy. In particular, the uncertainty in crystallographic coordinates yields an uncertainty of about 20% in the calculated couplings. Because quantum-chemical corrections are smaller than 20% in most biologically relevant cases, their considerable computational cost is rarely justified. We therefore recommend the electrostatic TrEsp method across the entire range of molecular separations and orientations because its cost is minimal and it generally agrees with quantum-chemical calculations to better than the geometric uncertainty. Understanding these uncertainties can guard against striving for unrealistic precision; at the same time, detailed benchmarks can allow important qualitative questions-which do not depend on the precise values of the simulation parameters-to be addressed with greater confidence about the conclusions.

  3. Coexistence of bound and virtual-bound states in shallow-core to valence x-ray spectroscopies

    NASA Astrophysics Data System (ADS)

    Sen Gupta, Subhra; Bradley, J. A.; Haverkort, M. W.; Seidler, G. T.; Tanaka, A.; Sawatzky, G. A.

    2011-08-01

    With the example of the non-resonant inelastic x-ray scattering (NIXS) at the O45 edges (5d→5f) of the actinides, we develop the theory for shallow-core to valence excitations, where the multiplet spread is larger than the core-hole attraction, such as if the core and valence orbitals have the same principal quantum number. This involves very strong final state configuration interaction (CI), which manifests itself as huge reductions in the Slater-Condon integrals, needed to explain the spectral shapes within a simple renormalized atomic multiplet theory. But more importantly, this results in a cross-over from bound (excitonic) to virtual-bound excited states with increasing energy, within the same core-valance multiplet structure, and in large differences between the dipole and high-order multipole transitions, as observed in NIXS. While the bound states (often higher multipole allowed) can still be modeled using local cluster-like models, the virtual-bound resonances (often dipole-allowed) cannot be interpreted within such local approaches. This is in stark contrast to the more familiar core-valence transitions between different principal quantum number shells, where all the final excited states almost invariably form bound core-hole excitons and can be modeled using local approaches. The possibility of observing giant multipole resonances for systems with high angular momentum ground states is also predicted. The theory is important to obtain ground state information from core-level x-ray spectroscopies of strongly correlated transition metal, rare-earth, and actinide systems.

  4. Singlet fission of hot excitons in π-conjugated polymers.

    PubMed

    Zhai, Yaxin; Sheng, Chuanxiang; Vardeny, Z Valy

    2015-06-28

    We used steady-state photoinduced absorption (PA), excitation dependence (EXPA(ω)) spectrum of the triplet exciton PA band, and its magneto-PA (MPA(B)) response to investigate singlet fission (SF) of hot excitons into two separated triplet excitons, in two luminescent and non-luminescent π-conjugated polymers. From the high energy step in the triplet EXPA(ω) spectrum of the luminescent polymer poly(dioctyloxy)phenylenevinylene (DOO-PPV) films, we identified a hot-exciton SF (HE-SF) process having threshold energy at E≈2E(T) (=2.8 eV, where ET is the energy of the lowest lying triplet exciton), which is about 0.8 eV above the lowest singlet exciton energy. The HE-SF process was confirmed by the triplet MPA(B) response for excitation at E>2E(T), which shows typical SF response. This process is missing in DOO-PPV solution, showing that it is predominantly interchain in nature. By contrast, the triplet EXPA(ω) spectrum in the non-luminescent polymer polydiacetylene (PDA) is flat with an onset at E=E(g) (≈2.25 eV). From this, we infer that intrachain SF that involves a triplet-triplet pair state, also known as the 'dark' 2A(g) exciton, dominates the triplet photogeneration in PDA polymer as E(g)>2E(T). The intrachain SF process was also identified from the MPA(B) response of the triplet PA band in PDA. Our work shows that the SF process in π-conjugated polymers is a much more general process than thought previously.

  5. Broken symmetry, excitons, gapless modes, and topological excitations in trilayer quantum Hall systems

    NASA Astrophysics Data System (ADS)

    Ye, Jinwu

    2005-03-01

    We study the interlayer coherent incompressible phase in trilayer quantum Hall systems (TLQH) at total filling factor νT=1 from three approaches: Mutual composite fermion (MCF), composite boson (CB), and wave function approach. Just like in bilayer quantum Hall system, CB approach is superior than MCF approach in studying TLQH with broken symmetry. The Hall and Hall drag resistivities are found to be quantized at h/e2 . Two neutral gapless modes with linear dispersion relations are identified and the ratio of the two velocities is close to 3 . The excitation spectra are classified into two classes, charge neutral bosonic two-body bound states and charge ±1 fermionic three-body bound states. In general, there are two two-body Kosterlize-Thouless (KT) transition temperatures and one three-body KT transition. The charge ±1 three-body fermionic bound states may be the main dissipation source of transport measurements. The broken symmetry in terms of SU (3) algebra is studied. The structure of excitons and their flowing patterns are given. The coupling between the two Goldstone modes will lead to the broadening in the zero-bias peak in the interlayer correlated tunnelings of the TLQH. Several interesting features unique to TLQH are outlined. Limitations of the CB approach are also pointed out.

  6. Designer Metallic Acceptor-Containing Halogen Bonding: General Strategies.

    PubMed

    Zhang, Xinxing; Bowen, Kit H

    2017-03-13

    Being electrostatic interactions in nature, hydrogen bonding (HB) and halogen bonding (XB) are considered to be two parallel worlds. In principle, all the applications that HB has could also be applied to XB. However, there has been no report on a metallic XB acceptor but metal anions have been observed to be good HB acceptors. This missing mosaic piece of XB is because common metal anions are reactive for XB donors. In view of this, we propose two strategies for designing metallic acceptor-containing XB using ab initio calculations. The first one is to utilize a metal cluster anion with a high electron detachment energy, such as the superatom, Al13- as the XB acceptor. The second strategy is to design a ligand passivated/protected metal core while it still can maintain the negative charge; several exotic clusters, such as PtH5-, PtZnH5- and PtMgH5-, are utilized as examples. Based on these two strategies, we anticipate that more metallic acceptor-containing XB will be discovered.

  7. Electron acceptor-dependent respiratory and physiological stratifications in biofilms.

    PubMed

    Yang, Yonggang; Xiang, Yinbo; Sun, Guoping; Wu, Wei-Min; Xu, Meiying

    2015-01-06

    Bacterial respiration is an essential driving force in biogeochemical cycling and bioremediation processes. Electron acceptors respired by bacteria often have solid and soluble forms that typically coexist in the environment. It is important to understand how sessile bacteria attached to solid electron acceptors respond to ambient soluble alternative electron acceptors. Microbial fuel cells (MFCs) provide a useful tool to investigate this interaction. In MFCs with Shewanella decolorationis, azo dye was used as an alternative electron acceptor in the anode chamber. Different respiration patterns were observed for biofilm and planktonic cells, with planktonic cells preferred to respire with azo dye while biofilm cells respired with both the anode and azo dye. The additional azo respiration dissipated the proton accumulation within the anode biofilm. There was a large redox potential gap between the biofilms and anode surface. Changing cathodic conditions caused immediate effects on the anode potential but not on the biofilm potential. Biofilm viability showed an inverse and respiration-dependent profile when respiring with only the anode or azo dye and was enhanced when respiring with both simultaneously. These results provide new insights into the bacterial respiration strategies in environments containing multiple electron acceptors and support an electron-hopping mechanism within Shewanella electrode-respiring biofilms.

  8. Modulation of quantum dot photoemission based on fluorescence resonance energy transfer to a photochromic dye acceptor

    NASA Astrophysics Data System (ADS)

    Medintz, Igor L.; Clapp, Aaron R.; Trammel, Scott A.; Mattoussi, Hedi M.

    2004-12-01

    We demonstrate the use of a photochromic dye to achieve fluorescence resonance energy transfer (FRET) modulation between a QD donor and the dye acceptor brought in close proximity in a selfassembled QD-protein-dye conjugate. The E. coli maltose binding protein (MBP) appended on its C-terminal with an oligohistidine attachment domain, immobilized onto CdSe-ZnS core-shell QDs was labeled with a sulfo-N-hydroxysuccinimide activated photochromic BIPS molecule (1',3-dihydro-1'-(2-carboxyethyl)-3,3-dimethyl-6-nitrospiro[2H-1-benzopyran-2,2'-(2H)-indoline]). Two different dye-to-MBP-protein ratios of 1:1 and 5:1 were used. The ability of MBP-BIPS to modulate QD photoluminescence was tested by switching BIPS from the colorless spiropyran (SP) to the colored merocyanine (MC) using irradiation with white light (>500 nm) or with UV light (~365 nm), respectively. QDs surrounded by ~20 MBP-BIPS with a dye to protein ratio of 1 showed ~25% loss in their photoemission with consecutive repeated switches, while QDs surrounded by ~20 MBP-BIPS with BIPS to MBP ratio of 5 produced a substantially more pronounced rate of FRET where the QD emission was quenched by ~60%. This result suggests the possibility of using QD-protein conjugates to assemble reversible FRET nanoassemblies where the QD emission can be controlled by changing the properties of the acceptors dyes bound to the protein.

  9. All-Polymer Solar Cell Performance Optimized via Systematic Molecular Weight Tuning of Both Donor and Acceptor Polymers.

    PubMed

    Zhou, Nanjia; Dudnik, Alexander S; Li, Ting I N G; Manley, Eric F; Aldrich, Thomas J; Guo, Peijun; Liao, Hsueh-Chung; Chen, Zhihua; Chen, Lin X; Chang, Robert P H; Facchetti, Antonio; Olvera de la Cruz, Monica; Marks, Tobin J

    2016-02-03

    The influence of the number-average molecular weight (Mn) on the blend film morphology and photovoltaic performance of all-polymer solar cells (APSCs) fabricated with the donor polymer poly[5-(2-hexyldodecyl)-1,3-thieno[3,4-c]pyrrole-4,6-dione-alt-5,5-(2,5-bis(3-dodecylthiophen-2-yl)thiophene)] (PTPD3T) and acceptor polymer poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2); N2200) is systematically investigated. The Mn effect analysis of both PTPD3T and N2200 is enabled by implementing a polymerization strategy which produces conjugated polymers with tunable Mns. Experimental and coarse-grain modeling results reveal that systematic Mn variation greatly influences both intrachain and interchain interactions and ultimately the degree of phase separation and morphology evolution. Specifically, increasing Mn for both polymers shrinks blend film domain sizes and enhances donor-acceptor polymer-polymer interfacial areas, affording increased short-circuit current densities (Jsc). However, the greater disorder and intermixed feature proliferation accompanying increasing Mn promotes charge carrier recombination, reducing cell fill factors (FF). The optimized photoactive layers exhibit well-balanced exciton dissociation and charge transport characteristics, ultimately providing solar cells with a 2-fold PCE enhancement versus devices with nonoptimal Mns. Overall, it is shown that proper and precise tuning of both donor and acceptor polymer Mns is critical for optimizing APSC performance. In contrast to reports where maximum power conversion efficiencies (PCEs) are achieved for the highest Mns, the present two-dimensional Mn optimization matrix strategy locates a PCE "sweet spot" at intermediate Mns of both donor and acceptor polymers. This study provides synthetic methodologies to predictably access conjugated polymers with desired Mn and highlights the importance of optimizing Mn for both polymer

  10. 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.

  11. Chiral exciton in the topological insulator Bi2Se3

    NASA Astrophysics Data System (ADS)

    Kung, Hsiang-Hsi; Salehi, Maryam; Wang, Xueyun; Koirala, Nikesh; Brahlek, Matthew; Lee, Alexander; Cheong, Sang-Wook; Oh, Seongshik; Blumberg, Girsh

    Materials with novel band structures can host ``chiral excitons'', where the exciton emission preserves the helicity of the excitation photon, as recently demonstrated in transition metal dichalcogenide monolayers. Here, we report the observation of a highly polarized photoluminescence peak, which is due to chiral exciton emission in the topological insulator Bi2Se3. Surprisingly, the energy of the emission is centered at 2.26 eV, much higher than the 0.3 eV bulk band gap of Bi2Se3. The excitation profile shows maximum polarization around 2.60 eV excitation, suggesting the chiral exciton is due to interband transition between the topological surface states and a bulk band. We demonstrate that the polarization of the exciton emission is insensitive to temperature and Bi2Se3 film thickness, providing a convenient and robust platform for optoelectronic applications. Gb, HHK and AL acknowledge support from NSF Award DMR-1104884. MS, NK, MB and SO are funded by Gordon and Betty Moore Foundation's EPiQS initiative (GBMF4418) and NSF(DMR-1308142). XYW and SWC acknowledge support from NSF Award DMREF-1233349.

