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Sputtered and selenized Sb2Se3 thin-film solar cells with open-circuit voltage exceeding 500??mV
摘要： Antimony selenide (Sb2Se3) is a potential absorber material for environment-friendly and cost-efficient photovoltaics and has achieved considerable progress in recent years. However, the severe open-circuit voltage (Voc) deficit ascribed to the interface and/or bulk defect states has become the main obstacle for further efficiency improvement. In this work, Sb2Se3 absorber layer was prepared by an effective combination reaction involving sputtered and selenized Sb precursor thin films. The self-assembled growth of Sb2Se3 thin films with large crystal grains, benign preferential orientation, and accurate chemical composition were successfully fulfilled under an appropriate thickness of Sb precursor and an optimized selenization scenario. Substrate structured Sb2Se3 thin-film solar cells, a champion device with a power-conversion efficiency of 6.84%, were fabricated. This device is comparable to state-of-the-art ones and represents the highest efficiency of sputtered Sb2Se3 solar cells. Importantly, the high Voc of 504 mV is closely related to the reduced deep level defect density for the Sb2Se3 absorber layer, the passivated interfacial defects for Sb2Se3/CdS heterojunction interface, and the additional heterojunction heat treatment-induced Cd and S inter-diffusion. This significantly improved Voc demonstrates remarkable potential to broaden its scope of applications for Sb2Se3 solar cells.
关键词： Open-circuit voltage,Selenization,Sb2Se3 solar Cell,Elemental inter-diffusion,Sputtering
更新于2025-09-23 15:21:01
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Hybrid Ligand Exchange of Cu(In,Ga)S <sub/>2</sub> Nanoparticles for Carbon Impurity Removal in Solution Processed Photovoltaics
摘要： The solution processing of Cu(In,Ga)(S,Se)2 photovoltaics from colloidal nanoparticles has long suffered from deleterious carbonaceous residues originating from long chain native ligands. This impurity carbon has been observed to hinder grain formation during selenization and leave a discrete residue layer between the absorber layer and the back contact. In this work, organic and inorganic ligand exchanges were investigated to remove tightly bound native oleylamine ligands from Cu(In,Ga)S2 nanoparticles, thereby removing the source of carbon contamination. However, incomplete ligand removal, poor colloidal stability, and/or selective metal etching was observed for these methods. As such, an exhaustive hybrid organic/inorganic ligand exchange was developed to bypass the limitations of individual methods. A combination of microwave-assisted solvothermal pyridine ligand stripping followed by inorganic capping with diammonium sulfide was developed and yielded greater than 98% removal of native ligands via a rapid process. Despite the aggressive ligand removal, the nanoparticle stoichiometry remained largely unaffected when making use of the hybrid ligand exchange. Furthermore, highly stable colloidal ink formulations using non-toxic dimethyl sulfoxide were developed, supporting stable nanoparticle mass concentrations exceeding 200 mg/mL. Scalable blade coating of the ligand exchanged nanoparticle inks yielded remarkably smooth and microcrack free films with RMS roughness less than 7 nm. Selenization of ligand exchanged nanoparticle films afforded substantially improved grain growth as compared to conventional non-ligand exchanged methods yielding an absolute improvement in device efficiency of 2.8%. Hybrid ligand exchange nanoparticle based devices reached total-area power conversion efficiencies of 12.0%, demonstrating the feasibility and promise of ligand exchanged colloidal nanoparticles for the solution processing of Cu(In,Ga)(S,Se)2 photovoltaics.
