Showing papers on "Exciton published in 2005"
TL;DR: It is found that the biexciton effect, which shifts the transition energy for absorption of a second photon, influences the early time transient absorption data and may contribute to a modulation observed when probing near the lowest interband transition.
Abstract: We report ultra-efficient multiple exciton generation (MEG) for single photon absorption in colloidal PbSe and PbS quantum dots (QDs). We employ transient absorption spectroscopy and present measurement data acquired for both intraband as well as interband probe energies. Quantum yields of 300% indicate the creation, on average, of three excitons per absorbed photon for PbSe QDs at photon energies that are four times the QD energy gap. Results indicate that the threshold photon energy for MEG in QDs is twice the lowest exciton absorption energy. We find that the biexciton effect, which shifts the transition energy for absorption of a second photon, influences the early time transient absorption data and may contribute to a modulation observed when probing near the lowest interband transition. We present experimental and theoretical values of the size-dependent interband transition energies for PbSe QDs. We present experimental and theoretical values of the size-dependent interband transition energies for ...
1,605 citations
TL;DR: Two-photon excitation spectroscopy bolsters the exciton picture and demonstrates the dominant role of many-body interactions in the excited-state properties of one-dimensional systems.
Abstract: Optical transitions in carbon nanotubes are of central importance for nanotube characterization. They also provide insight into the nature of excited states in these one-dimensional systems. Recent work suggests that light absorption produces strongly correlated electron-hole states in the form of excitons. However, it has been difficult to rule out a simpler model in which resonances arise from the van Hove singularities associated with the one-dimensional bond structure of the nanotubes. Here, two-photon excitation spectroscopy bolsters the exciton picture. We found binding energies of ∼400 millielectron volts for semiconducting single-walled nanotubes with 0.8-nanometer diameters. The results demonstrate the dominant role of many-body interactions in the excited-state properties of one-dimensional systems.
1,126 citations
TL;DR: In this article, the spin-orbit split heavy-hole states lie in the plane of the 2D layer of a light-emitting diode and a nonzero out-of-plane component of the angular momentum is detected.
Abstract: We report the experimental observation of the spin-Hall effect in a 2D hole system with spin-orbit coupling. The 2D hole layer is a part of a $p\mathrm{\text{\ensuremath{-}}}n$ junction light-emitting diode with a specially designed coplanar geometry which allows an angle-resolved polarization detection at opposite edges of the 2D hole system. In equilibrium the angular momenta of the spin-orbit split heavy-hole states lie in the plane of the 2D layer. When an electric field is applied across the hole channel, a nonzero out-of-plane component of the angular momentum is detected whose sign depends on the sign of the electric field and is opposite for the two edges. Microscopic quantum transport calculations show only a weak effect of disorder, suggesting that the clean limit spin-Hall conductance description (intrinsic spin-Hall effect) might apply to our system.
1,102 citations
Journal Article•
TL;DR: In the limit of a QD much smaller than the bulk exciton size, the linear spectrum will be a series of lines, and the phonon broadening of these lines is considered.
Abstract: We analyze theoretically the optical properties of ideal semiconductor crystallites so small that they show quantum confinement in all three dimensions [quantum dots (QD's)]. In the limit of a QD much smaller than the bulk exciton size, the linear spectrum will be a series of lines, and we consider the phonon broadening of these lines. The lowest interband transition will saturate like a two-level system, without exchange and Coulomb screening. Depending on the broadening, the absorption and the changes in absorption and refractive index resulting from saturation can become very large, and the local-field effects can become so strong as to give optical bistability without external feedback. The small QD limit is more readily achieved with narrow-band-gap semiconductors.
788 citations
TL;DR: In this paper, a brief review is given of electronic and transport properties of carbon nanotubes obtained mainly in a k · p scheme, including a giant Aharonov-Bohm effect on the band gap and a Landau-level formation in magnetic fields.
