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Voids in Kesterites and the Influence of Lamellae Preparation by Focused Ion Beam for Transmission Electron Microscopy Analyses
摘要： Kesterite solar cells based on Cu2 ZnSnS4 and Cu2 ZnSnSe4 (CZTSe) are potential future candidates to be used in thin-film solar cells. The technology still has to be developed to a great extent and for this to happen, high levels of confidence in the characterization methods are required, so that improvements can be made on solid interpretations. In this study, we show that the interpretations of one of the most used characterization techniques in kesterites, scanning transmission electron microscopy (STEM), might be affected by its specimen preparation when using focused ion beam (FIB). Using complementary measurements based on scanning electron microscopy and Raman scattering spectroscopy, compelling evidence shows that secondary phases of ZnSe mixed in the bulk of CZTSe are the likely cause of the appearance of voids in STEM lamellae. Sputtering simulations support this interpretation by showing that Zn in a ZnSe matrix is preferentially sputtered compared with any metal atom in a CZTSe matrix.
关键词： Cu2 ZnSn(S, Se)4 (CZTSSe),thin-film solar cells,transmission electron microscopy (TEM),focused ion beam (FIB),kesterite
更新于2025-09-23 15:22:29
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Numerical analysis of earth-abundant Cu2ZnSn(SxSe1-x)4 solar cells based on Spectroscopic Ellipsometry results by using SCAPS-1D
摘要： Mixed chalcogenide CZTSSe with earth abundant elements, inexpensive, environmental-friendly and impressive photovoltaic performance is a promising absorber material for kesterite thin film solar cells of third generation. In this work, a numerical simulation of p-CZTSSe/n-CdS heterojunction solar cells have been presented using one dimensional Solar Capacitance Simulator. The influence of composition, absorber thickness, defect density and working temperature on Voc, Jsc, FF and power conversion efficiency has been investigated. The optimized cell shows 23.16% efficiency with a Voc ~ 0.724 V corresponding to 40% of the ratio.
关键词： Composition and Spectroscopic Ellipsometry,Absorption coefficient,CZTSSe,Thin film solar cell,Third generation,SCAPS,Efficiency
更新于2025-09-23 15:21:01
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Boosting the efficiency of solution-based CZTSSe solar cells by using supercritical carbon dioxide treatment
摘要： Cu2ZnSn(S,Se)4 (CZTSSe) solar cells are receiving considerable attention in recent years, owing to the low cost and toxicity as well as high abundance of their constituent elements. Solution-based (mainly precursor solution) methods have been widely used in the fabrication of CZTSSe-based thin film solar cells. Though most record solar cells since 2009 have been achieved using solution-based methods, carbonaceous residues are always formed during post deposition treatment (PDT). These carbonaceous residues are detrimental to grain growth of CZTSSe to form large grains. The presence of unwanted small grains layers will increase the series resistance and reduce the fill factor of the solar cell, thus consequently hindering high efficiency in CZTSSe solar cells. Herein, we propose “green” supercritical carbon dioxide (SCCO2) treatment to overcome the challenge of carbonaceous residues. FT-IR、SEM、XRD and Raman characterizations were used to confirm the reducing of carbonaceous residues in CZTSSe films. The solar cell fabricated from selenized CZTSSe precursor film with SCCO2 treatment under optimal conditions showed the best conversion efficiency of 11.23 % (VOC = 0.456 V, JSC = 36.6 mA/cm2, FF = 67.1 %). To the best of our knowledge, it is the first report on boosting the efficiency of solution-based CZTSSe solar cells by using SCCO2 treatment. In addition, this unique SCCO2 treatment may also bring forth new ideas in other solution-based optoelectronic devices.
关键词： CZTSSe,Cu2ZnSn(S,Se)4,Carbonaceous residues,SCCO2 treatment,Supercritical carbon dioxide treatment
更新于2025-09-23 15:21:01
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Effect of selenium partial pressure on the performance of Cu2ZnSn(S, Se)4 solar cells
摘要： Sputtering followed by selenization is one of the most common methods for preparing CZTSSe thin films. However, the influence of selenium partial pressure on the crystallinity of the CZTSSe film has been rarely reported. In this study, CZTSSe thin films were prepared by selenization using quartz tubes of different lengths. The influence of Se saturated vapor pressure and temperature on the structure, composition, optical, and electrical properties of CZTSSe films and solar cells was analyzed and these results were used to optimize the performance of the CZTSSe film. It was found that the maximum partial pressure of selenium was 22,542 Pa when the selenization process was carried out in a quartz tube with a length of 30 cm, which largely improved the structural and electrical properties of CZTSSe. However, quartz tube with an over-short length would bring strong partial pressure during selenization, which resulted in a generation of secondary phases. Finally, CZTSSe thin-film solar cell with a maximum efficiency of 3.27% was obtained at an optimal selenium partial pressure of 22542 Pa.