关键词： hybrid ligand exchange,blade coating,diammonium sulfide,carbon impurity removal,photovoltaics,grain growth,Cu(In,Ga)(S,Se)2,solution processing,ligand exchange,selenization,microwave-assisted solvothermal,colloidal nanoparticles,device efficiency
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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Reaction Pathway for Efficient CZTSe Solar Cells from Alloyed Cu-Sn Precursor via a Cu-Rich Selenization Stage
摘要： A detailed reaction pathway for efficient CZTSe solar cells from alloyed Cu-Sn precursor via a Cu-rich selenization stage is presented. The study focuses on the selenization of stacked elemental metallic layers (Cu-Sn-Zn), a commonly reported approach in kesterite Cu2ZnSnSe4 (CZTSe) processing. The high volatility of binary selenides, such as SnSe2-x, at necessary annealing temperatures (500 – 550 °C) makes this reaction pathway prone to Sn loss, which challenges the control of the composition and quality of the grown material. The present work reports an approach based on stacked elemental and alloyed precursors, discussing the benefits of using a Zn/Cu-Sn/Zn configuration. The absence of non-alloyed elemental Sn helps in suppressing the formation and subsequent evaporation of SnSe2-x phases, preventing Sn loss from the film during selenization. This reaction pathway involves a process scheme which i) starts with the growth of CZTSe in a Cu-rich environment, ii) includes a shift of the composition by supply of SnSe2-x vapor, and iii) terminates in the Cu-poor regime, leading to device efficiencies above 10%. This composition shift in the presented process appears similar to the final stage of the commonly known CIGSe three-stage co-evaporation.
关键词： Reaction pathway,Selenization,Kesterite,Alloying
更新于2025-09-23 15:19:57
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Microstructural investigation of inkjet printed Cu(In,Ga)Se2 thin film solar cell with improved efficiency
摘要： Inkjet printed copper indium gallium diselenide (CIGS) thin film solar cell has attracted tremendous attention because of its various technological benefits as a non-vacuum process. Focused efforts in selenization of inkjet printed films to make the process feasible, are desired. In this work, microstructural investigation of inkjet printed precursor film selenized by rapid thermal processing (RTP) is presented. The optimization of selenization time for transforming metal nitrates precursor ink to CIGS thin film is investigated. Based on the results, the growth mechanism to form CIGS from inkjet printed CIG precursor films is proposed. Systematic study on the molybdenum diselenide (MoSe2) phase evolution during the two-step atmospheric pressure selenization process at the CIGS-Mo interface and its effect on device performance are carried out. Non-uniform inter-diffusion of indium (In) and gallium (Ga) during selenization, resulting in double-layered CIGS, one of the major reason limiting the performance of the devices is investigated through XRD, Raman, FESEM, EDS and Mott-Schottky analysis. The significant improvement in device efficiency from 0.4% to 4.2% is achieved due to microstructural improvement in CIGS films. Investigation on the mechanism of microstructural growth with selenization time affecting final device performance is presenting in this work.
关键词： CIGS,Rapid thermal processing,Microstructural growth,Inkjet printing,Atmospheric pressure selenization
更新于2025-09-23 15:19:57
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Controlled Sputtering Pressure on High-Quality Sb2Se3 Thin Film for Substrate Configurated Solar Cells
摘要： Magnetron sputtering has become an effective method in Sb2Se3 thin film photovoltaic. Research found that post-selenization treatments are essential to produce stoichiometric thin films with desired crystallinity and orientation for the sputtered Sb2Se3. However, the influence of the sputtering process on Sb2Se3 device performance has rarely been explored. In this work, the working pressure effect was thoroughly studied for the sputtered Sb2Se3 thin film solar cells. High-quality Sb2Se3 thin film was obtained when a bilayer structure was applied by sputtering the film at a high (1.5 Pa) and a low working pressure (1.0 Pa) subsequently. Such bilayer structure was found to be beneficial for both crystallization and preferred orientation of the Sb2Se3 thin film. Lastly, an interesting power conversion efficiency (PCE) of 5.5% was obtained for the champion device.
