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SOLAR ENERGY MATERIALS AND SOLAR CELLS · 2023 · IF 6.9

Improving the efficiency of Cu2ZnSn(S,Se)4 solar cell by using localized K-doped precursor film

Haoyu Xu,Yuzhou Sun,Zhou Shen,Qing Zhou,Qingyun Zhu,Haifeng Gao,Chao Gao,Xiaoyun Teng,Yu Wei

In this paper, we prepared Na–K co-doped Cu 2 ZnSn(S,Se) 4 (CZTSSe) films by solution method. By optimizing the distribution of the K-doping (uniform or localized K-doping) in the precursor films, the efficiencies of CZTSSe solar cells were improved. The effect of the K-doping distribution on the properties of CZTSSe films and solar cells were investigated. Compared to the solar cells without K-doping, the uniform K-doping in the precursor film increased the solar cell efficiency from 10.4% to 11.7%. In comparison, the localized K-doping in the bottom and in the top of the precursor films yielded solar cells with efficiencies of 12.4% and 10.1%, respectively. It was determined that the K-doping distribution primarily had an influence on carrier recombination in the depletion regions of CZTSSe solar cells. Whereas k-doping at the top of the precursor film greatly enhances the carrier recombination in the depletion region, the bottom doping has the opposite effect. The reason could be that the variation of the K-doping distribution modified the crystallization of the CZTSSe films. As the result, the defect properties of the CZTSSe films were altered. Moreover, the effect of the bottom K-doping on the back contact properties of CZTSSe solar cells was investigated by impedance spectroscopy . Though the K-doping can reduce the back contact barrier of the solar cell, the back contact barrier still achieved the height of 228 meV. The results indicated that the back contact barrier would be an important limiting factor for the efficiency of CZTSSe solar cell.

研究领域: 材料科学 · 能源科学
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SOLAR ENERGY MATERIALS AND SOLAR CELLS · 2024 · IF 6.3

Decreased interface defects in Cu2ZnSn(S,Se)4 solar cells via Cd2+&Ag+ double-ion interface deposition

Xiangyang Zhao,Lingling Wang,Yawei Wang,Xingyu Zhang,Rong Fang,Yue Zhou,Rui Guo,Xintong Zhang,Yichun Liu

Kesterite Cu 2 ZnSn(S,Se) 4 (CZTSSe) thin film solar cells are considered a promising new type of film cell, due to their rich elemental reservation and excellent photovoltaic performance. However, the deleterious defects at the heterojunction interface severely hinder charge transport, separation, and extraction, significantly limiting the photovoltaic performance of CZTSSe solar cells. In this study, a simple method involving the incorporation of Cd 2+ and Ag  +  dual-ion at the heterojunction interface was proposed to reduce interfacial defects. The results showed that Cd 2+ and Ag  +  dual-ion interface deposition effectively reduced the [2Cu zn  + Sn zn ] harmful defects near the heterojunction interface and subsequently reduced the number of recombination centers in the interface. This led to improved carrier recombination at the interface. Meanwhile, the devices achieved a wider depletion width, which was more favorable for carrier collection. Ultimately, the conversion efficiency increased by 32.81 %. This simple interface dual-ion deposition strategy offers a promising strategy for further enhancing the efficiency of CZTSSe cells.

CAS / MDL: 6046-93-1 10124-36-4
研究领域: 材料科学 · 光伏技术
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SOLAR ENERGY MATERIALS AND SOLAR CELLS · 2024 · IF 6.3

Cu2ZnSn(S,Se)4 solar cells with over 10% power conversion efficiency enabled by dual passivation strategy

Letu Siqin,Wenjing Xin,Ruijian Liu,Hongmei Luan,Lei Wang,Yiming Wang,Shuyu Li,Jingyuan Guo,Yu He,Jiayong Zhang,Bin Yao,Chengjun Zhu

Interfaces quality have always been considered the key factors in the fabrication of efficient Cu 2 ZnSn(S,Se) 4 (CZTSSe) solar cells, and harmful defects at the interface can significantly reduce the performance of the device. Here, we propose a dual passivation strategy by adding Na to the surface of the absorber layer (CZTSSe) to passivate the CZTSSe/CdS interface and treating the buffer layer (CdS) using ultraviolet (UV) irradiation to passivate the CdS/ZnO interface. Due to the Na doping passivation, the absorber surface conductivity increases while the roughness decreases and detrimental defects that can lead to nonradiative recombination are reduced. The power conversion efficiency (PCE) of the cell is improved by about 1 percentage point by Na passivation. The contributions of open-circuit voltage ( V oc ), short-circuit current density ( J sc ), and fill factor (FF) to the improvement of PCE have been quantified as 50.64%, −5.58%, and 54.94%, indicating that Na doping can significantly boost V oc and FF. UV-ozone passivation reduces residual carbon organics in the CdS buffer layer , weakens carrier recombination, allows for more light absorption , and widens the depletion region , which favors efficient carrier collection. The estimated contribution of V oc , J sc , and FF to the PCE of the device is 8.78%, 119.59%, and −28.37%, respectively, demonstrating that UV-ozone passivation can significantly improve the J sc of the device. The two passivation strategies complement each other's advantages and achieve a synergistic effect . Our prepared champion device exhibits a PCE of 10.69% and remarkable long-term stability.

