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In copper zinc tin sulfide (CZTS) based thin films, copper zinc antisite (CuZn) represents the major p-type acceptor defect with low formation energy. This antisite can create defect-dominated carrier recombination hotspots, which reduces power conversion efficiency. Extrinsic doping in cationic sites of the CZTS thin film during synthesis is an effective way to passivate this defect. It has previously been reported that employing Cd as a dopant can passivate this defect and improve film quality. Injecting toxic Cd into non-toxic CZTS may create more problems than it solves. Simultaneous doping of Cd and other atoms like Mg is hypothesized to accomplish this goal of lowering Cd concentration. For this, it is important to know the effect of doping Cd and Mg separately under analogous experimental conditions. The structural, morphological, and optical properties, as well as the chemical bonding states, of sol-gel spin-coated CZTS thin films were investigated in this study using independent and controlled Cd and Mg doping. The fabrication procedure consisted of two steps: sol-gel spin coating followed by sulfurization. As a solvent for precursors in creating sols for spin coating processes, dimethyl sulfoxide (DMSO) was employed. Each dopant's precursor concentration was chosen to ensure an identical mole percentage of zinc precursor in the solution. The fabricated films were characterized undoped and doped forms using X-ray diffractometry (XRD) with Rietveld refinements, Raman spectroscopy, Field emission scanning electron microscopy (FESEM), 3D profilometry, and Ultraviolet-visible near-infrared (UV-Vis NIR) spectroscopy. The elemental composition ratio and chemical bonding states of the fabricated films were probed by Energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), respectively. Fabricated thin films exhibit distinct synergistic features depending on the dopant types used in the fabrication process. The crystal structure of the doped absorber and the chemical valence states of the other elements (Cu, Zn, Sn, and S) were not changed as shown by XRD, Raman, and XPS analyses. The main diffraction peak at the (112) plane is found at Bragg's diffraction angle of 28.6° for an undoped sample. This peak shifts left upon Cd and Mg doping to 28.2° and 28.4° owing to different ionic radii of dopants relative to Zn ions, which indicates the presence of dopants in the fabricated films. Raman spectroscopy probes the Cu-Sn-S secondary phases: cubic Cu2SnS3 at 305 cm−1 in the undoped sample, tetragonal Cu2SnS3 at 296 cm−1 in the Cd-doped sample, and orthorhombic Cu3SnS4 at 291 cm−1 in the Mg-doped sample. From the EDS results, it appears that 45% of the Zn atoms in both the Cd-doped and Mg-doped samples are partially substituted by Cd and Mg, respectively. The optical band gap for Cd-doped samples decreases from 1.61 eV to 1.56 eV when compared to undoped samples. For Mg-doped samples, the optical band gap shrinks even more to 1.1 eV. This corresponds to shifting of absorbance spectra to higher wavelengths known as “redshift”. Urbach energy is determined to be 284 meV and 1072 meV for Cd and Mg doped samples, respectively, to address band tailing issues. Mg doping enhances crystallite size slightly while decreasing microstrain and dislocation density. The RMS surface roughness of Cd and Mg doped samples is 147 nm and 280 nm, respectively. Nevertheless, the primary peaks of Cu, Zn, Sn, S, Cd, Mg, and O, as well as the secondary photoelectron emission lines of these elements, are all found to be present and identified in both the doped samples. These results imply that Cd and Mg doping in the Zn-cationic site of virgin CZTS thin film can be regulated systematically to get appreciated features as a solar cell absorber.

Non-vacuum-based techniques are suitable for thin-film deposition with precision stoichiometric control. Among those, the Successive Ionic Layer Adsorption and Reaction (SILAR) method is gaining popularity for its aqueous-based almost room temperature deposition option. This method has many advantages, including the ability to control the elemental composition and stoichiometry of precursors. It is also suitable for large-area deposition. It has many runtime parameters, e.g., the number of cycles, dip time, rinse time, etc., that control the quantitative and qualitative physical properties of the deposited film. But manually controlling all these parameters for the whole process is very difficult and cumbersome. Although there are several reports published on this similar type of home-built prototype, for fast, accurate, and economically affordable deposition operations, we need to develop a machine that maintains all the properties of the SILAR process and can be made using cheap technologies. Here we report the SnapFib, a cost-effective automated tabletop prototype machine that is easy to build for thin-film deposition on soda-lime glass substrates by the SILAR method without almost any human intervention. SnapFib is built using linear actuators, an ATmega328P (a microcontroller available on Arduino boards), and some other parts collected from laboratory sites. The whole firmware needed for this device has been developed and maintained using the Arduino IDE (Integrated Development Environment). All required functional features and control parameters are encoded in the microcontroller firmware. The construction cost of this prototype is around 600 USD. We validated our construction through XRD (X-ray Diffraction) and FESEM (Field Emission Scanning Electron Microscope) characterizations of thin films that were deposited by SnapFib. Since this is built under the CC-BY license, students and researchers can freely perform and validate their experiments and modify the hardware and software as required. With how easy it is to make and how much it costs; we hope that many thin-film deposition labs will quickly start using SnapFib as an added benefit.