Murad J. Y. Tayebjee

Photochemical Upconversion Enhanced Solar Cells: Effect of a Back Reflector

Photochemical upconversion is applied to a hydrogenated amorphous silicon solar cell in the presence of a back-scattering layer. A custom-synthesized porphyrin was utilized as the sensitizer species, with rubrene as the emitter. Under a bias of 24 suns, a peak external quantum efficiency (EQE) enhancement of ~2 % was observed at a wavelength of 720 nm. Without the scattering layer, the EQE enhancement was half this value, indicating that the effect of the back-scatterer is to double the efficacy of the upconverting device. The results represent an upconversion figure of merit of 3.5 × 10–4 mA cm–2 sun–2, which is the highest reported to date.

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

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.

InGaAs/GaAsP quantum wells for hot carrier solar cells

Hot carrier solar cells have a fundamental efficiency limit well in excess of single junction devices. Developing a hot carrier absorber material, which exhibits sufficiently slow carrier cooling to maintain a hot carrier population under realistic levels of solar concentration is a key challenge in developing real-world hot carrier devices. We propose strain-balanced In0.25GaAs/GaAsP0.33 quantum wells as a suitable absorber material and present continuous-wave photoluminescence spectroscopy of this structure. Samples were optimised with deep wells and the GaAs surface buffer layer was reduced in thickness to maximise photon absorption in the well region. The effect of well thickness on carrier distribution temperature was also investigated. An enhanced hot carrier effect was observed in the optimised structures and a hot carrier distribution temperature was measured in the thick well (14 nm) sample under photon flux density equivalent to 1000 Suns concentration.

Hot carrier dynamics in InGaAs/GaAsP quantum well solar cells

A hot carrier solar cell is a device with a steady-state carrier population which is described by a higher temperature than the surrounding lattice. Thermalisation loss is reduced in such a device, offering the potential for substantial efficiency advantages over single junction solar cells. Despite clear efficiency benefits no real world device has ever been developed, partly because of the difficulty of developing a suitable absorber material with sufficiently limited interaction between excited carriers and lattice phonons. This study evaluates the suitability of strain balanced InGaAs/GaAsP quantum well structures as hot carrier absorbers. Ultrafast time resolved photoluminescence (TRPL) spectroscopy measurements are presented which demonstrate hot carrier populations beyond 2ns after excitation in a deep well sample. Continuous wave photoluminescence (CWPL) spectroscopy was used to compare steady-state carrier populations in deep and shallow well samples. In both cases hot distributions were observed under photon flux density greater than 10,000 Suns equivalent. Increasing incident photon flux density was shown to increase carrier distribution temperature, suggesting that the hot carrier effect might be enhanced in a multiple QW structure with better well region absorption. It was also found that the deep well sample achieved significantly higher carrier distribution temperatures than the shallow well sample, demonstrating that increasing quantum confinement further inhibits thermalisation pathways. This study provides a guide to the development of hot carrier solar cells as it indicates deep multiple quantum well samples might exhibit an enhanced hot carrier effect. Strain Balanced InGaAs/GaAsP is a particularly suitable material system for growing this type of structure, making it an exciting prospect for the development of a hot carrier absorber.

Tuning Singlet Fission in π-Bridge-π Chromophores

We have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the π-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet-triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF.

The efficiency limit of solar cells with molecular absorbers: A master equation approach

A master equation approach to the limiting efficiencies of solar cells with molecular absorbers is presented. A number of model absorbers are analyzed that possess identical absorption spectra, but with differing numbers of electronic excited states. The Shockley–Queisser limit is reproduced for a molecule resembling a semiconductor, with an infinity of electronic levels in the excited state manifold. However, when only a few electronic states contribute to the absorption spectrum, the limiting efficiency is reduced. In the extreme case, where only a single electronic excited state participates in the absorption spectrum, the efficiency limit is 28.9%. At high energy thresholds, built-in thermal up-conversion results in solar cells with efficiencies exceeding the Shockley–Queisser curve. The analysis is applicable to any single threshold photovoltaic device, including those based on semiconductor, polymer, and small molecule absorbers.

