Novel Au/Cu2NiSnS4 Nano-Heterostructure: Synthesis, Structure, Heterojunction Band Offset and Alignment, and Interfacial Charge Transfer Dynamics.

Considering the importance of physics and chemistry at material interfaces, we have explored the coupling of multinary chalcogenide semiconductor Cu2NiSnS4 nanoparticles (CNTS NPs) for the first time with the noble metal (Au) to form Au-CNTS nano-heterostructures (NHSs). The Au-CNTS NHSs is synthesized by a simple facile hot injection method. Synergistic experimental and theoretical approaches are employed to characterize the structural, optical, and electrical properties of the Au-CNTS NHSs. The absorption spectra demonstrate enhanced and broadened optical absorption in the ultraviolet-visible-near-infrared (UV-Vis-NIR) region, which is corroborated by cyclic voltammetry (CV) readings. CV measurements show type II staggered band alignment, with a conduction band offset (CBO) of 0.21 and 0.23 eV at the Au-CNTS/CdS and CNTS/CdS interface, respectively. Complementary first-principles density functional theory (DFT) calculations predict the formation of a stable Au-CNTS NHSs, with the Au nanoparticle transferring its electrons to the CNTS. Moreover, our interface analysis using ultrafast transient absorption experiments demonstrate that the Au-CNTS NHSs facilitates efficient transport and separation of photoexcited charge carriers when compared to pristine CNTS. The transient measurements further reveal a plasmonic electronic transfer from the Au nanoparticle to CNTS. Our advanced analysis and findings will prompt investigations into new functional materials and their photo/electrocatalysis and optoelectronic device applications in the future.

Fabrication of ZnO Scaffolded CdS Nanostructured Photoanodes with Enhanced Photoelectrochemical Water Splitting Activity under Visible Light.

CdS, characterized by its comparatively narrow energy band gap (∼2.4 eV), is an appropriate material for prospective use as a photoanode in photoelectrochemical water splitting. Regrettably, it encounters several obstacles for practical and large-scale applications, including issues such as bulk carrier recombination and diminished conductivity. Here, we have tried to address these challenges by fabricating a novel photoelectrode (ZnO/CdS) composed of one-dimensional ZnO nanorods (NRs) decorated with two-dimensional CdS nanosheets (NSs). A facile two-step chemical method comprising electrodeposition along with chemical bath deposition is employed to synthesize the ZnO NRs, CdS NSs, and ZnO/CdS nanostructures. The prepared nanostructures have been investigated by UV-visible absorption spectroscopy, X-ray diffraction, Raman spectroscopy, transmission electron microscopy (TEM), and scanning electron microscopy. The fabricated ZnO/CdS nanostructures have shown enhanced photoelectrochemical properties due to the improvement of the semiconductor junction surface area and thereby enhanced visible light absorption. The incorporation of CdS NSs has been further found to promote the rate of the charge separation and transfer process. Subsequently, the fabricated ZnO/CdS photoelectrodes achieved a photocurrent conversion efficiency 3 times higher than that of a planar ZnO NR photoanode and showed excellent performance under visible light irradiation. The highest applied bias photon-to-current conversion efficiency (% ABPE) of about ∼0.63% has been obtained for the sample with thicker CdS NSs on ZnO NRs with a photocurrent density of ∼1.87 mA/cm2 under AM 1.5 G illumination. The newly synthesized nanostructures further demonstrate that the full photovoltaic capacity of nanomaterials is yet to be exhausted.

Interfacial band offset engineering with barium-doping towards enhanced performance of all inorganic CsPbI2Br perovskite solar cells.

This study investigates the incorporation of Ba2+ at a low concentration into CsPbI2Br, resulting in the formation of mixed CsPb1-xBaxI2Br perovskite films. Photovoltaic devices utilizing these Ba-doped CsPbI2Br (Ba-CsPbI2Br) perovskite films achieved a higher stabilized power conversion efficiency of 14.07% compared to 11.60% for pure CsPbI2Br films. First-principles density functional theory calculations indicate that the improved device performance can be attributed to the efficient transport of conduction electrons across the interface between Ba-CsPbI2Br and the TiO2 electron transporting layer (ETL). The Ba-CsPbI2Br/TiO2 interface exhibits a type-II staggered band alignment with a smaller conduction band offset (CBO) of 0.25 eV, in contrast to the CsPbI2Br/TiO2 interface with a CBO of 0.48 eV. The reduced CBO at the Ba-CsPbI2Br/TiO2 interface diminishes the barrier for conduction electrons to transfer from the Ba-CsPbI2Br layer to the TiO2 layer, facilitating efficient charge transport.