  12. Multiple Exciton Generation in Semiconductor Nanostructures: DFT-based Computation

    NASA Astrophysics Data System (ADS)

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

    Multiple exciton generation (MEG) in nm-sized H-passivated Si nanowires (NWs), and quasi 2D nanofilms depends strongly on the degree of the core structural disorder as shown by the perturbation theory calculations based on the DFT simulations. In perturbation theory, we work to the 2nd order in the electron-photon coupling and in the (approximate) RPA-screened Coulomb interaction. We also include the effect of excitons for which we solve Bethe-Salpeter Equation. To describe MEG we calculate exciton-to-biexciton as well as biexciton-to-exciton rates and quantum efficiency (QE). We consider 3D arrays of Si29H36 quantum dots, NWs, and quasi 2D silicon nanofilms, all with both crystalline and amorphous core structures. Efficient MEG with QE of 1.3 up to 1.8 at the photon energy of about 3Egap is predicted in these nanoparticles except for the crystalline NW and film where QE ~=1. MEG in the amorphous nanoparticles is enhanced by the electron localization due to structural disorder. The exciton effects significantly red-shift QE vs. photon energy curves. Nm-sized a-Si NWs and films are predicted to have effective MEG within the solar spectrum range. Also, we find efficient MEG in the chiral single-wall Carbon nanotubes and in a perovskite nanostructure.

  13. Two-dimensional exciton properties in monolayer semiconducting phosphorus allotropes.

    PubMed

    Villegas, Cesar E P; Rodin, A S; Carvalho, Alexandra; Rocha, A R

    2016-10-12

    Excitons play a key role in technological applications since they have a strong influence on determining the efficiency of photovoltaic devices. Recently, it has been shown that the allotropes of phosphorus possess an optical band gap that can be tuned over a wide range of values including the near-infrared and visible spectra, which would make them promising candidates for optoelectronic applications. In this work we carry out ab initio many-body perturbation theory calculations to study the excitonic effects on the optical properties of two-dimensional phosphorus allotropes: the case of blue and black monolayers. We elucidate the most relevant optical transitions, exciton binding energy spectrum as well as real-space exciton distribution, particularly focusing on the absorption spectrum dependence on the incident light polarization. In addition, based on our results, we use a set of effective hydrogenic models, in which the electron-hole Coulomb interaction is included to estimate exciton binding energies and radii. Our results show an excellent agreement between the many-body methodology and the effective models.

  14. Incoherent exciton trapping in self-similar aperiodic lattices

    SciTech Connect

    Dominguez-Adame, F.; Macia, E. ); Sanchez, A. Escuela Politecnica Superior, Universidad Carlos III de Madrid, C./Butarque 15, E-28911 Leganes, Madrid )

    1995-01-01

    Incoherent exciton dynamics in one-dimensional perfect lattices with traps at sites arranged according to aperiodic deterministic sequences is studied. We focus our attention on Thue-Morse and Fibonacci systems as canonical examples of self-similar aperiodic systems. Solving numerically the corresponding master equation we evaluate the survival probability and the mean-square displacement of an exciton initially created at a single site. Results are compared to systems of the same size with the same concentration of traps randomly as well as periodically distributed over the whole lattice. Excitons progressively extend over the lattice on increasing time and, in this sense, they act as a probe of the particular arrangements of traps in each system considered. The analysis of the characteristic features of their time decay indicates that exciton dynamics in self-similar aperiodic arrangements of traps is quite close to that observed in periodic ones, but differs significantly from that corresponding to random lattices. We also report on characteristic features of exciton motion suggesting that Fibonacci and Thue-Morse orderings might be clearly observed by appropriate experimental measurements. In the conclusions we comment on the implications of our work on the way towards a unified theory of the ordering of matter.

  15. Interface exciton at lateral heterojunction of monolayer semiconductors

    NASA Astrophysics Data System (ADS)

    Lau, Ka Wai; Gong, Zhirui; Yu, Hongyi; Yao, Wang

    Heterostructures based on 2D transition metal dichalcogenides (TMDs) have attracted extensive research interest recently due to the appealing physical properties of TMDs and new geometries for forming heterostructures. One such heterostructure is the lateral heterojunctions seamlessly formed in a monolayer crystal between two different types of TMDs, e.g. WSe2 and MoSe2. Such heterojunction exhibits a type II band alignment, with electrons (holes) having lower energy on the MoSe2 (WSe2) region. Here we present the study of an interface exciton at the 1D lateral junction of monolayer TMDs. With the distance dependent screening, we find that the interface exciton can have strong binding even though the electron-hole separation is much larger compare to the 2D excitons in TMDs. Neutral excitons are studied using two different approaches: the solution based on a real-space tight binding model, and the perturbation expansion in a hydrogen-like basis in an effective mass model. We have also used the latter method to study charged excitons at a MoSe2-WSe2-MoSe2 nanoscale junction. The work is supported by the Research Grant Council of Hong Kong (HKU705513P, HKU9/CRF/13G), the Croucher Foundation, and the HKU OYRA.

  16. Improving Photoconductance of Fluorinated Donors with Fluorinated Acceptors

    SciTech Connect

    Garner, Logan E.; Larson, Bryon; Oosterhout, Stefan; Owczarczyk, Zbyslaw; Olson, Dana C.; Kopidakis, Nikos; Boltalina, Olga V.; Strauss, Steven H.; Braunecker, Wade A.

    2016-11-21

    This work investigates the influence of fluorination of both donor and acceptor materials on the generation of free charge carriers in small molecule donor/fullerene acceptor BHJ OPV active layers. A fluorinated and non-fluorinated small molecule analogue were synthesized and their optoelectronic properties characterized. The intrinsic photoconductance of blends of these small molecule donors was investigated using time-resolved microwave conductivity. Blends of the two donor molecules with a traditional non-fluorinated fullerene (PC70BM) as well as a fluorinated fullerene (C60(CF3)2-1) were investigated using 5% and 50% fullerene loading. We demonstrate for the first time that photoconductance in a 50:50 donor:acceptor BHJ blend using a fluorinated fullerene can actually be improved relative to a traditional non-fluorinated fullerene by fluorinating the donor molecule as well.

  17. An overview of molecular acceptors for organic solar cells

    NASA Astrophysics Data System (ADS)

    Hudhomme, Piétrick

    2013-07-01

    Organic solar cells (OSCs) have gained serious attention during the last decade and are now considered as one of the future photovoltaic technologies for low-cost power production. The first dream of attaining 10% of power coefficient efficiency has now become a reality thanks to the development of new materials and an impressive work achieved to understand, control and optimize structure and morphology of the device. But most of the effort devoted to the development of new materials concerned the optimization of the donor material, with less attention for acceptors which to date remain dominated by fullerenes and their derivatives. This short review presents the progress in the use of non-fullerene small molecules and fullerene-based acceptors with the aim of evaluating the challenge for the next generation of acceptors in organic photovoltaics.

  18. Electron acceptor taxis and blue light effect on bacterial chemotaxis.

    PubMed

    Taylor, B L; Miller, J B; Warrick, H M; Koshland, D E

    1979-11-01

    Salmonella typhimurium and Escherichia coli from anaerobic cultures displayed tactic responses to gradients of nitrate, fumarate, and oxygen when the appropriate electron transport pathway was present. Such responses were named "electron acceptor taxis" because they are elicited by terminal electron acceptors. Mutant strains of S. typhimurium and E. coli were used to establish that functioning electron transport pathways to nitrate and fumarate are required for taxis to these compounds. Aerotaxis in S. typhimurium was blocked by 1.0 mM KCN, which inhibited oxygen uptake. Similarly, a functioning electron transport pathway was shown to be essential for the tumbling response of S. typhimurium and E. coli to intense light (290 to 530 nm). Some inhibitors and uncouplers of respiration were repellents of S. typhimurium. We propose that behavioral responses to light or electron acceptors involve electron transport-mediated perturbations of the proton motive force.

  19. Gut inflammation provides a respiratory electron acceptor for Salmonella

    PubMed Central

    Winter, Sebastian E.; Thiennimitr, Parameth; Winter, Maria G.; Butler, Brian P.; Huseby, Douglas L.; Crawford, Robert W.; Russell, Joseph M.; Bevins, Charles L.; Adams, L. Garry; Tsolis, Renée M.; Roth, John R.; Bäumler, Andreas J.

    2010-01-01

    Salmonella enterica serotype Typhimurium (S. Typhimurium) causes acute gut inflammation by using its virulence factors to invade the intestinal epithelium and survive in mucosal macrophages. The inflammatory response enhances the transmission success of S. Typhimurium by promoting its outgrowth in the gut lumen through unknown mechanisms. Here we show that reactive oxygen species generated during inflammation reacted with endogenous, luminal sulphur compounds (thiosulfate) to form a new respiratory electron acceptor, tetrathionate. The genes conferring the ability to utilize tetrathionate as an electron acceptor produced a growth advantage for S. Typhimurium over the competing microbiota in the lumen of the inflamed gut. We conclude that S. Typhimurium virulence factors induce host-driven production of a new electron acceptor that allows the pathogen to use respiration to compete with fermenting gut microbes. Thus, the ability to trigger intestinal inflammation is crucial for the biology of this diarrhoeal pathogen. PMID:20864996

  20. Bounding Species Distribution Models

    NASA Technical Reports Server (NTRS)

    Stohlgren, Thomas J.; Jarnevich, Cahterine S.; Morisette, Jeffrey T.; Esaias, Wayne E.

    2011-01-01

    Species distribution models are increasing in popularity for mapping suitable habitat for species of management concern. Many investigators now recognize that extrapolations of these models with geographic information systems (GIS) might be sensitive to the environmental bounds of the data used in their development, yet there is no recommended best practice for "clamping" model extrapolations. We relied on two commonly used modeling approaches: classification and regression tree (CART) and maximum entropy (Maxent) models, and we tested a simple alteration of the model extrapolations, bounding extrapolations to the maximum and minimum values of primary environmental predictors, to provide a more realistic map of suitable habitat of hybridized Africanized honey bees in the southwestern United States. Findings suggest that multiple models of bounding, and the most conservative bounding of species distribution models, like those presented here, should probably replace the unbounded or loosely bounded techniques currently used [Current Zoology 57 (5): 642-647, 2011].

  1. Causality and Tsirelson's bounds

    SciTech Connect

    Buhrman, H.; Massar, S.

    2005-11-15

    We study the properties of no-signaling correlations that cannot be reproduced by local measurements on entangled quantum states. We say that such correlations violate Tsirelson bounds. We show that if these correlations are obtained by some reversible unitary quantum evolution U, then U cannot be written in the product form U{sub A}xU{sub B}. This implies that U can be used for signaling and for entanglement generation. This result is completely general and in fact can be viewed as a characterization of Tsirelson bounds. We then show how this result can be used as a tool to study Tsirelson bounds and we illustrate this by rederiving the Tsirelson bound of 2{radical}(2) for the Clauser-Horn-Shimony-Holt inequality, and by deriving a new Tsirelson bound for qutrits.

  2. Bounding species distribution models

    USGS Publications Warehouse

    Stohlgren, T.J.; Jarnevich, C.S.; Esaias, W.E.; Morisette, J.T.