Abstract: A brief review is given of electronic and transport properties of carbon nanotubes obtained mainly in a k · p scheme. The topics include a giant Aharonov–Bohm effect on the band gap and a Landau-level formation in magnetic fields, magnetic properties, interaction effects on the band structure, optical absorption spectra, and exciton effects. Transport properties are also discussed including absence of backward scattering except for scatterers with a potential range smaller than the lattice constant, its extension to multi-channel cases, a conductance quantization in the presence of short-range and strong scatterers such as lattice vacancies, and transport across junctions between nanotubes with different diameters. A continuum model for phonons in the long-wavelength limit and the resistivity determined by phonon scattering are reviewed as well.
734 citations
TL;DR: The observation of the strong-coupling regime between the excitonic transition of a single GaAs quantum dot and a discrete optical mode of a microdisk microcavity is reported on.
Abstract: We report on the observation of the strong-coupling regime between the excitonic transition of a single GaAs quantum dot and a discrete optical mode of a microdisk microcavity. Photoluminescence is performed at various temperatures to tune the quantum dot exciton with respect to the optical mode. At resonance, we observe a clear anticrossing behavior, signature of the strong-coupling regime. The vacuum Rabi splitting amounts to 400 microeV and is twice as large as the individual linewidths.
722 citations
TL;DR: In this paper, the binding energies of single-walled carbon nanotubes with diameters between 6.8 and 9.4 were determined by ab initio calculations, based on photoluminescence excitation experiments.
Abstract: Excitonic effects in the linear and nonlinear optical properties of single-walled carbon nanotubes are manifested by photoluminescence excitation experiments and ab initio calculations. One- and two-photon spectra showed a series of exciton states; their energy splitting is the fingerprint of excitonic interactions in carbon nanotubes. By ab initio calculations we determine the energies, wave functions, and symmetries of the excitonic states. Combining experiment and theory we find binding energies of $0.3\char21{}0.4\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ for nanotubes with diameters between 6.8 and $9.0\phantom{\rule{0.3em}{0ex}}\mathrm{\AA{}}$.
471 citations
TL;DR: In this paper, the authors present detailed analysis of the dynamics that govern the ultrafast growth of multi-exciton populations in CdSe and PbSe nanocrystals and propose a model of how such populations arise.
Abstract: We have previously demonstrated that absorption of a single photon by a nanocrystal quantum dot can generate multiple excitons with an efficiency of up to 100%. This effect, known as carrier multiplication, should lead to substantial improvements in the performance of a variety of optoelectronic and photocatalytic devices, including solar cells, low-threshold lasers and entangled photon sources. Here we present detailed analysis of the dynamics that govern the ultrafast growth of multi-exciton populations in CdSe and PbSe nanocrystals and propose a model of how such populations arise. Our analysis indicates that the generation of multi-excitons in these systems takes less than 200 fs, which suggests that it is an instantaneous event. We explain this in terms of their direct photogeneration via multiple virtual single-exciton states. This process relies on both the confinement-enhanced Coulomb coupling between single excitons and multi-excitons and the large spectral density of high-energy single- and multi-exciton resonances that occur in semiconductor nanocrystals.
445 citations
TL;DR: An analytic expression for numerical simulations of time- and frequency-resolved 2D photon echo signals is obtained and it is found that there are two noncascading exciton energy relaxation pathways.
Abstract: A theoretical description of femtosecond two-dimensional electronic spectroscopy of multichromophoric systems is presented. Applying the stationary phase approximation to the calculation of photon echo spectra and taking into account exciton relaxation processes, we obtain an analytic expression for numerical simulations of time- and frequency-resolved 2D photon echo signals. The delocalization of one-exciton states, spatial overlaps between the probability densities of different excitonic states, and their influences on both one- and two-dimensional electronic spectra are studied. The nature of the off-diagonal cross-peaks and the time evolution of both diagonal and off-diagonal peak amplitudes are discussed in detail by comparing experimentally measured and theoretically simulated 2D spectra of the natural Fenna−Matthews−Olson (FMO) photosynthetic light-harvesting complex. We find that there are two noncascading exciton energy relaxation pathways.
