Recombination Dynamics in Thin-film Photovoltaic Materials via Time-resolved Microwave Conductivity

A method for investigating recombination dynamics of photo-induced charge carriers in thin film semiconductors, specifically in photovoltaic materials ...

ARC Centre of Excellence in Exciton Science

University of New South Wales

Organic semiconductors offer expansive grounds to explore fundamental questions of spin physics in condensed matter systems. With the emergence of organic spintronics and renewed interest in magnetoresistive effects, which exploit the electron spin degree of freedom to encode and transmit information, there is much need to illuminate the underlying properties of spins in molecular electronic materials. For example, one may wish to identify over what length of time a spin maintains its orientation with respect to an external reference field. In addition, it is crucial to understand how adjacent spins arising, for example, in electrostatically coupled charge-carrier pairs, interact with each other. A periodic perturbation of the field may cause the spins to precess or oscillate, akin to a spinning top experiencing a torque. The quantum mechanical characteristic of the spin is then defined as the coherence time, the time over which an oscillating spin, or spin pair, maintains a fixed phase with respect to the driving field. Electron spins in organic semiconductors provide a remarkable route to performing "hands-on" quantum mechanics since permutation symmetries are controlled directly. Herein, we review some of the recent advances in organic spintronics and organic magnetoresistance, and offer an introductory description of the concept of pulsed, electrically detected magnetic resonance as a technique to manipulate and thus characterize the fundamental properties of electron spins. Spin-dependent dissociation and recombination allow the observation of coherent spin motion in a working device, such as an organic light-emitting diode. Remarkably, it is possible to distinguish between electron and hole spin resonances. The ubiquitous presence of hydrogen nuclei gives rise to strong hyperfine interactions, which appear to provide the basis for many of the magnetoresistive effects observed in these materials. Since hyperfine coupling causes quantum spin beating in electron-hole pairs, an extraordinarily sensitive probe for hyperfine fields in such pairs is given.

Coherent spin manipulation in molecular semiconductors: getting a handle on organic spintronics.

An appealing avenue for organic spintronics lies in direct coherent control of the spin population by means of pulsed electron spin resonance techniques. Whereas previous work has focused on the electrical detection of coherent spin dynamics, we demonstrate here the equivalence of an all-optical approach, allowing us to explore the influence of materials chemistry on the spin dynamics. We show that deuteration of the conjugated polymer side groups weakens the local hyperfine fields experienced by electron-hole pairs, thereby lowering the threshold for the resonant radiation intensity at which coherent coupling and spin beating occur. The technique is exquisitively sensitive to previously obscured material properties and offers a route to quantifying and tuning hyperfine fields in organic semiconductors.

Tuning hyperfine fields in conjugated polymers for coherent organic spintronics.

Quantum computers hold the promise of massive performance enhancements across a range of applications, from cryptography and databases to revolutionary scientific simulation tools. Such computers would make use of the same quantum mechanical phenomena that pose limitations on the continued shrinking of conventional information processing devices. Many of the key requirements for quantum computing differ markedly from those of conventional computers. However, silicon, which plays a central part in conventional information processing, has many properties that make it a superb platform around which to build a quantum computer.

Embracing the quantum limit in silicon computing.

Vascular dysfunction that accompanies obesity and insulin resistance may be mediated by lipid metabolites. We sought to determine if vascular ceramide leads to arterial dysfunction and to elucidate the underlying mechanisms. Pharmacological inhibition of de novo ceramide synthesis, using the Ser palmitoyl transferase inhibitor myriocin, and heterozygous deletion of dihydroceramide desaturase prevented vascular dysfunction and hypertension in mice after high-fat feeding. These findings were recapitulated in isolated arteries in vitro, confirming that ceramide impairs endothelium-dependent vasorelaxation in a tissue-autonomous manner. Studies in endothelial cells reveal that de novo ceramide biosynthesis induced protein phosphatase 2A (PP2A) association directly with the endothelial nitric oxide synthase (eNOS)/Akt/Hsp90 complex that was concurrent with decreased basal and agonist-stimulated eNOS phosphorylation. PP2A attenuates eNOS phosphorylation by preventing phosphorylation of the pool of Akt that colocalizes with eNOS and by dephosphorylating eNOS. Ceramide decreased the association between PP2A and the predominantly cytosolic inhibitor 2 of PP2A. We conclude that ceramide mediates obesity-related vascular dysfunction by a mechanism that involves PP2A-mediated disruption of the eNOS/Akt/Hsp90 signaling complex. These results provide important insight into a pathway that represents a novel target for reversing obesity-related vascular dysfunction.

Ceramide mediates vascular dysfunction in diet-induced obesity by PP2A-mediated dephosphorylation of the eNOS-Akt complex.

Physics. Nuclear-spin quantum memory poised to take the lead.

An agnostic approach.

Molecular materials afford abundant flexibility in the tunability of physical and electronic properties. As such, they are ideally suited to engineering low-cost, flexible, light-harvesting materials that break away from the single-threshold paradigm. Single-threshold solar cells are capable of harvesting a maximum of 33.7% of incident sunlight, whereas two-threshold cells are capable of energy harvesting efficiencies exceeding 45%. In this Perspective, we provide the theoretical background with which upper efficiency limits for various multiple-threshold solar cell architectures may be calculated and review and discuss various reports that employ processes such as triplet-triplet annihilation and singlet fission in multiple-threshold devices comprised of molecular materials.

Beyond Shockley-Queisser: Molecular Approaches to High-Efficiency Photovoltaics.

Photochemical upconversion via triplet-triplet annihilation is a promising technology for improving the efficiency of photovoltaic devices. Previous studies have shown that the efficiency of upconversion depends largely on two rate constants intrinsic to the emitting species. Here, we report that one of these rate constants can be altered by deuteration, leading to enhanced upconversion efficiency. For perylene, deuteration decreases the first order decay rate constant by 16 ± 9% at 298 K, which increases the linear upconversion response by 45 ± 21% in the low excitation regime.

Deuteration of Perylene Enhances Photochemical Upconversion Efficiency.

Elucidating the decay mechanisms of photoexcited charge carriers is key to improving the efficiency of solar cells based on organo-lead halide perovskites. Here we investigate the spectral dependence (via above-, inter- and sub-bandgap optical excitations) of direct and trap-mediated decay processes in CH3NH3PbI3 using time resolved microwave conductivity (TRMC). We find that the total end-of-pulse mobility is excitation wavelength dependent - the mobility is maximized (172 cm(2) V(-1) s(-1)) when charge carriers are excited by near bandgap light (780 nm) in the low charge carrier density regime (10(9) photons per cm(2)), and is lower for above- and sub-bandgap excitations. Direct recombination is found to occur on the 100-400 ns timescale across excitation wavelengths near and above the bandgap, whereas indirect recombination processes displayed distinct behaviour following above- and sub-bandgap excitations, suggesting the influence of different trap distributions on recombination dynamics.

Dane R. McCamey

ARC Centre of Excellence in Exciton Science

Recombination Dynamics in Thin-film Photovoltaic Materials via Time-resolved Microwave Conductivity