    2011-01-01

    Species distribution models are increasing in popularity for mapping suitable habitat for species of management concern. Many investigators now recognize that extrapolations of these models with geographic information systems (GIS) might be sensitive to the environmental bounds of the data used in their development, yet there is no recommended best practice for "clamping" model extrapolations. We relied on two commonly used modeling approaches: classification and regression tree (CART) and maximum entropy (Maxent) models, and we tested a simple alteration of the model extrapolations, bounding extrapolations to the maximum and minimum values of primary environmental predictors, to provide a more realistic map of suitable habitat of hybridized Africanized honey bees in the southwestern United States. Findings suggest that multiple models of bounding, and the most conservative bounding of species distribution models, like those presented here, should probably replace the unbounded or loosely bounded techniques currently used. ?? 2011 Current Zoology.

  3. Donor/Acceptor Molecular Orientation-Dependent Photovoltaic Performance in All-Polymer Solar Cells.

    PubMed

    Zhou, Ke; Zhang, Rui; Liu, Jiangang; Li, Mingguang; Yu, Xinhong; Xing, Rubo; Han, Yanchun

    2015-11-18

    The correlated donor/acceptor (D/A) molecular orientation plays a crucial role in solution-processed all-polymer solar cells in term of photovoltaic performance. For the conjugated polymers PTB7-th and P(NDI2OD-T2), the preferential molecular orientation of neat PTB7-th films kept face-on regardless of the properties of processing solvents. However, an increasing content of face-on molecular orientation in the neat P(NDI2OD-T2) films could be found by changing processing solvents from chloronaphthalene (CN) and o-dichlorobenzene (oDCB) to chlorobenzene (CB). Besides, the neat P(NDI2OD-T2) films also exhibited a transformation of preferential molecular orientation from face-on to edge-on when extending film drying time by casting in the same solution. Consequently, a distribution diagram of molecular orientation for P(NDI2OD-T2) films was depicted and the same trend could be observed for the PTB7-th/P(NDI2OD-T2) blend films. By manufacture of photovoltaic devices with blend films, the relationship between the correlated D/A molecular orientation and device performance was established. The short-circuit current (Jsc) of devices processed by CN, oDCB, and CB enhanced gradually from 1.24 to 8.86 mA/cm(2) with the correlated D/A molecular orientation changing from face-on/edge-on to face-on/face-on, which could be attributed to facile exciton dissociation at D/A interface with the same molecular orientation. Therefore, the power conversion efficiency (PCE) of devices processed by CN, oDCB, and CB improved from 0.53% to 3.52% ultimately.

  4. Novel Quantum Condensates in Excitonic Matter

    NASA Astrophysics Data System (ADS)

    Littlewood, P. B.; Keeling, J. M. J.; Simons, B. D.; Eastham, P. R.; Marchetti, F. M.; Szymańska, M. H.

    2009-08-01

    These lectures interleave discussion of a novel physical problem of a new kind of condensate with teaching of the fundamental theoretical tools of quantum condensed matter field theory. Polaritons and excitons are light mass composite bosons that can be made inside solids in a number of different ways. As bosonic particles, they are liable to make a phase coherent ground state—generically called a Bose-Einstein condensate (BEC)—and these lectures present some models to describe that problem, as well as general approaches to the theory. The focus is very much to explain how mean-field-like approximations that are often presented heuristically can be derived in a systematic fashion by path integral methods. Going beyond the mean field theory then produces a systematic approach to calculation of the excitation energies, and the derivation of effective low energy theories that can be generalised to more complex dynamical and spatial situations than is practicable for the full theory, as well as to study statistical properties beyond the semi-classical regime. in particular, for the polariton problem, it allows one to connect the regimes of equilibrium BEC and non-equilibrium laser. The lectures are self-sufficient, but not highly detailed. The methodological aspects are covered in standard quantum field theory texts and the presentation here is deliberately cursory: the approach will be closest to the book of Altland and Simons [1]. Since these lectures concern a particular type of condensate, reference should also be made to texts on BEC, for example by Pitaevskii and Stringari [2]. A recent theoretically focussed review of polariton systems is [3] covers many of the technical issues associated with the polariton problem in greater depth and provides many further references.

  5. 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.

  6. Dynamical frustration versus kinetic enhancement with excitons in strongly correlated bilayers

    NASA Astrophysics Data System (ADS)

    Rademaker, Louk

    2014-03-01

    Recently the condensation of electron-hole pairs in semiconductor bilayers has been achieved. This has opened up the pursuit of exciton condensation in other layered materials. Here I will present recent theoretical work on exciton physics in complex oxide heterostructures. The poorly understood high temperature superconducting cuprates are ideal candidates for bilayer exciton condensation. Therefore we study the dynamics and the phase diagram of bilayer excitons in a Mott insulating p/n heterostructure, which shows rich exciton-spin interaction phenomena. I will discuss the dynamical frustration experienced by an exciton moving through an antiferromagnetic background. In sharp contrast, I will show how in the exciton superfluid phase the magnetic excitations 'borrow' kinetic energy from the excitons.

  7. Acceptor specificity in the transglycosylation reaction using Endo-M.

    PubMed

    Tomabechi, Yusuke; Odate, Yuki; Izumi, Ryuko; Haneda, Katsuji; Inazu, Toshiyuki

    2010-11-22

    To determine the structural specificity of the glycosyl acceptor of the transglycosylation reaction using endo-β-N-acetylglucosaminidase (ENGase) (EC 3.2.1.96) from Mucor hiemalis (Endo-M), several acceptor derivatives were designed and synthesized. The narrow regions of the 1,3-diol structure from the 4- to 6-hydroxy functions of GlcNAc were found to be essential for the transglycosylation reaction using Endo-M. Furthermore, it was determined that Endo-M strictly recognizes a 1,3-diol structure consisting of primary and secondary hydroxyl groups.

  8. Donor-acceptor chemistry in the main group.

    PubMed

    Rivard, Eric

    2014-06-21

    This Perspective article summarizes recent progress from our laboratory in the isolation of reactive main group species using a general donor-acceptor protocol. A highlight of this program is the use of carbon-based donors in combination with suitable Lewis acidic acceptors to yield stable complexes of parent Group 14 element hydrides (e.g. GeH2 and H2SiGeH2). It is anticipated that this strategy could be extended to include new synthetic targets from throughout the Periodic Table with possible applications in bottom-up materials synthesis and main group element catalysis envisioned.

  9. Fingerprints of Through-Bond and Through-Space Exciton and Charge π-Electron Delocalization in Linearly Extended [2.2]Paracyclophanes.

    PubMed

    Zafra, José L; Molina Ontoria, Agustín; Mayorga Burrezo, Paula; Peña-Alvarez, Miriam; Samoc, Marek; Szeremeta, Janusz; Ramírez, Francisco J; Lovander, Matthew D; Droske, Christopher J; Pappenfus, Ted M; Echegoyen, Luis; López Navarrete, Juan T; Martín, Nazario; Casado, Juan

    2017-03-01

    New stilbenoid and thiophenic compounds terminally functionalized with donor-donor, acceptor-acceptor, or donor-acceptor moieties and possessing a central [2.2]paracyclophane unit have been prepared, and their properties interpreted in terms of through-bond and through space π-electron delocalization (i.e., π-conjugations). Based on photophysical data, their excited-state properties have been described with a focus on the participation of the central [2.2]paracyclophane in competition with through-bond conjugation in the side arms. To this end, two-photon and one-photon absorption and emission spectroscopy, as a function of temperature, solvent polarity, and pressure in the solid state have been recorded. Furthermore, charge delocalization through the [2.2]paracyclophane in the neutral state and in the oxidized species (radical cations, dications and radical trications) has been investigated, allowing the elucidation of the vibrational Raman fingerprint of through-space charge delocalization. Thus, a complementary approach to both "intermolecular" excitation and charge delocalizations in [2.2]paracyclophane molecules is shown which can serve as models of charge and exciton migration in organic semiconductors.

  10. Charged two-exciton emission from a single semiconductor nanocrystal

    SciTech Connect

    Hu, Fengrui; Zhang, Qiang; Zhang, Chunfeng; Wang, Xiaoyong; Xiao, Min

    2015-03-30

    Here, we study the photoluminescence (PL) time trajectories of single CdSe/ZnS nanocrystals (NCs) as a function of the laser excitation power. At the low laser power, the PL intensity of a single NC switches between the “on” and “off” levels arising from the neutral and positively charged single excitons, respectively. With the increasing laser power, an intermediate “grey” level is formed due to the optical emission from a charged multiexciton state composed of two excitons and an extra electron. Both the inter-photon correlation and the PL decay measurements demonstrate that lifetime-indistinguishable photon pairs are emitted from this negatively charged two-exciton state.

  11. Quantum confinement-induced tunable exciton states in graphene oxide

    PubMed Central

    Lee, Dongwook; Seo, Jiwon; Zhu, Xi; Lee, Jiyoul; Shin, Hyeon-Jin; Cole, Jacqueline M.; Shin, Taeho; Lee, Jaichan; Lee, Hangil; Su, Haibin

    2013-01-01

    Graphene oxide has recently been considered to be a potential replacement for cadmium-based quantum dots due to its expected high fluorescence. Although previously reported, the origin of the luminescence in graphene oxide is still controversial. Here, we report the presence of core/valence excitons in graphene-based materials, a basic ingredient for optical devices, induced by quantum confinement. Electron confinement in the unreacted graphitic regions of graphene oxide was probed by high resolution X-ray absorption near edge structure spectroscopy and first-principles calculations. Using experiments and simulations, we were able to tune the core/valence exciton energy by manipulating the size of graphitic regions through the degree of oxidation. The binding energy of an exciton in highly oxidized graphene oxide is similar to that in organic electroluminescent materials. These results open the possibility of graphene oxide-based optoelectronic device technology. PMID:23872608

  12. Huge excitonic effects in layered hexagonal boron nitride.

    PubMed

    Arnaud, B; Lebègue, S; Rabiller, P; Alouani, M

    2006-01-20

    The all-electron GW approximation energy band gap of bulk hexagonal boron nitride is shown to be of indirect type. The resulting computed in-plane polarized optical spectrum, obtained by solving the Bethe-Salpeter equation for the electron-hole two-particle Green function, is in excellent agreement with experiment and has a strong anisotropy compared to out-of-plane polarized spectrum. A detailed analysis of the excitonic structures within the band gap shows that the low-lying excitons belong to the Frenkel class and are tightly confined within the layers. The calculated exciton binding energy is much larger than that obtained by Watanabe et al. [Nat. Mater. 3, 404 (2004).] based on a Wannier model assuming h-BN to be a direct-band-gap semiconductor.

  13. Magnetic edge-state excitons in zigzag graphene nanoribbons.

    PubMed

    Yang, Li; Cohen, Marvin L; Louie, Steven G

    2008-10-31

    We present first-principles calculations of the optical properties of zigzag-edged graphene nanoribbons (ZGNRs) employing the GW-Bethe-Salpeter equation approach with the spin interaction included. Optical response of the ZGNRs is found to be dominated by magnetic edge-state-derived excitons with large binding energy. The absorption spectrum is composed of a characteristic series of exciton states, providing a possible signature for identifying the ZGNRs. The edge-state excitons are charge-transfer excitations with the excited electron and hole located on opposite edges; they moreover induce a spin transfer across the ribbon, resulting in a photoreduction of the magnetic ordering. These novel characteristics are potentially useful in the applications.

  14. Exciton coupling induces vibronic hyperchromism in light-harvesting complexes

    NASA Astrophysics Data System (ADS)

    Schulze, Jan; Torbjörnsson, Magne; Kühn, Oliver; Pullerits, Tõnu

    2014-04-01

    The recently suggested possibility that weak vibronic transitions can be excitonically enhanced in light-harvesting complexes is studied in detail. A vibronic exciton dimer model that includes ground-state vibrations is investigated using the multi-configuration time-dependent Hartree method with a parameter set typical to photosynthetic light-harvesting complexes. The absorption spectra are discussed based on the Coulomb coupling, the detuning of the site energies, and the number of vibrational modes. Fluorescence spectra calculations show that the spectral densities obtained from the low-temperature fluorescence line-narrowing measurements of light-harvesting systems need to be corrected for the effects of excitons. For the J-aggregate configuration, as in most light-harvesting complexes, the true spectral density has a larger amplitude than that obtained from the measurement.