436 citations
TL;DR: Extended Hückel tight-binding band calculations are employed to decipher the crystal orbital origins of the structural effects that fine-tune the band structure, and suggest that it may be possible to tune the band gap by as much as 1 eV using the templating influence of the organic cation.
Abstract: Structural distortions within the extensive family of organic/inorganic hybrid tin iodide perovskite semiconductors are correlated with their experimental exciton energies and calculated band gaps. The extent of the in- and out-of-plane angular distortion of the SnI42- perovskite sheets is largely determined by the relative charge density and steric requirements of the organic cations. Variation of the in-plane Sn−I−Sn bond angle was demonstrated to have the greatest impact on the tuning of the band gap, and the equatorial Sn−I bond distances have a significant secondary influence. Extended Huckel tight-binding band calculations are employed to decipher the crystal orbital origins of the structural effects that fine-tune the band structure. The calculations suggest that it may be possible to tune the band gap by as much as 1 eV using the templating influence of the organic cation.
433 citations
TL;DR: It is observed that heterostructures consisting of a spin-coated poly(p-phenylene vinylene) (PPV)-based derivative and evaporated C60 are ill-defined because of diffusion of C60 into the polymer, leading to an overestimation of the exciton diffusion length.
Abstract: Exciton diffusion and photoluminescence quenching in conjugated polymer/fullerene heterostructures are studied by time-resolved photoluminescence. It is observed that heterostructures consisting of...
TL;DR: Tuning the surface plasmon polariton resonance to the quantum dot exciton emission band results in an enhancement of up to approximately 50-fold in the overall fluorescence efficiency, in a design where each Ag nanoparticle is interconnected by a continuous Ag thin film.
Abstract: Nanoengineered fluorescent response is reported from semiconductor core-shell (CdSe/ZnS) quantum dots in proximity to the surface plasmon polariton field of periodic Ag nanoparticle arrays. Tuning the surface plasmon polariton resonance to the quantum dot exciton emission band results in an enhancement of up to approximately 50-fold in the overall fluorescence efficiency, in a design where each Ag nanoparticle is interconnected by a continuous Ag thin film. Propagating modes of surface plasmon resonances have a direct impact on the fluorescence enhancement.
TL;DR: New strategies for the rational design of NLO molecular assemblies are inferred on the basis of the acquired insights into the nature of fundamental excited-state dynamics and the nonlinear optical (NLO) response involved.
Abstract: To investigate the effect of branching on linear and nonlinear optical properties, a specific series of chromophores, epitome of (multi)branched dipoles, has been thoroughly explored by a combined theoretical and experimental approach. Excited-state structure calculations based on quantum-chemical techniques (time-dependent density functional theory) as well as a Frenkel exciton model nicely complement experimental photoluminescence and one- and two-photon absorption findings and contribute to their interpretation. This allowed us to get a deep insight into the nature of fundamental excited-state dynamics and the nonlinear optical (NLO) response involved. Both experiment and theory reveal that a multidimensional intramolecular charge transfer takes place from the donating moiety to the periphery of the branched molecules upon excitation, while fluorescence stems from an excited state localized on one of the dipolar branches. Branching is also observed to lead to cooperative enhancement of two-photon absorption (TPA) while maintaining high fluorescence quantum yield, thanks to localization of the emitting state. The comparison between results obtained in the Frenkel exciton scheme and ab initio results suggests the coherent coupling between branches as one of the possible mechanisms for the observed enhancement. New strategies for the rational design of NLO molecular assemblies are thus inferred on the basis of the acquired insights.
TL;DR: The high local electric fields at the junction between the suspended and supported parts of a single carbon nanotube molecule to produce unusually bright infrared emission under unipolar operation allows us to observe emission from higher excited states not seen by photoexcitation.
