Coherence Length of Excitons in a Semiconductor Quantum Well

We report on the first experimental determination of the coherence length of excitons in semiconductors using the combination of spatially resolved photoluminescence with phonon sideband spectroscopy. The coherence length of excitons in ZnSe quantum wells is determined to be 300 ~ 400 nm, about 25 ~ 30 times the exciton de Broglie wavelength. With increasing exciton kinetic energy, the coherence length decreases slowly. The discrepancy between the coherence lengths measured and calculated by only considering the acoustic phonon scattering suggests an important influence of static disorder.Comment: 4 Pages, 4 figure

Impedance spectroscopy of Sb₂Se₃ photovoltaics consisting of (Sb₄Se₆)_<i>n</i> nanoribbons under light illumination.

Sb2Se3, consisting of one-dimensional (Sb4Se6)n nanoribbons has drawn attention as an intriguing light absorber from the photovoltaics (PVs) research community. However, further research is required on the performance-limiting factors in Sb2Se3 PVs. In this study, we investigated the charge carrier behavior in Sb2Se3 PVs by impedance spectroscopy (IS) under light illumination. (Sb4Se6)n nanoribbons with two different orientations were used to investigate the effect of crystal orientation on the device performance. Regardless of the (Sb4Se6)n orientation, negative capacitance was observed at forward bias, representing a recombination pathway at the TiO2/Sb2Se3 interface. A comparison of the recombination resistances and lifetimes of two different Sb2Se3 PVs showed that a better interface could be formed by placing the (Sb4Se6)n ribbons parallel to the TiO2 layer. Based on these observations, an ideal structure of the Sb2Se3/TiO2 interface is proposed, which will enhance the performance of Sb2Se3 PVs toward its theoretical limit

Exploring excited states of Pt(ii) diimine catecholates for photoinduced charge separation

The intense absorption in the red part of the visible range, and the presence of a lowest charge-transfer excited state, render Platinum(II) diimine catecholates potentially promising candidates for light-driven applications. Here, we test their potential as sensitisers in dye-sensitised solar cells and apply, for the first time, the sensitive method of photoacoustic calorimetry (PAC) to determine the efficiency of electron injection in the semiconductor from a photoexcited Pt(II) complex. Pt(II) catecholates containing 2,2′-bipyridine-4,4′-di-carboxylic acid (dcbpy) have been prepared from their parent iso-propyl ester derivatives, complexes of 2,2′-bipyridine-4,4′-di-C(O)OiPr, (COOiPr)2bpy, and their photophysical and electrochemical properties studied. Modifying diimine Pt(II) catecholates with carboxylic acid functionality has allowed for the anchoring of these complexes to thin film TiO2, where steric bulk of the complexes (3,5-ditBu-catechol vs. catechol) has been found to significantly influence the extent of monolayer surface coverage. Dye-sensitised solar cells using Pt(dcbpy)(tBu2Cat), 1a, and Pt(dcbpy)(pCat), 2a, as sensitisers, have been assembled, and photovoltaic measurements performed. The observed low, 0.02–0.07%, device efficiency of such DSSCs is attributed at least in part to the short excited state lifetime of the sensitisers, inherent to this class of complexes. The lifetime of the charge-transfer ML/LLCT excited state in Pt((COOiPr)2bpy)(3,5-di-tBu-catechol) was determined as 250 ps by picosecond time-resolved infrared spectroscopy, TRIR. The measured increase in device efficiency for 2a over 1a is consistent with a similar increase in the quantum yield of charge separation (where the complex acts as a donor and the semiconductor as an acceptor) determined by PAC, and is also proportional to the increased surface loading achieved with 2a. It is concluded that the relative efficiency of devices sensitised with these particular Pt(II) species is governed by the degree of surface coverage. Overall, this work demonstrates the use of Pt(diimine)(catecholate) complexes as potential photosensitizers in solar cells, and the first application of photoacoustic calorimetry to Pt(II) complexes in general

Spatio-temporal dynamics of quantum-well excitons

We investigate the lateral transport of excitons in ZnSe quantum wells by using time-resolved micro-photoluminescence enhanced by the introduction of a solid immersion lens. The spatial and temporal resolutions are 200 nm and 5 ps, respectively. Strong deviation from classical diffusion is observed up to 400 ps. This feature is attributed to the hot-exciton effects, consistent with previous experiments under cw excitation. The coupled transport-relaxation process of hot excitons is modelled by Monte Carlo simulation. We prove that two basic assumptions typically accepted in photoluminescence investigations on excitonic transport, namely (i) the classical diffusion model as well as (ii) the equivalence between the temporal and spatial evolution of the exciton population and of the measured photoluminescence, are not valid for low-temperature experiments.Comment: 8 pages, 6 figure

Energy and Hole Transfer between Dyes Attached to Titania in Cosensitized Dye-Sensitized Solar Cells

Cosensitization of broadly absorbing ruthenium metal complex dyes with highly absorptive near-infrared (NIR) organic dyes is a clear pathway to increase near-infrared light harvesting in liquid- based dye-sensitized solar cells (DSCs). In cosensitized DSCs, dyes are intimately mixed, and intermolecular charge and energy transfer processes play an important role in device performance. Here, we demonstrate that an organic NIR dye incapable of hole regeneration is able to produce photocurrent via intermolecular energy transfer with an average excitation transfer efficiency of over 25% when cosensitized with a metal complex sensitizing dye (SD). We also show that intermolecular hole transfer from the SD to NIR dye is a competitive process with dye regeneration, reducing the internal quantum efficiency and the electron lifetime of the DSC. This work demonstrates the general feasibility of using energy transfer to boost light harvesting from 700 to 800 nm and also highlights a key challenge for developing highly efficient cosensitized dye-sensitized solar cells