  15. Multiple beats of weakly confined excitons with inverted selection rule

    NASA Astrophysics Data System (ADS)

    Yasuda, Hideki; Ishihara, Hajime

    2009-05-01

    The phenomenon of multiple beats (MBs) arising from nondipole-type excitons weakly confined in a thin film is theoretically elucidated using a nonlocal transient-response theory. Kojima previously demonstrated for a GaAs thin film that the degenerate four-wave mixing signals from the quantized levels of the center-of-mass motion of excitons exhibit complex interference between beats under femtosecond-order pulse incidence [Kojima , J. Phys. Soc. Jpn. 77, 044701 (2008)]. This leads to an ultrafast optical response on the order of femtoseconds. This effect occurs in a size region beyond the long-wavelength approximation regime due to the resonant enhancement of the internal field, wherein the usual dipole selection rule is violated. Our analysis of MBs employs a model of the nonlocal multilevel system that considers the spatial interplay between excitonic waves and the radiation field to elucidate the mechanism behind the observed ultrafast response.

  16. Computational study of exciton generation in suspended carbon nanotube transistors.

    PubMed

    Koswatta, Siyuranga O; Perebeinos, Vasili; Lundstrom, Mark S; Avouris, Phaedon

    2008-06-01

    Optical emission from carbon nanotube transistors (CNTFETs) has recently attracted significant attention due to its potential applications. In this paper, we use a self-consistent numerical solution of the Boltzmann transport equation in the presence of both phonon and exciton scattering to present a detailed study of the operation of a partially suspended CNTFET light emitter, which has been discussed in a recent experiment. We determine the energy distribution of hot carriers in the CNTFET and, as reported in the experiment, observe localized generation of excitons near the trench-substrate junction and an exponential increase in emission intensity with a linear increase in current versus gate voltage. We further provide detailed insight into device operation and propose optimization schemes for efficient exciton generation; a deeper trench increases the generation efficiency, and use of high-k substrate oxides could lead to even larger enhancements.

  17. Effects of fermion exchange on the polarization of exciton condensates.

    PubMed

    Combescot, Monique; Combescot, Roland; Alloing, Mathieu; Dubin, François

    2015-03-06

    Exchange interaction is responsible for the stability of elementary boson condensates with respect to momentum fragmentation. This remains true for composite bosons when single fermion exchanges are included but spin degrees of freedom are ignored. Here, we show that their inclusion can produce a spin fragmentation of the dark exciton condensate, i.e., an unpolarized condensate with an equal amount of spin (+2) and (-2) excitons not coupled to light. The composite boson many-body formalism allows us to predict that, for spatially indirect excitons, the condensate polarization switches from unpolarized to fully polarized when the distance between the layers confining electrons and holes increases. Importantly, the threshold distance for this switch lies in a regime fully accessible to experiments.

  18. Mapping the spatial overlap of excitons in a photosynthetic complex via coherent nonlinear frequency generation.

    PubMed

    Dawlaty, Jahan M; Bennett, Doran I G; Huxter, Vanessa M; Fleming, Graham R

    2011-07-28

    We experimentally demonstrate a nonlinear spectroscopic method that is sensitive to exciton-exciton interactions in a Frenkel exciton system. Spatial overlap of one-exciton wavefunctions leads to coupling between them, resulting in two-exciton eigenstates that have the character of many single-exciton pairs. The mixed character of the two-exciton wavefunctions gives rise to a four-wave-mixing nonlinear frequency generation signal. When only part of the linear excitation spectrum of the complex is excited with three spectrally tailored pulses with separate spatial directions, a frequency-shifted third-order nonlinear signal emerges in the phase-matched direction. We employ the nonlinear response function formalism to show that the emergence of the signal is mediated by and carries information about the two-exciton eigenstates of the system. We report experimental results for nonlinear frequency generation in the Fenna-Matthews-Olson (FMO) photosynthetic pigment-protein complex. Our theoretical analysis of the signal from FMO confirms that the emergence of the frequency-shifted signal is due to the interaction of spatially overlapped excitons. In this method, the signal intensity is directly measured in the frequency domain and does not require scanning of pulse delays or signal phase retrieval. The wavefunctions of the two-exciton states contain information about the spatial overlap of excitons and can be helpful in identifying coupling strengths and relaxation pathways. We propose this method as a facile experimental means of studying exciton correlations in systems with complicated electronic structures.

  19. Crossed excitons in a semiconductor nanostructure of mixed dimensionality

    SciTech Connect

    Owschimikow, Nina Kolarczik, Mirco; Kaptan, Yücel I.; Grosse, Nicolai B.; Woggon, Ulrike

    2014-09-08

    Semiconductor systems of reduced dimensionality, e.g., quantum dots or quantum wells, display a characteristic spectrum of confined excitons. Combining several of these systems may lead to the formation of “crossed” excitons, and thus new equilibrium states and scattering channels. We derive gain excitation spectra from two-color pump-probe experiments on an In(Ga)As based quantum dot semiconductor optical amplifier by analyzing the amplitudes of the traces. This grants access to the quantum dot response, even in the presence of strong absorption by the surroundings at the excitation energy. The gain excitation spectra yield evidence of crossed quantum dot-bulk states.

  20. Plasmon and exciton superconductivity mechanisms in layered structures

    NASA Technical Reports Server (NTRS)

    Gabovich, A. M.; Pashitskiy, E. A.; Uvarova, S. K.

    1977-01-01

    Plasmon and exciton superconductivity mechanisms are discussed. Superconductivity in a three layer metal semiconductor metal and insulator semimetal insulator sandwich structure was described in terms of the temperature dependent Green function of the longitudinal (Coulomb) field. The dependences of the superconducting transition temperature on structure parameters were obtained. In a semiconducting film, as a result of interactions of degenerate free carriers with excitons, superconductivity exists only in a certain range of parameter values, and the corresponding critical temperature is much lower than in the plasmon mechanism of superconductivity.

  1. Realization of an all optical exciton-polariton router

    SciTech Connect

    Marsault, Félix; Nguyen, Hai Son; Tanese, Dimitrii; Lemaître, Aristide; Galopin, Elisabeth; Sagnes, Isabelle; Amo, Alberto

    2015-11-16

    We report on the experimental realization of an all optical router for exciton-polaritons. This device is based on the design proposed by Flayac and Savenko [Appl. Phys. Lett. 103, 201105 (2013)], in which a zero-dimensional island is connected through tunnel barriers to two periodically modulated wires of different periods. Selective transmission of polaritons injected in the island, into either of the two wires, is achieved by tuning the energy of the island state across the band structure of the modulated wires. We demonstrate routing of ps polariton pulses using an optical control beam which controls the energy of the island quantum states, thanks to polariton-exciton interactions.

  2. Frequency combs with weakly lasing exciton-polariton condensates.

    PubMed

    Rayanov, K; Altshuler, B L; Rubo, Y G; Flach, S

    2015-05-15

    We predict the spontaneous modulated emission from a pair of exciton-polariton condensates due to coherent (Josephson) and dissipative coupling. We show that strong polariton-polariton interaction generates complex dynamics in the weak-lasing domain way beyond Hopf bifurcations. As a result, the exciton-polariton condensates exhibit self-induced oscillations and emit an equidistant frequency comb light spectrum. A plethora of possible emission spectra with asymmetric peak distributions appears due to spontaneously broken time-reversal symmetry. The lasing dynamics is affected by the shot noise arising from the influx of polaritons. That results in a complex inhomogeneous line broadening.

  3. Exciton dynamics in solid-state green fluorescent protein

    NASA Astrophysics Data System (ADS)

    Dietrich, Christof P.; Siegert, Marie; Betzold, Simon; Ohmer, Jürgen; Fischer, Utz; Höfling, Sven

    2017-01-01

    We study the decay characteristics of Frenkel excitons in solid-state enhanced green fluorescent protein (eGFP) dried from solution. We further monitor the changes of the radiative exciton decay over time by crossing the phase transition from the solved to the solid state. Complex interactions between protonated and deprotonated states in solid-state eGFP can be identified from temperature-dependent and time-resolved fluorescence experiments that further allow the determination of activation energies for each identified process.

  4. Environment-assisted quantum walks in excitonic energy transport

    NASA Astrophysics Data System (ADS)

    Mohseni, Masoud; Rebentrost, Patrick; Lloyd, Seth; Aspuru-Guzik, Alan

    2010-03-01

    Long-lived quantum coherence has recently been observed experimentally via ultrafast nonlinear spectroscopy in excitonic energy transfer within light-harvesting photosynthetic complexes, conjugated polymers, and marine alga even at room temperature. Here, we demonstrate that directed quantum walks lead to an enhancement of energy transfer efficiency in such systems. We introduce two complementary theoretical approaches, based on a Green's function method and energy transfer susceptibilities, to partition open quantum dynamics. We quantify the role of fundamental physical processes involved in energy transport. In particular, we examine the contributions of classical hopping, coherent excitonic Hamiltonian, and phonon-induced decoherence effects for pure dephasing, Markovian, and non-Markovian limits.

  5. Enhanced energy transport in genetically engineered excitonic networks

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  6. Strong coupling between Tamm plasmon and QW exciton

    NASA Astrophysics Data System (ADS)

    Homeyer, Estelle; Symonds, Clémentine; Lemaître, Aristide; Plenet, Jean-Claude; Bellessa, Joel

    2011-03-01

    We report on the strong coupling between a Tamm plasmon mode and excitons from inorganic quantum wells. The sample is formed by an AlAs/GaAlAs Bragg reflector containing InGaAs QWs in its high refractive index layers, on top of which a thin silver film is deposited. Angle resolved reflectometry experiments at low temperature (77 K) show a clear anticrossing in the dispersion relations, evidencing the strong coupling regime. The Rabi splitting amounts to 11.5 meV. Emission from low and high energy Tamm plasmon/exciton polaritons is also demonstrated. Experimental data are in very good agreement with transfer matrix simulations.

  7. Exciton autoionization in ion-induced electron emission.

    PubMed

    Bajales, N; Cristina, L; Mendoza, S; Baragiola, R A; Goldberg, E C; Ferrón, J

    2008-06-06

    We report on measurements of electron emission spectra from surfaces of highly oriented pyrolytic graphite (HOPG) excited by 1-5 keV He+ and Li+ which, for He+, exhibit a previously unreported high-energy structure. Through a full quantum dynamic description that allows for the calculation of neutralization and electron-hole pair excitation, we show that these high-energy electrons can arise from autoionization of excitons formed by electron promotion to conduction band states close to the vacuum level. The same calculation explains the observed absence of high-energy excitons for Li+ on HOPG.

  8. Three Redox States of a Diradical Acceptor-Donor-Acceptor Triad: Gating the Magnetic Coupling and the Electron Delocalization.

    PubMed

    Souto, Manuel; Lloveras, Vega; Vela, Sergi; Fumanal, Maria; Ratera, Imma; Veciana, Jaume

    2016-06-16

    The diradical acceptor-donor-acceptor triad 1(••), based on two polychlorotriphenylmethyl (PTM) radicals connected through a tetrathiafulvalene(TTF)-vinylene bridge, has been synthesized. The generation of the mixed-valence radical anion, 1(•-), and triradical cation species, 1(•••+), obtained upon electrochemical reduction and oxidation, respectively, was monitored by optical and ESR spectroscopy. Interestingly, the modification of electron delocalization and magnetic coupling was observed when the charged species were generated and the changes have been rationalized by theoretical calculations.

  9. Electron Acceptor-Electron Donor Interactions. XV and XVI.

    DTIC Science & Technology

    mixtures exhibit simple eutectic phase diagrams and the thermochromic effect is interpreted as a randomized structure in the liquid , whereas the solid is a...two-phase aggregate of isolated acceptor and onor crystals . The charge-transfer spectra of solutions of tungsten and molybdenum hexafluorides and iodine heptafluoride in n-hexane and cyclohexane were obtained.