Abstract: We used the high local electric fields at the junction between the suspended and supported parts of a single carbon nanotube molecule to produce unusually bright infrared emission under unipolar operation. Carriers were accelerated by band-bending at the suspension interface, and they created excitons that radiatively recombined. This excitation mechanism is ∼1000 times more efficient than recombination of independently injected electrons and holes, and it results from weak electron-phonon scattering and strong electron-hole binding caused by one-dimensional confinement. The ensuing high excitation density allows us to observe emission from higher excited states not seen by photoexcitation. The excitation mechanism of these states was analyzed.
TL;DR: In this article, the acceptor energy level of Sb dopant is estimated to be 0.2 eV above the valence band, which is an excellent dopant for reliable and reproducible p-type ZnO fabrication.
Abstract: Reproducible Sb-doped p-type ZnO films were grown on n-Si (100) by electron-cyclotron-resonance-assisted molecular-beam epitaxy. The existence of Sb in ZnO:Sb films was confirmed by low-temperature photoluminescence measurements. An acceptor-bound exciton (A°X) emission was observed at 3.358 eV at 8 K. The acceptor energy level of the Sb dopant is estimated to be 0.2 eV above the valence band. Temperature-dependent Hall measurements were performed on Sb-doped ZnO films. At room temperature, one Sb-doped ZnO sample exhibited a low resistivity of 0.2Ωcm, high hole concentration of 1.7×1018cm−3 and high mobility of 20.0cm2∕Vs. This study suggests that Sb is an excellent dopant for reliable and reproducible p-type ZnO fabrication.
TL;DR: The observed anticrossing occurs between excitons with predominant spatially direct and indirect character and reveals a field driven transition of the nature of the molecular ground state exciton wave function.
Abstract: We report the direct observation of quantum coupling in individual quantum dot molecules and its manipulation using static electric fields. A pronounced anticrossing of different excitonic transitions is observed as the electric field is tuned. A comparison of our experimental results with theory shows that the observed anticrossing occurs between excitons with predominant spatially direct and indirect character and reveals a field driven transition of the nature of the molecular ground state exciton wave function. Finally, the interdot quantum coupling strength is deduced optically and its dependence on the interdot separation is calculated.
TL;DR: A theoretical analysis and first-principles calculation of the radiative lifetime of excitons in semiconducting carbon nanotubes finds an effective lifetime of the order of 10 ns at room temperature, in good accord with recent experiments.
Abstract: We present a theoretical analysis and first-principles calculation of the radiative lifetime of excitons in semiconducting carbon nanotubes. An intrinsic lifetime of the order of 10 ps is computed for the lowest optically active bright excitons. The intrinsic lifetime is, however, a rapid increasing function of the exciton momentum. Moreover, the electronic structure of the nanotubes dictates the existence of dark excitons near in energy to each bright exciton. Both effects strongly influence measured lifetime. Assuming a thermal occupation of bright and dark exciton bands, we find an effective lifetime of the order of 10 ns at room temperature, in good accord with recent experiments.
Journal Article•
TL;DR: A general scheme is established within the effective-mass approximation to calculate systematically the excitonic energy spectra in a semiconductor quantum dot including the dielectric confinement effect including the subband mixing effect due to the electron-hole Coulomb interaction.
Abstract: A general scheme is established within the effective-mass approximation to calculate systematically the excitonic energy spectra in a semiconductor quantum dot including the dielectric confinement effect. This effect is found to appear most pronounced in the quantum-dot structure in comparison with the quantum-well and quantum-wire structures. A formula of the lowest exciton energy in the strong confinement regime is derived and the significance of the dielectric confinement effect is clarified. We investigate the dependence of the binding energy and the oscillator strength of the lowest-energy excitonic state on the quantum-dot radius, the electron-to-hole mass ratio, and the dielectric-constant ratio between the quantum dot and the surrounding medium. The subband mixing effect due to the electron-hole Coulomb interaction gives a finite oscillator strength to excitonic transitions which are forbidden in the absence of the Coulomb interaction. This effect is shown unambiguously in the calculated excitonic energy spectra. Furthermore, the electron-hole exchange interaction in a quantum dot is discussed. The short-range part of the exchange energy is shown to increase in proportion to the inverse of the volume of the quantum dot as the quantum-dot size is reduced. On the other hand, the long-range part of the exchange energy is found to be sensitively dependent on the shape of the quantum dot. In particular, it vanishes for the optically allowed excitonic states in a spherical quantum dot.