关键词： CZTSSe,thin-film solar cells,selenium partial pressure,selenization
更新于2025-09-23 15:19:57
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Flexible high-efficiency CZTSSe solar cells on diverse flexible substrates via an adhesive-bonding transfer method
摘要： Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells are showing great promise due to using earth-abundant and non-toxic materials and tuning the bandgap through the amount of S and Se. Flexible high-efficiency CZTSSe solar cells are one of the outstanding research challenges because they currently require the use of thick glass substrates due to the high-temperature heat treatment process, and for this reason, few flexible CZTSSe solar cells have been reported. Furthermore, most researchers have used thin glass and metal substrates with little flexibility; the power conversion efficiency (PCE or ?) values of the solar cells made with them have been somewhat lower. To overcome these hurdles, we transferred high-efficiency CZTSSe solar cells formed on a soda-lime glass substrate to flexible substrates via an adhesive-bonding transfer method. Via this method, we were able to achieve the PCE of 5.8 to 7.1% on completely flexible substrates such as cloth, paper, and polyethylene terephthalate (PET). In particular, we were able to produce a CZTSSe solar cell on a PET substrate with a PCE of 7.1%, which is the highest among fully-flexible CZTSSe solar cells currently known to us. In addition, we deeply analyzed the PCE degradation of the flexible CZTSSe solar cell fabricated by the transfer method through a panoramic focused ion-beam image and nanoindentation. From the results of our work, we provide an insight into the possibility of making flexible high-efficiency CZTSSe solar cells using our transfer method.
关键词： thin-film solar cell,transfer method,polyethylene terephthalate (PET),Cu2ZnSn(S,Se)4 (CZTSSe),diverse flexible substrates
更新于2025-09-19 17:13:59
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Effect of evaporated Sb layer on performance of flexible CZTSSe thin film solar cell
摘要： Cu2ZnSn(S,Se)4 (CZTSSe) chalcogenide with natural-abundance, environment-friendly and impressive photovoltaic performance is promising material for kesterite thin film solar cell. In this paper, the effects of evaporated Sb layer on performance of flexible CZTSSe thin film solar cell are investigated. Systematic studies show that the quasi-liquid Sb2Se3 plays productive roles in promoting grain growth, subsequently volatilizes in the elevated selenization temperature without entering into the CZTSSe lattice. Obvious improvements in crystallinity, grain size, surface roughness, hole concentration and device performance are obtained after optimizing the thickness of Sb layer. The electrostatic potential fluctuation extracted from the PL results is found to decrease from 115.9 meV to 60.7 meV after introducing 20 nm evaporated Sb layer. Finally, 20 nm evaporated Sb layer takes effect to the fullest extent which shows a 69% increase in photoelectric conversion efficiency (PCE). The incorporation of Sb opens up access to opportunity in roll-to-roll process for thin film solar cells.
关键词： Flexible,PL,CZTSSe,Sb incorporation,Solar cell
更新于2025-09-19 17:13:59
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Efficient flexible Mo foil-based Cu2ZnSn(S, Se)4 solar cells from In-doping technique
摘要： Cation substitution has an important impact on the power conversion efficiency (PCE) of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Herein, a significant PCE enhancement of flexible indium-doped CZTSSe solar cells has been achieved by partially substituting Sn4+ with In3+. Systematic measurements indicate that In doping in CZTSSe film effectively improves the crystallinity and carrier concentration of the absorber layer. Meanwhile, the treatment reduces interface recombination and band tailing by passivating deep defects and increases the open-circuit voltage (Voc) of the solar cells. By physical analysis, the key parameters for the solar cell diode such as A, J0, Rs and Rsh are significantly improved after In-doping, indicating better PN junction quality. Under the optimal In-doping (x ? In/(Sn t In) ? 9%), the flexible Cu2ZnSn1-xInx(S,Se)4 solar cell has been successfully obtained with the best efficiency of 7.19% and the Voc enhancement of 62 mV due to reduced Voc deficit and band tailing.