  10. Poly(trifluoromethyl)azulenes: structures and acceptor properties.

    PubMed

    Clikeman, Tyler T; Bukovsky, Eric V; Kuvychko, Igor V; San, Long K; Deng, Shihu H M; Wang, Xue-Bin; Chen, Yu-Sheng; Strauss, Steven H; Boltalina, Olga V

    2014-06-14

    Six new poly(trifluoromethyl)azulenes prepared in a single high-temperature reaction exhibit strong electron accepting properties in the gas phase and in solution and demonstrate the propensity to form regular π-stacked columns in donor-acceptor crystals when mixed with pyrene as a donor.

  11. Development of imide- and imidazole-containing electron acceptors for use in donor-acceptor conjugated compounds and polymers

    NASA Astrophysics Data System (ADS)

    Li, Duo

    Conjugated organic compounds and polymers have attracted significant attention due to their potential application in electronic devices as semiconducting materials, such as organic solar cells (OSCs). In order to tune band gaps, donor-acceptor (D-A) structure is widely used, which has been proved to be one of the most effective strategies. This thesis consists of three parts: 1) design, syntheses and characterization of new weak acceptors based on imides and the systematic study of the structure-property relationship; (2) introduction of weak and strong acceptors in one polymer to achieve a broad coverage of light absorption and improve the power conversion efficiency (PCE); (3) modification of benzothiadiazole (BT) acceptor in order to increase the electron withdrawing ability. Imide-based electron acceptors, 4-(5-bromothiophen-2-y1)-2-(2-ethylhexyl)-9- phenyl- 1H-benzo[f]isoindole-1,3(2H)-dione (BIDO-1) and 4,9-bis(5-bromothiophen-2-yl)-2-(2-ethylhexyl)-benzo[f]isoindole-1,3-dione (BIDO-2), were designed and synthesized. In this design, naphthalene is selected as its main core to maintain a planar structure, and thienyl groups are able to facilitate the bromination reaction and lower the band gap. BIDO-1 and BIDO-2 were successfully coupled with different donors by both Suzuki cross-coupling and Stille cross-coupling reactions. Based on the energy levels and band gaps of the BIDO-containing compounds and polymers, BIDO-1 and BIDO-2 are proved to be weak electron acceptors. Pyromellitic diimide (PMDI) was also studied and found to be a stronger electron acceptor than BIDO . In order to obtain broad absorption coverage, both weak acceptor ( BIDO-2) and strong acceptor diketopyrrolopyrrole (DPP) were introduced in the same polymer. The resulting polymers show two absorption bands at 400 and 600 nm and two emission peaks at 500 and 680 nm. The band gaps of the polymers are around 1.6 eV, which is ideal for OSC application. The PCE of 1.17% was achieved. Finally

  12. Anaerobic methanotrophy in tidal wetland: Effects of electron acceptors

    NASA Astrophysics Data System (ADS)

    Lin, Li-Hung; Yu, Zih-Huei; Wang, Pei-Ling

    2016-04-01

    Wetlands have been considered to represent the largest natural source of methane emission, contributing substantially to intensify greenhouse effect. Despite in situ methanogenesis fueled by organic degradation, methanotrophy also plays a vital role in controlling the exact quantity of methane release across the air-sediment interface. As wetlands constantly experience various disturbances of anthropogenic activities, biological burrowing, tidal inundation, and plant development, rapid elemental turnover would enable various electron acceptors available for anaerobic methanotrophy. The effects of electron acceptors on stimulating anaerobic methanotrophy and the population compositions involved in carbon transformation in wetland sediments are poorly explored. In this study, sediments recovered from tidally influenced, mangrove covered wetland in northern Taiwan were incubated under the static conditions to investigate whether anaerobic methanotrophy could be stimulated by the presence of individual electron acceptors. Our results demonstrated that anaerobic methanotrophy was clearly stimulated in incubations amended with no electron acceptor, sulfate, or Fe-oxyhydroxide. No apparent methane consumption was observed in incubations with nitrate, citrate, fumarate or Mn-oxides. Anaerobic methanotrophy in incubations with no exogenous electron acceptor appears to proceed at the greatest rates, being sequentially followed by incubations with sulfate and Fe-oxyhydroxide. The presence of basal salt solution stimulated methane oxidation by a factor of 2 to 3. In addition to the direct impact of electron acceptor and basal salts, incubations with sediments retrieved from low tide period yielded a lower rate of methane oxidation than from high tide period. Overall, this study demonstrates that anaerobic methanotrophy in wetland sediments could proceed under various treatments of electron acceptors. Low sulfate content is not a critical factor in inhibiting methane

  13. Virial Expansion Bounds

    NASA Astrophysics Data System (ADS)

    Tate, Stephen James

    2013-10-01

    In the 1960s, the technique of using cluster expansion bounds in order to achieve bounds on the virial expansion was developed by Lebowitz and Penrose (J. Math. Phys. 5:841, 1964) and Ruelle (Statistical Mechanics: Rigorous Results. Benjamin, Elmsford, 1969). This technique is generalised to more recent cluster expansion bounds by Poghosyan and Ueltschi (J. Math. Phys. 50:053509, 2009), which are related to the work of Procacci (J. Stat. Phys. 129:171, 2007) and the tree-graph identity, detailed by Brydges (Phénomènes Critiques, Systèmes Aléatoires, Théories de Jauge. Les Houches 1984, pp. 129-183, 1986). The bounds achieved by Lebowitz and Penrose can also be sharpened by doing the actual optimisation and achieving expressions in terms of the Lambert W-function. The different bound from the cluster expansion shows some improvements for bounds on the convergence of the virial expansion in the case of positive potentials, which are allowed to have a hard core.

  14. Fresh look at electron-transfer mechanisms via the donor/acceptor bindings in the critical encounter complex.

    PubMed

    Rosokha, Sergiy V; Kochi, Jay K

    2008-05-01

    Seminal insights provided by the iconic R. S. Mulliken and his "charge-transfer" theory, H. Taube and his "outer/inner-sphere" mechanisms, R. A. Marcus and his "two-state non-adiabatic" theory, and N. S. Hush and his "intervalence" theory are each separately woven into the rich panoramic tapestry constituting chemical research into electron-transfer dynamics, and its mechanistic dominance for the past half century and more. In this Account, we illustrate how the simultaneous melding of all four key concepts allows sharp focus on the charge-transfer character of the critical encounter complex to evoke the latent facet of traditional electron-transfer mechanisms. To this end, we exploit the intervalence (electronic) transition that invariably accompanies the diffusive encounter of electron-rich organic donors (D) with electron-poor acceptors (A) as the experimental harbinger of the collision complex, which is then actually isolated and X-ray crystallographically established as loosely bound pi-stacked pairs of various aromatic and olefinic donor/acceptor dyads with uniform interplanar separations of r(DA) = 3.1 +/- 0.2 A. These X-ray structures, together with the spectral measurements of their intervalence transitions, lead to the pair of important electron-transfer parameters, H(DA) (electronic coupling element) versus lambdaT (reorganization energy), the ratio of which generally defines the odd-electron mobility within such an encounter complex in terms of the resonance stabilization of the donor/acceptor assembly [D, A] as opposed to the reorganization-energy penalty required for its interconversion to the electron-transfer state [D(+*), A(-*)]. We recognize the resonance-stabilization energy relative to the intrinsic activation barrier as the mechanistic binding factor, Q = 2H(DA)/lambdaT, to represent the quantitative measure of the highly variable continuum of inner-sphere/outer-sphere interactions that are possible within various types of precursor complexes

  15. Strongly Enhanced Free-Exciton Luminescence in Microcrystalline CsPbBr3 Films

    NASA Astrophysics Data System (ADS)

    Kondo, Shin-ichi; Kakuchi, Mitsugu; Masaki, Atsushi; Saito, Tadaaki

    2003-07-01

    The luminescence properties of CsPbBr3 films prepared via the amorphous phase by crystallization are dominated by free-exciton emission, and only a weak trace of emission due to trapped excitons was observed, in contrast to the case of bulk CsPbBr3 crystals. In particular, the films in the microcrystalline state show by more than an order of magnitude stronger free-exciton emission than in the polycrystalline state. The enhanced free-exciton emission is suggestive of excitonic superradiance.

  16. All-optical depletion of dark excitons from a semiconductor quantum dot

    SciTech Connect

    Schmidgall, E. R.; Schwartz, I.; Cogan, D.; Gershoni, D.; Gantz, L.; Heindel, T.; Reitzenstein, S.

    2015-05-11

    Semiconductor quantum dots are considered to be the leading venue for fabricating on-demand sources of single photons. However, the generation of long-lived dark excitons imposes significant limits on the efficiency of these sources. We demonstrate a technique that optically pumps the dark exciton population and converts it to a bright exciton population, using intermediate excited biexciton states. We show experimentally that our method considerably reduces the dark exciton population while doubling the triggered bright exciton emission, approaching thereby near-unit fidelity of quantum dot depletion.

  17. Exciton-plasmon and spin-plasmon interactions in hybrid semiconductor-metal nanostructures

    NASA Astrophysics Data System (ADS)

    Govorov, Alexander

    2011-03-01

    Coulomb and electromagnetic interactions between excitons and plasmons in nanocrystals cause several effects: energy transfer between nanoparticles, plasmon enhancement, Lamb shifts of exciton lines, Fano interference. In a complex composed of semiconductor quantum dot and metal nanoparticle, plasmons interact with spin-polarized excitons. This interaction leads to the formation of coupled spin-plasmon excitations and to spin-dependent Fano resonances. If an exciton-plasmon system includes chiral elements (chiral molecules or nanocrystals), the exciton-plasmon interaction is able to create new plasmonic lines in circular dichroism spectra.

  18. Evidence for dark excitons in a single carbon nanotube due to the Aharonov-Bohm effect.

    PubMed

    Matsunaga, Ryusuke; Matsuda, Kazunari; Kanemitsu, Yoshihiko

    2008-10-03

    We studied exciton structures and the Aharonov-Bohm effect in a single carbon nanotube using micro-photoluminescence (PL) spectroscopy under a magnetic field at low temperatures. A single sharp PL peak from the bright exciton state of a single carbon nanotube was observed under zero magnetic field, and the additional PL of dark exciton state appeared below the bright exciton peak under high magnetic fields. It was found that the split between the bright and dark exciton states is several millielectron volts at zero field. The tube diameter dependence of the splitting arises from the intervalley short-range Coulomb interaction.

  19. Singlet fission in pentacene through multiple exciton quantum states

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiyong; Zimmerman, Paul; Musgrave, Charles

    2010-03-01

    Multi-exciton generation (MEG) has been reported for several materials and may dramatically increase solar cell efficiency. Singlet fission is the molecular analogue of MEG and has been observed in various systems, including tetracene and pentacene, however, no fundamental mechanism for singlet fission has yet been described, although it may govern MEG processes in a variety of materials. Because photoexcited states have single-exciton character, singlet fission to produce a pair of triplet excitons must involve an intermediate state that: (1) exhibits multi-exciton (ME) character, (2) is accessible from S1 and satisfies the fission energy requirement, and (3) efficiently dissociates into multiple electron-hole pairs. Here, we use sophisticated ab initio calculations to show that singlet fission in pentacene proceeds through a dark state (D) of ME character that lies just below S1, satisfies the fission energy requirement (ED>2ET0), and splits into two triplets (2xT0). In tetracene, D lies just above S1, consistent with the observation that singlet fission is thermally activated in tetracene. Rational design of photovoltaic systems that exploit singlet fission will require ab initio analysis of ME states such as D.

  20. Optical dynamics of exciton and polaron formation in molecular aggregates

    NASA Astrophysics Data System (ADS)

    de Boer, Steven; Wiersma, Douwe A.