TL;DR: In this paper, a high-boiling-point solvent, 1,2,4-trichlorobenzene, instead of chloroform for spin-coating, was used to obtain a threefold increase in solar power conversion efficiency in devices based on CdSe tetrapods and poly(p-phenylenvinylene) derivative OC1C10-PPV.
Abstract: Solution-processed photovoltaic devices based on blends of conjugated polymers and inorganic semiconductor tetrapods show high efficiencies due to the good electron transport perpendicular to the plane of the film. Here, we show that by using a high-boiling-point solvent, 1,2,4-trichlorobenzene, instead of chloroform for spin-coating, we can typically obtain a threefold increase in solar power conversion efficiency in devices based on CdSe tetrapods and the poly(p-phenylenvinylene) derivative OC1C10-PPV. The optimized devices show AM1.5 solar power conversion efficiencies of typically 2.1% with some devices as high as 2.8%. The results can be explained by the occurrence of vertical phase separation which leads to an optimal structure for charge collection. Evidence for this structure is obtained by environmental scanning electron microscopy, photocurrent action spectra measurements, time-resolved photoluminescence, and spectroscopic measurements of exciton dissociation and charge-carrier recombination.
TL;DR: The experimental data indicate faster exciton migration in films with respect to solution as a result of the emergence of efficient channels involving hopping between chains in close contact, and theoretical simulations based on an improved Forster model predict faster intermolecular energy transfer.
Abstract: The dynamics of interchain and intrachain excitation energy transfer taking place in a polyindenofluorene endcapped with perylene derivatives is explored by means of ultrafast spectroscopy combined with correlated quantum-chemical calculations. The experimental data indicate faster exciton migration in films with respect to solution as a result of the emergence of efficient channels involving hopping between chains in close contact. These findings are supported by theoretical simulations based on an improved Forster model. Within this model, the rates are expressed according to the Fermi golden rule on the basis of (i) electronic couplings that take account of the detailed shape of the excited-state wave functions (through the use of a multicentric monopole expansion) and (ii) spectral overlap factors computed from the simulated acceptor absorption and donor emission spectra with explicit coupling to vibrations (considered within a displaced harmonic oscillator model); inhomogeneity is taken into account by assuming a distribution of chromophores with different conjugation lengths. The calculations predict faster intermolecular energy transfer as a result of larger electronic matrix elements and suggest a two-step mechanism for intrachain energy transfer with exciton hopping along the polymer backbone as the limiting step. Injecting the calculated hopping rates into a set of master equations allows the modeling of the dynamics of exciton transport along the polyindenofluorene chains and yields ensemble-averaged energy-transfer rates in good agreement with experiment.
TL;DR: In this paper, the temperature dependence of photoluminescence transitions associated with various excitons and their phonon replicas in high-purity bulk ZnO has been studied at temperatures from 12 K to above room temperature (320 K).
Abstract: The temperature dependence of the photoluminescence (PL) transitions associated with various excitons and their phonon replicas in high-purity bulk ZnO has been studied at temperatures from 12 K to above room temperature (320 K). Several strong PL emission lines associated with LO phonon replicas of free and bound excitons are clearly observed. The room temperature PL spectrum is dominated by the phonon replicas of the free exciton transition with the maximum at the first LO phonon replica. The results explain the discrepancy between the transition energy of free exciton determined by reflection measurement and the peak position obtained by the PL measurement.