关键词： Solution process,In dopant,Mo foil,Flexible CZTSSe solar cells
更新于2025-09-19 17:13:59
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Effect of solid-H <sub/>2</sub> S gas reactions on CZTSSe thin film growth and photovoltaic properties of a 12.62% efficiency device
摘要： We fabricated CZTSSe thin films using optimized SLG-Mo/Zn/Cu/Sn (MZCT) as a stacked structure and described the phenomenon of Zn elemental volatilization using the MZCT stacked structure. We introduced H2S gas to effectively control the S/(S + Se) ratio of the film in the sulfo-selenization process and to suppress Zn volatilization. Unlike during the selenization process, a stable ZnSSe thin film was formed on the precursor surface during the sulfo-selenization process. The formation of the ZnSSe thin film inhibited Zn volatilization, which facilitated control of the thin film stoichiometry and played an important role in crystal growth. In addition, the sulfo-selenization process using H2S forms a grading of the S/(S + Se) ratio in the depth direction in the ZnSSe layer. The ZnSSe layer with this property causes the band gap grading in the CZTSSe absorption layer. Finally, through our optimized annealing process, we realized a world record CZTSSe solar cell with a certified power conversion efficiency of 12.62% and a centimetre-scale (1.1761 cm2) efficiency of 11.28%.
关键词： CZTSSe,H2S gas,photovoltaic,sulfo-selenization,Zn volatilization,thin film,band gap grading
更新于2025-09-16 10:30:52
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Flexible CZTSSe thin film solar cells fabricated at low temperature with relieved residual stress by Sb incorporation
摘要： The troublesome residual stress is always a stumbling block that drags the progress pace of flexible CZTSSe thin film solar cells, which urgently needs to be noticed and solved. In this paper, low-temperature prepared CZTSSe absorber with relieved residual stress (0.558 GPa) is realized by Sb incorporation. Owing to the evaporated 20 nm Sb layer under CZTS precursor, the crystalline quality and band mismatching of CZTSSe/CdS interface are simultaneously improved. Additionally, the spatial potential fluctuation extracted from the PL results is found to decrease from 63.26 meV to 41.57 meV, indicating a reduction in band tailing and disorder of CZTSSe absorber. Compared with the general solar cells fabricated at 580 °C, flexible devices with Sb incorporation can maintain a slightly higher performance at a lower temperature about 60 °C. The best power conversion efficiency (PCE) of 4.41% is obtained in the solar cell with 550 °C-selenized CZTSSe absorber after incorporating 20 nm Sb layer, featuring 351.20 mV Voc, 25.73 mA/cm2 Jsc and 48.79% FF. Finally, low-temperature prepared flexible CZTSSe thin film solar cell can retain over 83% of the original PCE after bending at 180° for 40 cycles. The mechanical durability paves a promising way for flexible CZTSSe thin film solar cell in roll-to-roll production.
关键词： CZTSSe,Sb incorporation,Residual stress,Low temperature
更新于2025-09-16 10:30:52
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Theoretical investigation on enhancement of output performance of CZTSSe based solar cell
摘要： CZTSSe offers cheap, environmental friendly and earth abundant material for solar devices, yet the record power conversion efficiency for such solar cells has stagnated at about 12 percent over the years. The main reason for low output voltage and overall performance is because of the extreme non radiative recombination in the heterojunction region. To find the overall optimization of solar cell and suitable buffer layer numerical simulation has been performed by SCAPS-1D software. Here, CZTSSe was used as a absorber layer, Al doped ZnO as a transparent conducting layer and ZnO as a window layer. CdS, Cd0.4Zn0.6S and ZnSe was used as a different buffer layer. The impact of thickness of absorber layer and buffer layer on Voc, Jsc, FF and efficiency has been investigated. Also, the effect of temperature on the above-mentioned parameter of the solar cell was studied.
关键词： Heterojunction,Buffer layer,Efficiency,CZTSSe,Solar devices,Absorber layer
更新于2025-09-16 10:30:52