    1989-03-01

    Results of femtosecond accumulated photon echo, picosecond pump-probe and fluorescence lifetime measurements are reported on aggregates of the dyes pseudoisocyanine (PIC) and substituted thiapyrylium (TPY), embedded in a polycarbonate matrix. It is concluded that in the PIC aggregate, delocalized excitations (excitons) are formed, which are weakly coupled to the aggregate's nuclear frame. In the TPY aggregate, excitons are also initially formed, but through strong local electron-phonon coupling these excitons are not stable and decay into polarons, which become trapped. It is suggested that the nature of the excitations in aggregates crucially depends on the change of electron density distribution upon optical excitation. When this change is large, as revealed by a large change of dipole moment, polarons will be formed. In the other limit of a small change of dipole moment on optical excitation, excitons with an enhanced radiative lifetime are formed, which coherently propagate over that part of the aggregate where the molecules are electronically strongly coupled. The relevance of these findings towards energy transport in photo-biological systems is also discussed.

  1. Exciton-polariton condensation in transition metal dichalcogenide bilayer heterostructure

    NASA Astrophysics Data System (ADS)

    Lee, Ki Hoon; Jeong, Jae-Seung; Min, Hongki; Chung, Suk Bum

    For the bilayer heterostructure system in an optical microcavity, the interplay of the Coulomb interaction and the electron-photon coupling can lead to the emergence of quasiparticles consisting of the spatially indirect exciton and cavity photons known as dipolariton, which can form the Bose-Einstein condensate above a threshold density. Additional physics comes into play when each layer of the bilayer system consists of the transition metal dichalcogenide (TMD) monolayer. The TMD monolayer band structure in the low energy spectrum has two valley components with nontrivial Berry phase, which gives rise to a selection rule in the exciton-polariton coupling, e.g. the exciton from one (the other) valley can couple only to the clockwise (counter-clockwise) polarized photon. We investigate possible condensate phases of exciton-polariton in the bilayer TMD microcavity changing relevant parameters such as detuning, excitation density and interlayer distance. This work was supported in part by the Institute for Basic Science of Korea (IBS) under Grant IBS-R009-Y1 and by the National Research Foundation of Korea (NRF) under the Basic Science Research Program Grant No. 2015R1D1A1A01058071.

  2. Multiple Exciton Generation for Highly Efficient Solar Cells

    NASA Astrophysics Data System (ADS)

    Nozik, Arthur

    2007-03-01

    In order to utilize solar power for the production of electricity and fuel on a massive scale, it will be necessary to develop solar photon conversion systems that have an appropriate combination of high efficiency and low capital cost (/m^2). One new potential approach to high solar cell efficiency is to utilize the unique properties of semiconductor quantum dot nanostructures to control the relaxation dynamics of photogenerated carriers to produce either enhanced photocurrent through efficient multiple exciton generation (MEG) or enhanced photopotential through hot electron transport and transfer processes. To achieve these desirable effects it is necessary to understand and control the dynamics of electron relaxation, cooling, multiple exciton generation , transport, and interfacial electron transfer of the photogenerated carriers with fs to ns time resolution. We have been studying these fundamental dynamics in bulk and nanoscale semiconductors (quantum dots, quantum wires, and quantum wells) using femtosecond transient absorption, photoluminescence, and THz spectroscopy. This work will be summarized and recent advances in creating multiple excitons from a single photon will be discussed, including a unique model to explain efficient MEG based on the coherent superposition of multiple excitonic states. Various possible configurations for quantum dot solar cells that could produce ultra-high conversion efficiencies for the production of electricity, as well as for producing solar fuels (for example, hydrogen from water splitting), will be discussed, along with associated thermodynamic calculations that show the increase in the maximum theoretical gain in solar photon conversion efficiency for both electricity and fuel production.

  3. Strong quantum coherence between Fermi liquid Mahan excitons

    DOE PAGES

    Paul, J.; Stevens, C. E.; Liu, C.; ...

    2016-04-14

    In modulation doped quantum wells, the excitons are formed as a result of the interactions of the charged holes with the electrons at the Fermi edge in the conduction band, leading to the so-called “Mahan excitons.” The binding energy of Mahan excitons is expected to be greatly reduced and any quantum coherence destroyed as a result of the screening and electron-electron interactions. Surprisingly, we observe strong quantum coherence between the heavy hole and light hole excitons. Such correlations are revealed by the dominating cross-diagonal peaks in both one-quantum and two-quantum two-dimensional Fourier transform spectra. Theoretical simulations based on the opticalmore » Bloch equations where many-body effects are included phenomenologically reproduce well the experimental spectra. Furthermore, time-dependent density functional theory calculations provide insight into the underlying physics and attribute the observed strong quantum coherence to a significantly reduced screening length and collective excitations of the many-electron system.« less

  4. Strong quantum coherence between Fermi liquid Mahan excitons

    SciTech Connect

    Paul, J.; Stevens, C. E.; Liu, C.; Dey, P.; McIntyre, C.; Turkowski, V.; Reno, J. L.; Hilton, D. J.; Karaiskaj, D.

    2016-04-14

    In modulation doped quantum wells, the excitons are formed as a result of the interactions of the charged holes with the electrons at the Fermi edge in the conduction band, leading to the so-called “Mahan excitons.” The binding energy of Mahan excitons is expected to be greatly reduced and any quantum coherence destroyed as a result of the screening and electron-electron interactions. Surprisingly, we observe strong quantum coherence between the heavy hole and light hole excitons. Such correlations are revealed by the dominating cross-diagonal peaks in both one-quantum and two-quantum two-dimensional Fourier transform spectra. Theoretical simulations based on the optical Bloch equations where many-body effects are included phenomenologically reproduce well the experimental spectra. Furthermore, time-dependent density functional theory calculations provide insight into the underlying physics and attribute the observed strong quantum coherence to a significantly reduced screening length and collective excitations of the many-electron system.

  5. Organic photosensitive optoelectronic device having a phenanthroline exciton blocking layer

    DOEpatents

    Thompson, Mark E.; Li, Jian; Forrest, Stephen; Rand, Barry

    2011-02-22

    An organic photosensitive optoelectronic device, having an anode, a cathode, and an organic blocking layer between the anode and the cathode is described, wherein the blocking layer comprises a phenanthroline derivative, and at least partially blocks at least one of excitons, electrons, and holes.

  6. Connecting molecular structure and exciton diffusion length in rubrene derivatives.

    PubMed

    Mullenbach, Tyler K; McGarry, Kathryn A; Luhman, Wade A; Douglas, Christopher J; Holmes, Russell J

    2013-07-19

    Connecting molecular structure and exciton diffusion length in rubrene derivatives demonstrates how the diffusion length of rubrene can be enhanced through targeted functionalization aiming to enhance self-Förster energy transfer. Functionalization adds steric bulk, forcing the molecules farther apart on average, and leading to increased photoluminescence efficiency. A diffusion length enhancement greater than 50% is realized over unsubstituted rubrene.

  7. Vibrational exciton mediated quantum state transfer: Simple model

    NASA Astrophysics Data System (ADS)

    Pouthier, Vincent

    2012-06-01

    A communication protocol is proposed in which quantum state transfer is mediated by a vibrational exciton. We consider two distant molecular groups grafted on the sides of a one-dimensional lattice. These groups behave as two quantum computers where the information in encoded and received. The lattice plays the role of a communication channel along which the exciton propagates and interacts with a phonon bath. Special attention is paid to describing the system involving an exciton dressed by a single phonon mode. The Hamiltonian is thus solved exactly so that the relevance of the perturbation theory is checked. Within the nonadiabatic weak-coupling limit, it is shown that the system supports three quasidegenerate states that define the relevant paths followed by the exciton to tunnel between the computers. When the model parameters are judiciously chosen, constructive interferences take place between these paths. Phonon-induced decoherence is minimized and a high-fidelity quantum state transfer occurs over a broad temperature range.

  8. Exploration of exciton delocalization in organic crystalline thin films

    NASA Astrophysics Data System (ADS)

    Hua, Kim; Manning, Lane; Rawat, Naveen; Ainsworth, Victoria; Furis, Madalina

    The electronic properties of organic semiconductors play a crucial role in designing new materials for specific applications. Our group recently found evidence for a rotation of molecular planes in phthalocyanines that is responsible for the disappearance of a delocalized exciton in these systems for T >150K.................()().......1 In this study, we attempt to tune the exciton delocalization of small organic molecules using strain effects and alloying different molecules in the same family. The exciton behavior is monitored using time- and polarization resolved photolumniscence (PL) spectroscopy as a function of temperature. Specifically, organic crystalline thin films of octabutoxy phthalocyanine (H2OBPc), octyloxy phthalocyanines and H-bonded semiconductors such as the quinacridone and indigo derivatives are deposited on flexible substrates (i.e. Kapton and PEN) using an in-house developed pen-writing method.........2 that results in crystalline films with macroscopic long range order. The room temperature PL studies show redshift and changes in polarization upon bending of the film. Crystalline thin films of alloyed H2OBPc and octabutoxy naphthalocyanine with ratios ranging from 1:1 to 100:1 fabricated on both sapphire and flexible substrates are also explored using the same PL spectroscopy to elucidate the behaviors of delocalized excitons. .1N. Rawat, et al., J Phys Chem Lett 6, 1834 (2015). 2R. L. Headrick, et al., Applied Physics Letters 92, 063302 (2008). NSF DMR-1056589, NSF DMR-1062966.

  9. Heavy ion collisions and the pre-equilibrium exciton model

    SciTech Connect

    Betak, E.

    2012-10-20

    We present a feasible way to apply the pre-equilibrium exciton model in its masterequation formulation to heavy-ion induced reactions including spin variables. Emission of nucleons, {gamma}'s and also light clusters is included in our model.

  10. Coherent Exciton Dynamics in the Presence of Underdamped Vibrations.

    PubMed

    Dijkstra, Arend G; Wang, Chen; Cao, Jianshu; Fleming, Graham R

    2015-02-19

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

  11. Two-dimensional electrostatic lattices for indirect excitons

    NASA Astrophysics Data System (ADS)

    Remeika, M.; Fogler, M. M.; Butov, L. V.; Hanson, M.; Gossard, A. C.

    2012-02-01

    We report on a method for the realization of two-dimensional electrostatic lattices for excitons using patterned interdigitated electrodes. Lattice structure is set by the electrode pattern and depth of the lattice potential is controlled by applied voltages. We demonstrate square, hexagonal, and honeycomb lattices created by this method.

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

    PubMed Central

    2015-01-01

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

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

    PubMed

    Armstrong, Claire L; Price, Michael B; Muñoz-Rojas, David; Davis, Nathaniel J K L; Abdi-Jalebi, Mojtaba; Friend, Richard H; Greenham, Neil C; MacManus-Driscoll, Judith L; Böhm, Marcus L; Musselman, Kevin P

    2015-12-22

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

  14. Physical model of the vapor-liquid (insulator-metal) transition in an exciton gas

    SciTech Connect

    Khomkin, A. L. Shumikhin, A. S.

    2015-04-15

    We propose a simple physical model describing the transition of an exciton gas to a conducting exciton liquid. The transition occurs due to cohesive coupling of excitons in the vicinity of the critical point, which is associated with transformation of the exciton ground state to the conduction band and the emergence of conduction electrons. We calculate the cohesion binding energy for the exciton gas and, using it, derive the equations of state, critical parameters, and binodal. The computational method is analogous to that used by us earlier [5] for predicting the vapor-liquid (insulator-metal) phase transition in atomic (hypothetical, free of molecules) hydrogen and alkali metal vapors. The similarity of the methods used for hydrogen and excitons makes it possible to clarify the physical nature of the transition in the exciton gas and to predict more confidently the existence of a new phase transition in atomic hydrogen.

  15. Extension of the radiative lifetime of Wannier-Mott excitons in semiconductor nanoclusters

    SciTech Connect

    Kukushkin, V. A.

    2015-01-15

    The purpose of the study is to calculate the radiative lifetime of Wannier-Mott excitons in three-dimensional potential wells formed of direct-gap narrow-gap semiconductor nanoclusters in wide-gap semiconductors and assumed to be large compared to the exciton radius. Calculations are carried out for the InAs/GaAs heterosystem. It is shown that, as the nanocluster dimensions are reduced to values on the order of the exciton radius, the exciton radiative lifetime becomes several times longer compared to that in a homogeneous semiconductor. The increase in the radiative lifetime is more pronounced at low temperatures. Thus, it is established that the placement of Wannier-Mott excitons into direct-gap semiconductor nanoclusters, whose dimensions are of the order of the exciton radius, can be used for considerable extension of the exciton radiative lifetime.