Journal Article•
TL;DR: In this paper, the authors investigated the temperature dependence of the width and energy of excitons by electroabsorption and calculated the coupling constant (the Huang-Rhys parameter) on the radius of microcrystallites.
Abstract: Exciton-LO-phonon couplings in CdS x Sc 1-x semiconductor microcrystallites (x=0.12±0.05) are investigated by measuring the temperature dependence of the width and energy of excitons by electroabsorption. The LO phonons are shown semiquantitatively to contribute to the experimentally obtained temperaure dependencies of the width and energy of excitons. The dependence of the coupling constant (the Huang-Rhys parameter) on the radius of microcrystallites is calculated for CdSe and GaAs microcrystallites. The phonon confinement effects are considered with "free-standing" and "rigid"-boundary conditions. As for the exciton state, nonparabolicity of the conduction band and the valence-band mixing are considered in order to obtain a precise exciton wave function, which is crucially important in calculating the Huang-Rhys parameter in a microcrystallite. The exciton-confined-optical-phonon interaction Harniltonian is constructed for a microcrystallite. It is found that the Huang-Rhys parameters have a minimum at a radius of 70 A for CdSe and 270 A for GaAs microcrystallites. The size dependence of the Huang-Rhys parameter is also calculated for a microcrystallite with an extra charge at the spherical-particle center. The lowest (s,S 3/2 ) state in the trapped state is found to have small transition probability and g values of 1 in CdSe (R =30 A) and 0.01 in GaAs? = 100 A). The higher states are found to have larger transition probability and g values of 0.7 in CdSe (R =30 A) and 0.01 in GaAs (R = 100 A). These results suggest that large g values observed experimentally in CdS and CdSe microcrystallites originate from extrinsic effects such as the presence of charged point defects inside the microcrystallite.
TL;DR: In this paper, a conversion from ohmic to rectifying behavior is observed for Au contacts on atomically ordered polar ZnO surfaces following remote, room-temperature oxygen plasma treatment.
Abstract: A conversion from ohmic to rectifying behavior is observed for Au contacts on atomically ordered polar ZnO surfaces following remote, room-temperature oxygen plasma treatment. This transition is accompanied by reduction of the “green” deep level cathodoluminescence emission, suppression of the hydrogen donor-bound exciton photoluminescence and a ∼0.75eV increase in n-type band bending observed via x-ray photoemission. These results demonstrate that the contact type conversion involves more than one mechanism, specifically, removal of the adsorbate-induced accumulation layer plus lowered tunneling due to reduction of near-surface donor density and defect-assisted hopping transport.
TL;DR: In this paper, the photoluminescence (PL) spectra revealed an acceptor bound exciton peak at 3.355 eV and a conduction band to the acceptor transition caused by a phosphorus related level at 3,310 eV.
Abstract: Phosphorus-doped p-type ZnO thin films were grown on sapphire by radio-frequency magnetron sputtering. The photoluminescence (PL) spectra revealed an acceptor bound exciton peak at 3.355 eV and a conduction band to the acceptor transition caused by a phosphorus related level at 3.310 eV. A study of the dependence of the excitation laser power density and temperature on the characteristics of the PL spectra suggests that the emission lines at 3.310 and 3.241 eV can be attributed to a conduction band to the phosphorus-related acceptor transition and a donor to the acceptor pair transition, respectively. The acceptor energy level of the phosphorus dopant was estimated to be located 127 meV above the valence band.
TL;DR: In this paper, two-photon excitation spectroscopy was used to measure exciton binding energies, as well as band-gap energies, in a range of individual species of semiconducting carbon nanotubes.
Abstract: The optical transitions of semiconducting carbon nanotubes have been ascribed to excitons. Here we use two-photon excitation spectroscopy to measure exciton binding energies, as well as band-gap energies, in a range of individual species of semiconducting SWNTs. Exciton binding energies are large and vary inversely with nanotube diameter, as predicted by theory. Band-gap energies are significantly blue-shifted from values predicted by tight-binding calculations.
