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We report the synthesis of tungsten sulfide (WS2) films using RF‐magnetron sputtering at different RF powers. X‐ray diffraction (XRD) data confirm the hexagonal crystal structure of WS2 with an average crystallite size of ∼44.54 Å. With increased RF power, the preferred orientation of WS2 crystallites shifts from (002) to (100). Linear sweep voltammetry (LSV) was used to assess the Photoelectrochemical (PEC) activity of WS2 films. The film deposited at 150 W demonstrated the highest photocurrent density of 5.44 mA/cm2. The 150 W film also showed a lower Tafel slope of ∼0.374 V/decade, indicating superior PEC activity. Mott Schottky's (MS) analysis revealed a notable shift in the flat band potential towards the negative side, suggesting a shifting of the Fermi level towards the conduction band. WS2 film grown at 150 W demonstrated a majority charge carrier density of 6.2×1021 cm−3 and a depletion layer width of 1.54 nm. The observed low charge transfer resistance of 155 Ω contributed to the enhanced PEC activity with a relaxation time constant of 37 ms. These properties suggest that WS2 can be suitable for PEC water splitting. [ABSTRACT FROM AUTHOR]

Layered bismuth triiodide (BiI 3 ) is a 2D material that has emerged as an ideal choice for optical sensors. Although BiI 3 has been prepared using vacuum-based deposition techniques, there is a dearth of research studies on synthesizing this material using chemical route. The present work uses a facile spin coating method with varying rotation speeds (rpm) to fabricate BiI 3 material thin films for photodetection applications. The structural, optical, and morphological study of BiI 3 thin films prepared at 3000-6000 rpm were investigated. XRD analysis indicates formation of BiI 3 films and revealed that BiI 3 has a rhombohedral crystal structure. FESEM analysis showed that BiI 3 films prepared at different rpm are homogeneous, dense, and free from cracks, flaws, and protrusions. In addition, films show an island-like morphology with grain boundaries having different grain sizes, micro gaps, and the evolution of the granular morphology of BiI 3 particles. The UV spectroscopy and photoluminescence analysis revealed that BiI 3 films strongly absorb light in the visible region of spectra with a high absorption coefficient of ∼10 4 cm -1 , have an optical band gap of ∼1.51 eV. A photodetector was realised using fabricated BiI 3 film obtained at an optimum spin speed of 4000 rpm. It showed rapid rise and decay times of 0.4 s and 0.5 s, a responsivity of ∼100 μA W -1 , external quantum efficiency of 2.1 × 10 -4 %, and detectivity of ∼3.69 × 10 6 Jones at a bias voltage of 0 V. Our results point towards a new direction for layered 2D BiI 3 materials for the application in self-biased photodetectors., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

ZrBi 2 Se 6 nanoflower-like morphology was successfully prepared using a solvothermal method, followed by a quenching process for photoelectrochemical water splitting applications. The formation of ZrBi 2 Se 6 was confirmed by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The estimated value of work function and band gap were found to be 5.5 and 2.26 eV measured using diffuse reflection spectroscopy and ultraviolet photoelectron spectroscopy, suggesting the potential candidate for water splitting. The highest current density of 9.7 μA/cm 2 has been observed for the ZrBi 2 Se 6 photoanode for the applied potential of 0.5 V vs SCE. The flat-band potential value was -0.46 V, and the 1.85 nm width of the depletion region is estimated from the Mott-Schottky (MS) analysis. It also reveals that the charge carrier density for the ZrBi 2 Se 6 nanoflowers is 4.8 × 10 15 cm -3 . The negative slope of the MS plot indicates that ZrBi 2 Se 6 is a p-type semiconductor. It was observed that ZrBi 2 Se 6 nanoflowers had a high charge transfer resistance of ∼730 kΩ and equivalent capacitance of ∼40 nF calculated using electrochemical impedance spectroscopy (EIS) measurements. Using chronoamperometry, the estimated rise time and decay time were 50 ms and 0.25 s, respectively, which reveals the fast photocurrent response and excellent PEC performance of the ZrBi 2 Se 6 photoanode. Furthermore, an attempt has been made to explain the PEC activity of ZrBi 2 Se 6 nanoflowers using an energy band diagram. Thus, the initial results on ZrBi 2 Se 6 nanoflowers appear promising for the PEC activity toward water splitting., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Ternary Cu 2 SnS 3 (CTS) is an attractive nontoxic and earth-abundant absorber material with suitable optoelectronic properties for cost-effective photoelectrochemical applications. Herein, we report the synthesis of high-quality CTS nanoparticles (NPs) using a low-cost facile hot injection route, which is a very simple and nontoxic synthesis method. The structural, morphological, optoelectronic, and photoelectrochemical (PEC) properties and heterojunction band alignment of the as-synthesized CTS NPs have been systematically characterized using various state-of-the-art experimental techniques and atomistic first-principles density functional theory (DFT) calculations. The phase-pure CTS NPs confirmed by X-ray diffraction (XRD) and Raman spectroscopy analyses have an optical band gap of 1.1 eV and exhibit a random distribution of uniform spherical particles with size of approximately 15-25 nm as determined from high-resolution transmission electron microscopy (HR-TEM) images. The CTS photocathode exhibits excellent photoelectrochemical properties with PCE of 0.55% (fill factor (FF) = 0.26 and open circuit voltage (Voc) = 0.54 V) and photocurrent density of -3.95 mA/cm 2 under AM 1.5 illumination (100 mW/cm 2 ). Additionally, the PEC activities of CdS and ZnS NPs are investigated as possible photoanodes to create a heterojunction with CTS to enhance the PEC activity. CdS is demonstrated to exhibit a higher current density than ZnS, indicating that it is a better photoanode material to form a heterojunction with CTS. Consistently, we predict a staggered type-II band alignment at the CTS/CdS interface with a small conduction band offset (CBO) of 0.08 eV compared to a straddling type-I band alignment at the CTS/ZnS interface with a CBO of 0.29 eV. The observed small CBO at the type-II band aligned CTS/CdS interface points to efficient charge carrier separation and transport across the interface, which are necessary to achieve enhanced PEC activity. The facile CTS synthesis, PEC measurements, and heterojunction band alignment results provide a promising approach for fabricating next-generation Cu-based light-absorbing materials for efficient photoelectrochemical applications., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)