  16. 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.

  17. 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

  18. 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.

  19. Exciton diffusion and relaxation in methyl-substituted polyparaphenylene polymer films.

    PubMed

    Gulbinas, V; Mineviciūte, I; Hertel, D; Wellander, R; Yartsev, A; Sundström, V

    2007-10-14

    Exciton diffusion in ladder-type methyl-substituted polyparaphenylene film and solution was investigated by means of femtosecond pump-probe spectroscopy using a combined approach, analyzing exciton-exciton annihilation, and transient absorption depolarization properties. We show that the different views on the exciton dynamics offered by anisotropy decay and annihilation are required in order to obtain a correct picture of the energy transfer dynamics. Comparison of the exciton diffusion coefficient and exciton diffusion radius obtained for polymer film with the two techniques reveals that there is substantial short-range order in the film. Also in isolated chains there is considerable amount of order, as revealed from only partial anisotropy decay, which shows that only a small fraction of the excitons move to differently oriented polymer segments. It is further concluded that interchain energy transfer is faster than intrachain transfer, mainly as a result of shorter interchain distances between chromophoric units.

  20. Excitonic energy transfer in polymer wrapped carbon nanotubes in gradually grown nanoassemblies.

    PubMed

    Karachevtsev, Victor A; Plokhotnichenko, Alexander M; Glamazda, Alexander Yu; Leontiev, Victor S; Levitsky, Igor A

    2014-06-14

    We investigate the exciton energy transfer (ET) in nanoassemblies (nanotube based aggregates) formed by polymer wrapped single-walled carbon nanotubes (SWNTs) using photoluminescence (PL) spectroscopy and simulation. The distinctive feature of this study is the gradual growth of such nanostructures in aqueous medium induced by increasing the concentration of porphyrin molecules stitching nanotube-polymer complexes in densely packed assemblies. Experimental dependencies of PL intensity on the porphyrin concentration for different types of semiconducting SWNTs demonstrate step-like behavior controlled by the amount of bound nanotubes and are in good agreement with the simulating model. The simulation algorithm determines the criterion of the aggregate formation depending on the number of porphyrin molecules per tube and the cascade exciton energy transfer between neighboring semiconducting nanotubes of different chiralities. Aggregates of small sizes (up to six-eight individual tubes) contain mostly semiconducting species, while aggregates of a larger size (up to several tens of tubes) incorporate metallic SWNTs, inducing strong PL quenching. From the fitting procedure, an ET rate of 0.6 × 10(10) s(-1) has been determined which is consistent with the center to center distance (∼2.3 nm) between adjacent tubes separated by polymer and porphyrin molecules. The threshold of the dimer formation corresponds to one porphyrin molecule per ∼20 nm of tube lengths that was supported by molecular dynamics simulation. These findings provide insight into the ET mechanism in SWNT nanoassemblies of variable sizes, which can be gradually controlled by the external factor (the concentration of porphyrin molecules).

  1. 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.

  2. Microscopic simulations of electronic excitations in donor-acceptor heterojunctions of small-molecule based solar cells

    NASA Astrophysics Data System (ADS)

    Baumeier, Bjoern

    2015-03-01

    Fundamental processes involving electronic excitations govern the functionality of molecular materials in which the dynamics of excitons and charges is determined by an interplay of molecular electronic structure and morphological order. To understand, e.g., charge separation and recombination at donor-acceptor heterojunctions in organic solar cells, knowledge about the microscopic details influencing these dynamics in the bulk and across the interface is required. For a set of prototypical heterojunctions of small-molecule donor materials with C60, we employ a hybrid QM/MM approach linking density-functional and many-body Green's functions theory and analyze the charged and neutral electronic excitations therein. We pay special attention the spatially-resolved electron/hole transport levels, as well as the relative energies of Frenkel and charge-transfer excitations at the interface. Finally, we link the molecular architecture of the donor material, its orientation on the fullerene substrate as well as mesoscale order to the solar cell performance.

  3. Mechanisms of electron acceptor utilization: Implications for simulating anaerobic biodegradation

    USGS Publications Warehouse

    Schreiber, M.E.; Carey, G.R.; Feinstein, D.T.; Bahr, J.M.

    2004-01-01

    Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum- contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and

  4. Validation of EMP bounds

    SciTech Connect

    Warne, L.K.; Merewether, K.O.; Chen, K.C.; Jorgenson, R.E.; Morris, M.E.; Solberg, J.E.; Lewis, J.G.; Derr, W.

    1996-07-01

    Test data on canonical weapon-like fixtures are used to validate previously developed analytical bounding results. The test fixtures were constructed to simulate (but be slightly worse than) weapon ports of entry but have known geometries (and electrical points of contact). The exterior of the test fixtures exhibited exterior resonant enhancement of the incident fields at the ports of entry with magnitudes equal to those of weapon geometries. The interior consisted of loaded transmission lines adjusted to maximize received energy or voltage but incorporating practical weapon geometrical constraints. New analytical results are also presented for bounding the energies associated with multiple bolt joints and for bounding the exterior resonant enhancement of the exciting fields.

  5. Fused Nonacyclic Electron Acceptors for Efficient Polymer Solar Cells.

    PubMed

    Dai, Shuixing; Zhao, Fuwen; Zhang, Qianqian; Lau, Tsz-Ki; Li, Tengfei; Liu, Kuan; Ling, Qidan; Wang, Chunru; Lu, Xinhui; You, Wei; Zhan, Xiaowei

    2017-01-25

    We design and synthesize four fused-ring electron acceptors based on 6,6,12,12-tetrakis(4-hexylphenyl)-indacenobis(dithieno[3,2-b;2',3'-d]thiophene) as the electron-rich unit and 1,1-dicyanomethylene-3-indanones with 0-2 fluorine substituents as the electron-deficient units. These four molecules exhibit broad (550-850 nm) and strong absorption with high extinction coefficients of (2.1-2.5) × 10(5) M(-1) cm(-1). Fluorine substitution downshifts the LUMO energy level, red-shifts the absorption spectrum, and enhances electron mobility. The polymer solar cells based on the fluorinated electron acceptors exhibit power conversion efficiencies as high as 11.5%, much higher than that of their nonfluorinated counterpart (7.7%). We investigate the effects of the fluorine atom number and position on electronic properties, charge transport, film morphology, and photovoltaic properties.

  6. An organic donor/acceptor lateral superlattice at the nanoscale.

    PubMed

    Otero, Roberto; Ecija, David; Fernandez, Gustavo; Gallego, José María; Sanchez, Luis; Martín, Nazario; Miranda, Rodolfo

    2007-09-01

    A precise control of the nanometer-scale morphology in systems containing mixtures of donor/acceptor molecules is a key factor to improve the efficiency of organic photovoltaic devices. Here we report on a scanning tunneling microscopy study of the first stages of growth of 2-[9-(1,3-dithiol-2-ylidene)anthracen-10(9H)-ylidene]-1,3-dithiole, as electron donor, and phenyl-C61-butyric acid methyl ester, as electron acceptor, on a Au(111) substrate under ultrahigh vacuum conditions. Due to differences in bonding strength with the substrate and different interactions with the Au(111) herringbone surface reconstruction, mixed thin films spontaneously segregate into a lateral superlattice of interdigitated nanoscale stripes with a characteristic width of about 10-20 nm, a morphology that has been predicted to optimize the efficiency of organic solar cells.

  7. Cross-conjugated chromophores: synthesis of iso-polydiacetylenes with Donor/Acceptor substitution

    PubMed

    Ciulei; Tykwinski

    2000-11-16

    The iterative construction of cross-conjugated donor (D), acceptor (A), and donor-acceptor (D-A) substituted iso-polydiacetylene (iso-PDA) oligomers has been achieved utilizing palladium-catalyzed cross-coupling techniques. Structure-property relationships for these compounds have been analyzed for cross-conjugated pi-electronic communication as a result of contributions from donor, acceptor, or donor-acceptor functionalization.

  8. Engineered oligosaccharyltransferases with greatly relaxed acceptor site specificity

    PubMed Central

    Ollis, Anne A.; Zhang, Sheng; Fisher, Adam C.; DeLisa, Matthew P.

    2015-01-01

    The Campylobacter jejuni protein glycosylation locus (pgl) encodes machinery for asparagine-linked (N-linked) glycosylation and serves as the archetype for bacterial N-glycosylation. This machinery has been functionally transferred into Escherichia coli, thereby enabling convenient mechanistic dissection of the N-glycosylation process in this genetically tractable host. Here, we sought to identify sequence determinants in the oligosaccharyltransferase PglB that restrict its specificity to only those glycan acceptor sites containing a negatively charged residue at the −2 position relative to asparagine. This involved creation of a genetic assay named glycoSNAP (glycosylation of secreted N-linked acceptor proteins) that facilitates high-throughput screening of glycophenotypes in E. coli. Using this assay, we isolated several C. jejuni PglB variants that were capable of glycosylating an array of noncanonical acceptor sequences including one in a eukaryotic N-glycoprotein. Collectively, these results underscore the utility of glycoSNAP for shedding light on poorly understood aspects of N-glycosylation and for engineering designer N-glycosylation biocatalysts. PMID:25129029

  9. Income-generating activities for family planning acceptors.

    PubMed

    1989-07-01

    The Income Generating Activities program for Family Planning Acceptors was introduced in Indonesia in 1979. Capital input by the Indonesian National Family Planning Coordination Board and the UN Fund for Population Activities was used to set up small businesses by family planning acceptors. In 2 years, when the businesses become self-sufficient, the loans are repaid, and the money is used to set up new family planning acceptors in business. The program strengthens family planning acceptance, improves the status of women, and enhances community self-reliance. The increase in household income generated by the program raises the standards of child nutrition, encourages reliance on the survival of children, and decreases the value of large families. Approximately 18,000 Family Planning-Income Generating Activities groups are now functioning all over Indonesia, with financial assistance from the central and local governments, the World Bank, the US Agency for International Development, the UN Population Fund, the Government of the Netherlands, and the Government of Australia through the Association of South East Asian Nations.

  10. Design directed self-assembly of donor-acceptor polymers.

    PubMed

    Marszalek, Tomasz; Li, Mengmeng; Pisula, Wojciech

    2016-09-21

    Donor-acceptor polymers with an alternating array of donor and acceptor moieties have gained particular attention during recent years as active components of organic electronics. By implementation of suitable subunits within the conjugated backbone, these polymers can be made either electron-deficient or -rich. Additionally, their band gap and light absorption can be precisely tuned for improved light-harvesting in solar cells. On the other hand, the polymer design can also be modified to encode the desired supramolecular self-assembly in the solid-state that is essential for an unhindered transport of charge carriers. This review focuses on three major factors playing a role in the assembly of donor-acceptor polymers on surfaces which are (1) nature, geometry and substitution position of solubilizing alkyl side chains, (2) shape of the conjugated polymer defined by the backbone curvature, and (3) molecular weight which determines the conjugation length of the polymer. These factors adjust the fine balance between attractive and repulsive forces and ensure a close polymer packing important for an efficient charge hopping between neighboring chains. On the microscopic scale, an appropriate domain formation with a low density of structural defects in the solution deposited thin film is crucial for the charge transport. The charge carrier transport through such thin films is characterized by field-effect transistors as basic electronic elements.