TL;DR: In this article, the authors proposed an ideal electron acceptor for polymeric solar cells that exhibits high electron affinity and high electrical conductivity in the form of quantum dots and single wall carbon nanotubes (SWNTs).
TL;DR: In this article, the interaction between O 2 and silicon nanocrystals was explored, which can be employed in the photosynthesis of singlet oxygen, and it was shown that nanoscale Si has entirely new properties owing to morphological and quantum size effects, i.e., large accessible surface areas and excitons of variable energies.
Abstract: Molecular oxygen plays an important role in many of the chemical reactions involved in the synthesis of biological life. In this review, we explore the interaction between O 2 and silicon nanocrystals, which can be employed in the photosynthesis of singlet oxygen. We demonstrate that nanoscale Si has entirely new properties owing to morphological and quantum size effects, i.e., large accessible surface areas and excitons of variable energies and with well-defined spin structures. These features result in new emerging functionality for nanoscale silicon: it is a very efficient spin-flip activator of O 2 , and therefore, a chemically and biologically active material. This whole effect is based on energy transfer from long-lived electronic excitations confined in Si nanocrystals to surrounding O 2 via the exchange of single electrons of opposite spin, thus enabling the spin-flip activation of O 2 . Further, we discuss the implications of these findings for physics, chemistry, biology, and medicine.
TL;DR: Frequency-resolved femtosecond transient absorption spectra and kinetics measured by optical excitation of the second and first electronic transitions of the (8,3) single-walled carbon nanotube species reveal a unique mutual response between these transitions.
Abstract: Frequency-resolved femtosecond transient absorption spectra and kinetics measured by optical excitation of the second and first electronic transitions of the (8,3) single-walled carbon nanotube species reveal a unique mutual response between these transitions. Based on the analysis of the spectra, kinetics, and their distinct amplitude dependence on the pump intensity observed at these transitions, we conclude that these observations originate from both the excitonic origin of the spectrum and nonlinear exciton annihilation.
TL;DR: In this article, the generation and decay dynamics of charges and excitons in a model polymer semiconductor (MEH-PPV) in solution and drop-cast thin films, by recording the sub-ps transient complex conductivity using THz time-domain spectroscopy.
Abstract: We compare the generation and decay dynamics of charges and excitons in a model polymer semiconductor (MEH-PPV) in solution and drop-cast thin films, by recording the sub-ps transient complex conductivity using THz time-domain spectroscopy. The results show that the quantum efficiency of charge generation is two orders of magnitude smaller in solution (~10–5) than in the solid film (~10–3). The proximity of neighboring chains in the films apparently facilitates (hot) exciton dissociation, presumably by allowing the electron and hole to separate on different polymer strands. For both samples, photoexcitation leads to the predominant formation of bound charge pairs (excitons) that can be detected through their polarizability. Surprisingly, the polarizability per absorbed photon is a factor of 3 larger in solution than in the film, suggesting that interchain interactions in the film do not result in a substantial delocalization of the exciton wave function.
TL;DR: In this paper, the authors used time-resolved luminescence spectroscopy to investigate exciton diffusion in thin films of poly($p$-phenylene vinylene) (PPV)-based derivatives.
Abstract: Time-resolved luminescence spectroscopy has been used to investigate exciton diffusion in thin films of poly($p$-phenylene vinylene) (PPV)--based derivatives. Due to chemical modifications the PPV derivatives differ by three orders of magnitude in charge carrier mobility as a result of a reduced energetic disorder. From the photoluminescence decay curves of PPV/fullerene heterostructures, the exciton diffusion coefficient was found to increase by one order of magnitude with decreasing disorder. This increase in the diffusion coefficient is compensated by a decrease of the exciton lifetime, leading to an exciton diffusion length of $5--6\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$ for the various PPV derivatives.