关键词： Sb2Se3,magnetron sputtering,substrate configuration,post-selenization,working pressure,thin film solar cell
更新于2025-09-23 15:19:57
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Effect of selenization temperature on the properties of Sb2Se3 thin films and solar cells by two-step method
摘要： In this work, antimony selenide (Sb2Se3) thin films were prepared using electron-beam (e-beam) evaporation followed by selenization process (two-step method) for the first time. The effect of selenization temperature on the properties of Sb2Se3 thin films and solar cells was investigated systematically. Formation of pure polycrystalline Sb2Se3 was confirmed and the intensity of (hk1) and (hk2) patterns was found to decrease while that of (hk0) to increase with temperature elevating. However, when the temperature became higher than 360 °C, the shape of Sb2Se3 grains gradually changed to rod-like shape from round shape and some craters and cracks in the films can be observed. Sb2Se3 films prepared at 360 °C showed an average grain size of 450 nm, a roughness of 42 nm, an optical bandgap of 1.24 eV and a carrier concentration of 4.99 × 1012 cm?3. The corresponding Sb2Se3 solar cells exhibited an optimal power conversion efficiency of 1.15%. Our results demonstrated that the process of e-beam evaporation of Sb followed by selenization at appropriate temperature is a good way to prepare high quality Sb2Se3 thin films for solar cells.
关键词： Sb2Se3,e-beam evaporation,solar cells,selenization temperature,thin films
更新于2025-09-19 17:13:59
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Spark plasma sintering of Sb2Se3 sputtering target towards highly efficient thin film solar cells
摘要： Antimony selenide (Sb2Se3) is a potential absorber material for environment-friendly and cost-efficiently photovoltaics due to its material advantages and superior optoelectronic properties. In this work, we proposed a facile and versatile method of ball milling followed with spark plasma sintering (SPS) to prepare high-quality Sb2Se3 sputtering target. Then the highly crystalline Sb2Se3 thin film consisted of large crystal grains can be prepared by using radio frequency (RF) magnetron sputtering with an additional post-selenization heat treatment. An efficient substrate structured Sb2Se3 thin film solar cell with configuration of Mo/Sb2Se3/CdS/ITO/Ag was fabricated and a champion device with highly interesting power conversion efficiency (PCE) of 5.08% has been achieved. Superior device performances are closely related to the Sb2Se3 absorber layer with benign growth orientation and the Sb2Se3/CdS heterojunction interface with smooth contact, which induced less recombination loss. The combined features of homemade sputtering target and advantageous thin film preparation technology further demonstrated its attractive application potential in thin film photovoltaic scenarios.
关键词： Sb2Se3,Post-selenization,Sputtering target,Magnetron sputtering,Spark plasma sintering,Thin film solar cells
更新于2025-09-19 17:13:59
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An effective combination reaction involved with sputtered and selenized Sb precursors for efficient Sb2Se3 thin film solar cells
摘要： Sputtering followed by post annealing is extensively used for fabrication of copper indium gallium selenide (CIGS), copper zinc tin sulfide (CZTS) and copper zinc tin sulfur selenide (CZTSSe) thin film solar cells. In this work, Sb2Se3 as an emerging alternative absorber was fabricated by an effective combination reaction of annealing sputtered Sb metallic precursors under Se vapor. Self-assembled growth of Sb2Se3 thin films consist of large grains that across the whole films have been successfully fulfilled via this combination reaction. Sb2Se3 thin films with desired orientation, stoichiometric composition and high-quality Sb2Se3/CdS heterojunction could be achieved once a proper selenization scenario was employed. Further, by selecting Sb films as precursors, the thickness of interfacial MoSe2 located at the back-contact region can be well controlled, leading to a significant enhancement in fill factor (FF) of the devices. This is in good accordance with our DFT simulation results which demonstrated Se vapor would be prone to react with the Sb lattice thermodynamically and thus limiting the thickness of the MoSe2 layer. Finally, a champion Sb2Se3 thin film solar cell with power conversion efficiency of 6.15% was achieved, which represents the highest efficiency of sputtered Sb2Se3 solar cells.
关键词： DFT calculations,Sb2Se3 solar cell,Magnetron sputtering,Selenization,Combination reaction
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