  11. Quantum dots as FRET acceptors for highly sensitive multiplexing immunoassays

    NASA Astrophysics Data System (ADS)

    Geissler, Daniel; Hildebrandt, Niko; Charbonnière, Loïc J.; Ziessel, Raymond F.; Löhmannsröben, Hans-Gerd

    2009-02-01

    Homogeneous immunoassays have the benefit that they do not require any time-consuming separation steps. FRET is one of the most sensitive homogeneous methods used for immunoassays. Due to their extremely strong absorption over a broad wavelength range the use of quantum dots as FRET acceptors allows for large Foerster radii, an important advantage for assays in the 5 to 10 nm distance range. Moreover, because of their size-tunable emission, quantum dots of different sizes can be used with a single donor for the detection of different analytes (multiplexing). As the use of organic dyes with short fluorescence decay times as donors is known to be inefficient with quantum dot acceptors, lanthanide complexes with long luminescence decays are very efficient alternatives. In this contribution we present the application of commercially available biocompatible CdSe/ZnS core/shell quantum dots as multiplexing FRET acceptors together with a single terbium complex as donor in a homogeneous immunoassay system. Foerster radii of 10 nm and FRET efficiencies of 75 % are demonstrated. The high sensitivity of the terbium-toquantum dot FRET assay is shown by sub-100-femtomolar detection limits for two different quantum dots (emitting at 605 and 655 nm) within the same biotin-streptavidin assay. Direct comparison to the FRET immunoassay "gold standard" (FRET from Eu-TBP to APC) yields a three orders of magnitude sensitivity improvement, demonstrating the big advantages of quantum dots not only for multiplexing but also for highly sensitive nanoscale analysis.

  12. Fullerene derivatives as electron acceptors for organic photovoltaic cells.

    PubMed

    Mi, Dongbo; Kim, Ji-Hoon; Kim, Hee Un; Xu, Fei; Hwang, Do-Hoon

    2014-02-01

    Energy is currently one of the most important problems humankind faces. Depletion of traditional energy sources such as coal and oil results in the need to develop new ways to create, transport, and store electricity. In this regard, the sun, which can be considered as a giant nuclear fusion reactor, represents the most powerful source of energy available in our solar system. For photovoltaic cells to gain widespread acceptance as a source of clean and renewable energy, the cost per watt of solar energy must be decreased. Organic photovoltaic cells, developed in the past two decades, have potential as alternatives to traditional inorganic semiconductor photovoltaic cells, which suffer from high environmental pollution and energy consumption during production. Organic photovoltaic cells are composed of a blended film of a conjugated-polymer donor and a soluble fullerene-derivative acceptor sandwiched between a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)-coated indium tin oxide positive electrode and a low-work-function metal negative electrode. Considerable research efforts aim at designing and synthesizing novel fullerene derivatives as electron acceptors with up-raised lowest unoccupied molecular orbital energy, better light-harvesting properties, higher electron mobility, and better miscibility with the polymer donor for improving the power conversion efficiency of the organic photovoltaic cells. In this paper, we systematically review novel fullerene acceptors synthesized through chemical modification for enhancing the photovoltaic performance by increasing open-circuit voltage, short-circuit current, and fill factor, which determine the performance of organic photovoltaic cells.

  13. 2012 ELECTRON DONOR-ACCEPTOR INTERACTIONS GORDON RESEARCH CONFERENCE, AUGUST 5-10, 2012

    SciTech Connect

    McCusker, James

    2012-08-10

    The upcoming incarnation of the Gordon Research Conference on Electron Donor Acceptor Interactions will feature sessions on classic topics including proton-coupled electron transfer, dye-sensitized solar cells, and biological electron transfer, as well as emerging areas such as quantum coherence effects in donor-acceptor interactions, spintronics, and the application of donor-acceptor interactions in chemical synthesis.

  14. Computing Graphical Confidence Bounds

    NASA Technical Reports Server (NTRS)

    Mezzacappa, M. A.

    1983-01-01

    Approximation for graphical confidence bounds is simple enough to run on programmable calculator. Approximation is used in lieu of numerical tables not always available, and exact calculations, which often require rather sizable computer resources. Approximation verified for collection of up to 50 data points. Method used to analyze tile-strength data on Space Shuttle thermal-protection system.

  15. Nonlinear Nano-Optics: Probing One Exciton at a Time

    NASA Astrophysics Data System (ADS)

    Bonadeo, Nicolas H.

    1998-03-01

    Optical studies in single quantum dots (QD's) have recently been possible with the use of high spatial resolution techniques (K. Brunner,et al., Phys. Rev. Lett. 69, 3216 (1992).)^,(H. F. Hess,et al., Science 264, 1740 (1994).)^,(D. Gammon, et al., Phys. Rev. Lett. 76, 3005 (1996).). The various approaches remove the spectral blurring caused by inhomogeneous broadening in ensemble measurements revealing extremely sharp resonances that result from the complete energy quantization of the zero-dimensional exciton. Previous experiments in single QD's have been based uniquely in photoluminescence (PL) detection and were mainly performed in the frequency domain. In this work, we present data from two different experimental approaches that go beyond these limitations and open up a new direction of research for direct measurements of exciton dynamics, coherent transients and optical nonlinearities in QD's. The first set of experiments combines the elegance and power of CW coherent nonlinear optical spectroscopy with the breakthrough of single QD probing producing the first nonlinear measurement in a single QD. The nonlinear measurements allow us to identify an incoherent and coherent contribution to the resonant electronic response, extract the excitation decoherence time and energy relaxation rate, as well as demonstrate a behavior similar to two beam coupling. In the second set of experiments, using two phase-locked lasers pulses, we show the possibility to control the population(A. P. Heberly, J.J. Baumberg, and Kohler, Phys. Rev. Lett. 74, 3596 (1995))of a single QD in times shorter than the excitonic lifetime and taking thus, coherent-control to the ultimate quantum limit of a single exciton per control box. In addition, we performed a series of transient experiments that includes the first direct measurement of the decoherence time in single QD. The measurements are performed at T=6K in a narrow (42 Åsingle MBE grown GaAs quantum well with 250 ÅAl _0.3Ga_0.7As

  16. Excitonic complexes in GaN/(Al,Ga)N quantum dots

    NASA Astrophysics Data System (ADS)

    Elmaghraoui, D.; Triki, M.; Jaziri, S.; Muñoz-Matutano, G.; Leroux, M.; Martinez-Pastor, J.

    2017-03-01

    Here we report a theoretical investigation of excitonic complexes in polar GaN/(Al,Ga)N quantum dots (QDs). A sum rule between the binding energies of charged excitons is used to calculate the biexciton binding energy. The binding energies of excitonic complexes in GaN/AlN are shown to be strongly correlated to the QD size. Due to the large hole localization, the positively charged exciton energy is found to be always blueshifted compared to the exciton one. The negatively charged exciton and the biexciton energy can be blueshifted or redshifted according to the QD size. Increasing the size of GaN/AlN QDs makes the identification of charged excitons difficult, and the use of an Al0.5Ga0.5N barrier can be advantageous for clear identification. Our theoretical results for the binding energy of exciton complexes are also confronted with values deduced experimentally for InAs/GaAs QDs, confirming our theoretical prediction for charged excitonic complexes in GaN/(Al,Ga)N QDs. Finally, we realize that the trends of excitonic complexes in QDs are significantly related to competition between the local charge separation (whatever its origin) and the correlation effect. Following our findings, entangled photons pairs can be produced in QDs with careful control of their size in order to obtain zero exciton–biexciton energy separation.

  17. Spectral, thermal and kinetic studies of charge-transfer complexes formed between the highly effective antibiotic drug metronidazole and two types of acceptors: σ- and π-acceptors.

    PubMed

    Refat, Moamen S; Saad, Hosam A; Adam, Abdel Majid A

    2015-04-15

    Understanding the interaction between drugs and small inorganic or organic molecules is critical in being able to interpret the drug-receptor interactions and acting mechanism of these drugs. A combined solution and solid state study was performed to describe the complexation chemistry of drug metronidazole (MZ) which has a broad-spectrum antibacterial activity with two types of acceptors. The acceptors include, σ-acceptor (i.e., iodine) and π-acceptors (i.e., dichlorodicyanobenzoquinone (DDQ), chloranil (CHL) and picric acid (PA)). The molecular structure, spectroscopic characteristics, the binding modes as well as the thermal stability were deduced from IR, UV-vis, (1)H NMR and thermal studies. The binding ratio of complexation (MZ: acceptor) was determined to be 1:2 for the iodine acceptor and 1:1 for the DDQ, CHL or PA acceptor, according to the CHN elemental analyses and spectrophotometric titrations. It has been found that the complexation with CHL and PA acceptors increases the values of enthalpy and entropy, while the complexation with DDQ and iodine acceptors decreases the values of these parameters compared with the free MZ donor.

  18. Spectral, thermal and kinetic studies of charge-transfer complexes formed between the highly effective antibiotic drug metronidazole and two types of acceptors: σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2015-04-01

    Understanding the interaction between drugs and small inorganic or organic molecules is critical in being able to interpret the drug-receptor interactions and acting mechanism of these drugs. A combined solution and solid state study was performed to describe the complexation chemistry of drug metronidazole (MZ) which has a broad-spectrum antibacterial activity with two types of acceptors. The acceptors include, σ-acceptor (i.e., iodine) and π-acceptors (i.e., dichlorodicyanobenzoquinone (DDQ), chloranil (CHL) and picric acid (PA)). The molecular structure, spectroscopic characteristics, the binding modes as well as the thermal stability were deduced from IR, UV-vis, 1H NMR and thermal studies. The binding ratio of complexation (MZ: acceptor) was determined to be 1:2 for the iodine acceptor and 1:1 for the DDQ, CHL or PA acceptor, according to the CHN elemental analyses and spectrophotometric titrations. It has been found that the complexation with CHL and PA acceptors increases the values of enthalpy and entropy, while the complexation with DDQ and iodine acceptors decreases the values of these parameters compared with the free MZ donor.

  19. Role of strain relaxation in exciton resonance energies of ZnO epitaxial layers grown on SiC substrates

    NASA Astrophysics Data System (ADS)

    Almamun Ashrafi, Abm

    2004-03-01

    The wide bandgap ZnO semiconductor is currently the subject of interest for the study of physics as well as investigations in response to the industrial demand for applications in optoelectronics devices. The most exciting physical properties of ZnO are the largest exciton binding energy of 60 meV and this can be tuned up to 120 meV by controlling the ZnO active layers1. Towards these goals, a great deal of efforts has been made on ZnO layers grown mostly on Al2O3 substrates. It is noted that the lattice mismatch in ZnO/Al2O3 is 18structural defects, and higher residual carrier concentration. To overcome these basic but unavoidable problems for crystalline quality, nearly-matched SiC substrate may play a role including reproducible p-type conductivity in ZnO layers2. Considering the ZnO lattice constant, the estimated lattice mismatch between the ZnO and SiC is to be 5may explore the ZnO epitaxy with the superior crystalline as well as optical properties towards the study of quantum physics in nanoscale level where strain governs the local atomic mechanisms in principle. Recently, we have reported the superior ZnO crystalline quality grown on SiC substrates compared to the ZnO/Al2O3 samples by MOCVD3. In progress to these results, strain relaxation effects in exciton resonance energies of ZnO layers have been addressed in this letter. The surface morphology of ZnO layers grown on SiC exhibited hexagons geometry for the VI/II falux raio of 4 by reflecting the +c ZnO surface. From these layers, therefore, free exciton (FX) emission was appeared with A and B bands to the corresponding energies of 3.377 and 3.390 eV4. With the increase of temperature, however, the FXs emission showed the quenching of excitons energy as well as intensity which may be a subject of overlapping the A and donor-bound (D0X) excitons4. The deduced activation energies of A and D0X exciton emissions suggested a consistency with an inclusion of exciton-defect binding energy in optical bands. The

  20. Method for producing and regenerating a synthetic CO[sub 2] acceptor

    DOEpatents

    Lancet, M. S.; Curran, G. P.; Gorin, E.

    1982-05-18

    A method is described for producing a synthetic CO[sub 2] acceptor by feeding a mixture of finely divided silica and at least one finely divided calcium compound selected from the group consisting of calcium oxide and calcium carbonate to a fluidized bed; operating the fluidized bed at suitable conditions to produce pellets of synthetic CO[sub 2] acceptor and recovering the pellets of synthetic CO[sub 2] acceptor from the fluidized bed. Optionally, spent synthetic CO[sub 2] acceptor can be charged to the fluidized bed to produce regenerated pellets of synthetic CO[sub 2] acceptor. 1 fig.