Structural, Optical, Photoelectrochemical, and Electronic Properties of the Photocathode CuS and the Efficient CuS/CdS Heterojunction.

We report a facile synthesis of CuS and CdS nanoparticles using a cheap solution-processed chemical bath method forming heterogeneous nucleation. The optical, structural, photoelectrochemical (PEC), and electronic properties are studied by implementing relevant experimental techniques. The estimated optical band gap of ∼2.10 eV of CuS designates potential application in inexpensive photocatalysis and solar cells. Further, the valence band and conduction band positions of CuS and CdS are evaluated using cyclic voltammetry curves. Narrow conduction and valence band offset potentials measured at the CuS/CdS heterojunction are encouraging factors for the PEC application. The electronic properties are supported by the current density vs potential plots (J-V) with an improved short-circuit current density of 0.71 mA cm-2 for the heterojunction compared to bare CuS showing 0.15 µA cm-2. The determined PCE of the heterojunction CuS/CdS is 0.65%.

Ternary Cu2SnS3: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment.

Ternary Cu2SnS3 (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/cm2 under AM 1.5 illumination (100 mW/cm2). 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.