Flexible electrodes, particularly paper electrodes modified with polypyrrole, have shown promise in energy-related applications. We have earlier demonstrated the usage of paper electrodes modified with polypyrrole as a flexible and suitable photoanode for photoelectrochemical water splitting (PEC). Further, modification of this electrode system with an appropriate tandem absorber system for solar fuel production is interesting in developing efficient photoanodes. In this study, we study the PEC performance of flexible polypyrrole-based paper photoanodes (PPy-PAs) by decorating them with rGO@Cu2Zn- SnS4 chalcopyrites (rGO@CZTS/PPy-PAs). The lower bandgap (~ 1.5 eV) of the rGO@CZTS/PPy-PAs system allows for efficient visible light absorption, substantially improving PEC water-splitting reactions. The rGO@CZTS/PPy-PAs exhibited an enhanced current density of ~ 13.2 mA/cm2 at 1.23 V vs RHE, ABPE of ~ 1.5%, and a hydrogen evolution rate of 177 μmoles/min/cm2. Overall, rGO@CZTS/PPy-PAs showed 2.1-fold, 1.1-fold, and 1.4-fold enhancement in photocurrent activity over PPy-PAs, CZTS/PPy-PAs, and rGO/PPy-PAs, respectively. The usability of rGO@CZTS/PPy-PAs is established in the form of stable photocurrent for more than 200 min. These findings open new possibilities for developing modified PPy PAs as flexible PEs for efficient solar-driven PEC devices and give directions on improving flexible PEs for flexible and efficient solar-driven PEC systems.

This study reports the effects of H2S gas concentration on the properties of Cu2ZnSnS4(CZTS) thin films. Specifically, sulfurization process with low H2S concentrations of 0.05% and 0.1%, along with 5% H2S gas, was studied. CZTS films were directly synthesized on Mo/Si substrates by chemical bath deposition method using copper sulfate, zinc sulfate heptahydrate, tin chloride dihydrate, and sodium thiosulfate pentahydrate. Smooth CZTS films were grown on substrates at optimized chemical bath deposition condition. The CZTS films sulfurized at low H2S concentrations of 0.05 % and 0.1% showed very rough and porous film morphology, whereas the film sulfurized at 5% H2S yielded a very smooth and dense film morphology. The CZTS films were fully crystallized in kesterite crystal form when they were sulfurized at 500 oC for 1 h. The kesterite CZTS film showed a reasonably good room-temperature photoluminescence spectrum that peaked in a range of 1.4 eV to 1.5 eV, consistent with the optimal bandgap for CZTS solar cell applications.

The effect of a sputter deposition sequence of Cu, Zn, and Sn metal layers on the properties of Cu2ZnSnS4 (CZTS) was systematically studied for solar cell applications. The set of Cu/Sn/Zn/Cu multi metal films was deposited on a Mo/SiO2/Si wafer using dc sputtering. CZTS films were prepared through a sulfurization process of the Cu/Sn/Zn/Cu metal layers at 500˚C in a H2S gas environment. H2S (0.1%) gas of 200 standard cubic centimeters per minute was supplied in the cold-wall sulfurization reactor. The metal film prepared by one-cycle deposition of Cu(360 nm)/Sn(400 nm)/Zn(400 nm)/Cu(440 nm) had a relatively rough surface due to a well-developed columnar structure growth. A dense and smooth metal surface was achieved for two- or three-cycle deposition of Cu/Sn/Zn/Cu, in which each metal layer thickness was decreased to 200 nm. Moreover, the three-cycle deposition sample showed the best CZTS kesterite structures after 5 hr sulfurization treatment. The two- and three-cycle Cu/Sn/Zn/Cu samples showed high-efficient photoluminescence (PL) spectra after a 3 hr sulfurization treatment, wheres the one-cycle sample yielded poor PL efficiency. The PL spectra of the three-cycle sample showed a broad peak in the range of 700-1000 nm, peaked at 870 nm (1.425 eV). This result is in good agreement with the reported bandgap energy of CZTS.

The Cu2ZnSnS4 (CZTS) thin film solar cell is a candidate next generation thin film solar cell. For the application of an absorption layer in solar cells, CZTS thin films were deposited by pulsed laser deposition (PLD) at substrate temperature of 300˚C without post annealing process. Deposition time was carefully adjusted as the main experimental variable. Regardless of deposition time, single phase CZTS thin films are obtained with no existence of secondary phases. Irregularly-shaped grains are densely formed on the surface of CZTS thin films. With increasing deposition time, the grain size increases and the thickness of the CZTS thin films increases from 0.16 to 1μm. The variation of the surface morphology and thickness of the CZTS thin films depends on the deposition time. The stoichiometry of all CZTS thin films shows a Cu-rich and S-poor state. Sn content gradually increases as deposition time increases. Secondary ion mass spectrometry was carried out to evaluate the elemental depth distribution in CZTS thin films. The optimal deposition time to grow CZTS thin films is 150 min. In this study, we show the effect of deposition time on the structural properties of CZTS thin film deposited on soda lime glass (SLG) substrate using PLD. We present a comprehensive evaluation of CZTS thin films.