Hot carrier solar cells: Challenges and recent progress

The limiting efficiency on the conversion efficiency of terrestrial global sunlight is not circa 31%, as commonly assumed, but 74%. To reach the lowest possible costs and hence to attain its intrinsic potential as a major source of future sustainable energy supplies, it would appear photovoltaics has to evolve to devices targeting the latter efficiency rather than the former. The hot carrier solar cell, although presenting substantial device challenges, is arguably the highest efficiency photovoltaic device concept yet suggested and hence worthy of efforts to investigate its practicality. Challenges in the implementation of hot carrier cells are identified and progress in overcoming these are discussed.

Extended hot carrier lifetimes observed in bulk In0.265±0.02Ga0.735N under high-density photoexcitation

We have investigated the ultrafast carrier dynamics in a 1 μm bulk In0.265Ga0.735N thin film grown using energetic neutral atom-beam lithography/epitaxy molecular beam epitaxy. Cathodoluminescence and X-ray diffraction experiments are used to observe the existence of indium-rich domains in the sample. These domains give rise to a second carrier population and bi-exponential carrier cooling is observed with characteristic lifetimes of 1.6 and 14 ps at a carrier density of 1.3 × 1016 cm−3. A combination of band-filling, screening, and hot-phonon effects gives rise to a two-fold enhanced mono-exponential cooling rate of 28 ps at a carrier density of 8.4 × 1018 cm−3. This is the longest carrier thermalization time observed in bulk InGaN alloys to date.

Limitations and design considerations for donor–acceptor systems in luminescent solar concentrators: the effect of coupling-induced red-edge absorption

Luminescent solar concentrators (LSCs) use luminescence and waveguiding to concentrate photons within thin dielectric slabs for use in photovoltaic, lighting, and photobioreactor applications. Donor–acceptor systems of organic chromophores are widely used in LSCs to broaden the sunlight absorption range and attempt to reduce loss-inducing reabsorption by the emitting chromophore. We use raytrace simulations across a large parameter space to model the performance of LSCs containing two novel donor–acceptor trimers based on the perylene moiety. We find that under certain conditions, trimers outperform single-dye LSCs as expected. However, at higher concentrations, a slight increase in red-edge absorption by the trimers increases reabsorption and has a deleterious effect on LSC performance. This underscores the large effect that even small changes in the red edge can have, and may discourage the use of donor–acceptor schemes with high interchromophore coupling that promotes red-edge absorption. Finally, we show that for a LSC-PV pair, selecting a PV cell that is well-matched with the LSC emission spectrum has a large effect on the flux gain of the system, and that the systems studied here are well-matched to emerging PV technologies.

A medium-energy photoemission and ab-initio investigation of cubic yttria-stabilised zirconia

Experimental and theoretical investigations into the electronic properties and structure of cubic yttria-stabilized zirconia are presented. Medium-energy x-ray photoemission spectroscopy measurements have been carried out for material with a concentration of 8-9 mol. % yttria. Resonant photoemission spectra are obtained for a range of photon energies that traverse the L2 absorption edge for both zirconium and yttrium. Through correlation with results from density-functional theory (DFT) calculations, based on structural models proposed in the literature, we assign photoemission peaks appearing in the spectra to core lines and Auger transitions. An analysis of the core level features enables the identification of shifts in the core level energies due to different local chemical environments of the constituent atoms. In general, each core line feature can be decomposed into three contributions, with associated energy shifts. Their identification with results of DFT calculations carried out for proposed atomic structures, lends support to these structural models. The experimental results indicate a multi-atom resonant photoemission effect between nearest-neighbour oxygen and yttrium atoms. Near-edge x-ray absorption fine structure spectra for zirconium and yttrium are also presented, which correlate well with calculated Zr- and Y-4d electron partial density-of-states and with Auger electron peak area versus photon energy curve.