Semiconductors group

Abstract:

Efficient charge-carrier transport is critical to the success of emergent semiconductors in photovoltaic applications. So far, disorder has been considered detrimental for charge-carrier transport, lowering mobilities and causing fast recombination. This work demonstrates that, when properly engineered, cation disorder in a multinary chalcogenide semiconductor can considerably enhance the charge-carrier mobility and extend the charge-carrier lifetime. Here, the properties of AgBiS₂ nanocrystals (NCs) are explored where Ag and Bi cation-ordering can be modified via thermal-annealing. Local Ag-rich and Bi-rich domains formed during hot-injection synthesis are transformed to induce homogeneous disorder (random Ag-Bi distribution). Such cation engineering results in a six-fold increase in the charge-carrier mobility, reaching ∼2.7 cm²V⁻¹s⁻¹ in AgBiS₂ NC thin films. It is further demonstrated that homogeneous cation disorder reduces charge-carrier localisation, a hallmark of charge-carrier transport recently observed in silver-bismuth semiconductors. This work proposes that cation-disorder engineering flattens the disordered electronic landscape, removing tail states that would otherwise exacerbate Anderson localisation of small polaronic states. Together, these findings unravel how cation-disorder engineering in multinary semiconductors can enhance the efficiency of renewable energy applications.

Abstract:

Topological materials have rapidly gained interest as contenders for development of coherent, controllable terahertz emitters. Possessing Weyl nodes either at the surface or within the bulk, they host spin-polarised, helicity-dependent currents that offer possibility to control the emitted THz pulse by changing the polarization of the optical pulses generating the radiation. Here, we show that upon near-infrared excitation at oblique incidence, multi-cycle pulses are generated with a narrow bandwidth of ∼0.4 THz for cadmium arsenide bulk crystals and nanowire ensembles. Both the bandwidth and peak emission frequency of the generated THz radiation can be tuned by respectively varying the photon helicity and angle of incidence of the photoexcitation light.

Abstract:

Harnessing nonequilibrium hot carriers from plasmonic metal nanostructures constitutes a vibrant research field with the potential to control photochemical reactions, particularly for solar fuel generation. However, a comprehensive understanding of the interplay of plasmonic hot-carrier-driven processes in metal/semiconducting heterostructures has remained elusive. In this work, we reveal the complex interdependence among plasmon excitation, hot-carrier generation, transport, and interfacial collection in plasmonic photocatalytic devices, uniquely determining the charge injection efficiency at the solid/liquid interface. Measuring the internal quantum efficiency of ultrathin (14–33 nm) single-crystalline plasmonic gold (Au) nanoantenna arrays on titanium dioxide substrates, we find that the performance of the device is limited by hot hole collection at the metal/electrolyte interface. Our solid- and liquid-state experimental approach, combined with ab initio simulations, demonstrates more efficient collection of high-energy d-band holes traveling in the [111] orientation, enhancing oxidation reactions on {111} surfaces. These findings establish new guidelines for optimizing plasmonic photocatalytic systems and optoelectronic devices

Abstract:

Metal halide perovskite semiconductors have shown significant potential for use in photovoltaic (PV) devices. While fabrication of perovskite thin films can be achieved through a variety of techniques, thermal vapor deposition is particularly promising, allowing for high-throughput fabrication. However, the ability to control the nucleation and growth of these materials, particularly at the charge-transport layer/perovskite interface, is critical to unlocking the full potential of vapor-deposited perovskite PV. In this study, we explore the use of a templating layer to control the growth of coevaporated perovskite films and find that such templating leads to highly oriented films with identical morphology, crystal structure, and optoelectronic properties independent of the underlying layers. Solar cells incorporating templated FA0.9Cs0.1PbI3–xClx show marked improvements with steady-state power conversion efficiency over 19.8%. Our findings provide a straightforward and reproducible method of controlling the charge-transport layer/coevaporated perovskite interface, further clearing the path toward large-scale fabrication of efficient PV devices.