Solar energy has been recognized as an alternative energy source that can help address fuel depletion and climate change issues. As a renewable energy alternative to fossil fuels, it is an eco-friendly and unlimited energy source. Among solar cells, thin film Cu2ZnSn(S,Se)4 (CZTSSe) is currently being actively studied as an alternative to heavily commercialized Cu (In,Ga)Se2 (CIGS) thin film solar cells, which rely upon costly and scarce indium and gallium. Currently, the highest efficiency achieved by CZTSSe cells is 14.9 %, lower than the CIGS record of 23.35 %. When applied to devices, CZTSSe thin films perform poorly compared to other materials due to problems including lattice defects, conduction band offset, secondary phase information, and narrow stable phase regions, so improving their performance is essential. Research into ways of improving performance by doping with Germanium and Cadmium is underway. Specifically, Ge can be doped into CZTSSe, replacing Sn to reduce pinholes and bulk recombination. Additionally, partially replacing Zn with Cd can facilitate grain growth and suppress secondary phase formation. In this study, we analyzed the device’s performance after doping Ge into CZTSSe thin film using evaporation, and doping Cd using chemical bath deposition. The Ge doped thin film showed a larger bandgap than the undoped reference thin film, achieving the highest Voc of 494 mV in the device. The Cd doped thin film showed a smaller bandgap than the undoped reference thin film, with the highest Jsc of 36.9 mA/cm2. As a result, the thin film solar cells achieved a power conversion efficiency of 10.84 %, representing a 20 % improvement in power conversion efficiency compared to the undoped reference device.

Cu2ZnSn(S,Se)4 (CZTSSe) based thin-film solar cells have attracted growing attention because of their earthabundant and non-toxic elements. However, because of their large open-circuit voltage (Voc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)2 (CIGS) and CdTe based solar cells. One of the main causes of this large Voc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 oC to 540 oC during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.

Recent advances in technology using ultra-thin noble metal film in oxide/metal/oxide structures have attracted attention because this material is a promising alternative to meet the needs of transparent conduction electrodes (TCE). AZO/ Ag/AZO multilayer films are prepared by magnetron sputtering for Cu2ZnSn(S,Se)4 (CZTSSe) of kesterite solar cells. It is shown that the electrical and optical properties of the AZO/Ag/AZO multilayer films can be improved by the very low resistivity and surface plasmon effects due to the deposition of different thicknesses of Ag layer between oxide layers fixed at AZO 30 nm. The AZO/Ag/AZO multilayer films of Ag 15 nm show high mobility of 26.4 cm2/Vs and low resistivity and sheet resistance of 3.58*10−5 Ωcm and 5.0 Ω/sq. Also, the AZO/Ag (15 nm)/AZO multilayer film shows relatively high transmittance of more than 65% in the visible region. Through this, we fabricated CZTSSe thin film solar cells with 7.51% efficiency by improving the short-circuit current density and fill factor to 27.7 mV/cm2 and 62 %, respectively.

Cu2ZnSn(S,Se)4(CZTSSe) thin film solar cells areone of the most promising candidates for photovoltaic devices due to their earth-abundant composition, high absorption coefficient and appropriate band gap. The sputtering process is the main challenge to achieving high efficiency of CZTSSe solar cells for industrialization. In this study, we fabricated CZTSSe absorbers on Mo coated soda lime glass using different pressures during the annealing process. As an environmental strategy, the annealing process is performed with S and Se powder, without any toxic H2Se and/or H2S gases. Because CZTSSe thin films have a very narrow stable phase region, it is important to control the condition of the annealing process to achieve high efficiency of the solar cell. To identify the effect of process pressure during the sulfo-selenization, we experiment with varying initial pressure from 600 Torr to 800 Torr. We fabricate a CZTSSe thin film solar cell with 8.24 % efficiency, with 435 mV for open circuit voltage(VOC) and 36.98 mA/cm2 for short circuit current density(JSC), under a highest process pressure of 800 Torr.

Cu2ZnSn(S,Se)4 (CZTSSe) films were prepared on Mo coated soda lime glass substrates by sulfo-selenization of sputtered stacked Zn-Sn-Cu(CZT) precursor films. The precursor was dried in a capped state with aqueous NaOH solution. The CZT precursor films were sulfo-selenized in the S + Se vapor atmosphere. Sodium was doped during the sulfo-selenization treatment. The effect of sodium doping on the structural and electrical properties of the CZTSSe thin films were studied using FE-SEM(field-emission scanning electron microscopy), XRD(X-ray diffraction), XRF(X-ray fluorescence spectroscopy), dark current, SIMS(secondary ion mass spectrometry), conversion efficiency. The XRD, XRF, FE-SEM, Dark current, SIMS and cell efficiency results indicated that the properties of sulfo-selenized CZTSSe thin films were strongly related to the sodium doping. Further detailed analysis and discussion for effect of sodium doping on the properties CZTSSe thin films will be discussed.

Cu2ZnSn(Sx,Se1-x)4 (CZTSSe) thin films were prepared by sulfurization of evaporated precursor thin films. Precursor was prepared using evaporation method at room temperature. The sulfurization was carried out in a graphite box with S powder at different temperatures. The temperatures were varied in a four step process from 520˚C to 580˚C. The effects of the sulfurization temperature on the micro-structural, morphological, and compositional properties of the CZTSSe thin films were investigated using X-ray diffraction (XRD), Raman spectra, field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The XRD and Raman results showed that the sulfurized thin films had a single kesterite crystal CZTSSe. From the FE-SEM and TEM results, the Mo(Sx,Se1-x)2 (MoSSe) interfacial layers of the sulfurized CZTS thin films were observed and their thickness was seen to increase with increasing sulfurization temperature. The microstructures of the CZTSSe thin films were strongly related to the sulfurization temperatures. The voids in the CZTSSe thin films increased with the increasing sulfurization temperature.

Chalcogenide-based semiconductors, such as CuInSe2, CuGaSe2, Cu(In,Ga)Se2 (CIGS), and CdTe have attracted considerable interest as efficient materials in thin film solar cells (TFSCs). Currently, CIGS and CdTe TFSCs have demonstrated the highest power conversion efficiency (PCE) of over 11% in module production. However, commercialized CIGS and CdTe TFSCs have some limitations due to the scarcity of In, Ga, and Te and the environmental issues associated with Cd and Se. Recently, kesterite CZTS, which is one of the In- and Ga- free absorber materials, has been attracted considerable attention as a new candidate for use as an absorber material in thin film solar cells. The CZTS-based absorber material has outstanding characteristics such as band gap energy of 1.0 eV to 1.5 eV, high absorption coefficient on the order of 104cm-1, and high theoretical conversion efficiency of 32.2% in thin film solar cells. Despite these promising characteristics, research into CZTS-based thin film solar cells is still incomprehensive and related reports are quite few compared to those for CIGS thin film solar cells, which show high efficiency of over 20%. The recent development of kesterite-based CZTS thin film solar cells is summarized in this work. The new challenges for enhanced performance in CZTS thin films are examined and prospective issues are addressed as well.