研究领域: 材料科学 · 光伏技术 · 界面工程
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ENERGY & FUELS · 2024 · IF 5.2

Exploring New Cadmium Salts to Enhance the Photovoltaic Conversion Efficiency of Cu2ZnSn(S,Se)4 Solar Cells

Haixuan Gao,Chuanhe Ma,Jinhui Zhang,Jinchun Jiang,Ye Chen,Lin Sun,Hailong Wang

In the prior art of CZTSSe solar cells, the traditional cadmium salt (Cd-salt) CdSO4 is widely considered as a common raw material for preparing CdS buffer layers. However, in this study, we systematically demonstrated the phase structure and transmission spectra improvement effect of the other three types of Cd-salts, Cd(NO3)2, CdCl2, and CdAc2, on the CZTSSe/CdS heterojunction (HJT) compared to CdSO4. CZTSSe/CdS HJT prepared by Cd(NO3)2 showed the strongest CdS phonon characteristic peaks at 295.9 and 597.6 cm–1, indicating a pure crystal phase. The transmittance of CdS films prepared by Cd(NO3)2 is 20–35% higher than the other three Cd-salts in the light range of 350–1000 nm, which effectively improved the band gap of the films (2.41 eV) and depressed the photon absorption and scattering. Accordingly, CZTSSe solar cells based on the aforementioned Cd-salts showed that Cd(NO3)2 possessed the best ability to improve the photovoltaic conversion efficiency (PCE), about 5.7% more than the traditional CdSO4 salt. After Sn2+ replaced by Sn4+ in the precursor solution, the PCE of CZTSSe solar cells using Cd(NO3)2 exceeded 10% (Total area = 0.21 cm2, PCE = 10.23%, VOC = 0.485 V, JSC = 31.4 mA/cm2, FF = 67.1%, without MgF2 antireflective layer).

研究领域: 材料科学 · 光伏技术 · 可再生能源 · 半导体物理
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JOURNAL OF POWER SOURCES · 2020 · IF 8.247

Ionic liquid-assisted green solution approach for high-performance Cu2ZnSn(S,Se)4 thin film solar cells

Xinan Shi,Lijian Huang,Daocheng Pan

In this research, a facile and environmentally friendly solution approach is developed to deposit Cu 2 ZnSn(S,Se) 4 thin films by addition of n -butylammonium butyrate ionic liquid . n -Butylammonium butyrate plays a critical role in solution deposition of Cu 2 ZnSnS 4 precursor thin film. We find that liquid n -butylammonium butyrate can dissolve a number of metal oxides , including Cu 2 O, ZnO, and SnO as well as various metal chlorides , metal nitrates and metal acetates. Smell-free Cu 2 ZnSnS 4 precursor solution is synthesized by dissolving Cu 2 O, ZnO, SnCl 2 and thiourea in an ethanol solution of n -butylammonium butyrate. Thermally degradable n -butylammonium butyrate can be completely removed by a low-temperature sintering process , forming high quality Cu 2 ZnSnS 4 nanoparticle thin film. A power conversion efficiency of 8.79% is obtained by this facile and green solution approach.

研究领域: 材料科学 · 能源科学
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CRYSTENGCOMM · 2016 ·Vol. 18 ·期 25 ·4744-4748 · IF 3.849

Fabrication of a Cu2MnSn(S,Se)4 thin film based on a low-cost degradable solution process

Wangen Zhao,Daocheng Pan,Shengzhong (Frank) Liu

Achieving micro-sized and closely packed grains is an essential requirement for high-performance chalcogenide thin film solar cells. Here, I2–II–IV–VI4 (Cu2MnSn(S,Se)4) (CMTSSe) thin films were successfully deposited by carrying out a simple, degradable solution-based process. The structure, composition, and morphology were characterized by powder X-ray diffraction (XRD), energy dispersive spectrometry (EDS), and scanning electron microscopy (SEM), and the Hall effect was also measured. These characterizations indicated that CMTSSe thin films may find applications in photovoltaic absorbing materials. In addition, different substrates were found to affect the morphology and compactness of the grains of the thin film.

研究领域: 材料科学 · 太阳能技术
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Journal of Materials Chemistry C · 2022 ·Vol. 10 ·期 41 ·15638-15646 · IF 8.067

Preparation of band-gap-grading Cu2ZnSn(S,Se)4 thin-film solar cells by post-sulfo-selenization treatment

Xiang Li,Xinghuan Hu,Hua Liao,Shuai Yang,Xinyu Li,Qiulian Li,Xin Liu,Yonggang Zhao,Shurong Wang

In this study, a simple and reproducible two-step annealing process was demonstrated to prepare Cu2ZnSn(S,Se)4 (CZTSSe) thin film with band-gap grading by selenization followed by post-sulfo-selenization (PSS) treatment. The effects of PSS treatment on the composition and electrical properties of the CZTSSe thin film were investigated. The crystal structure, surface morphology, surface roughness and element composition of the CZTSSe thin film were characterized by GIXRD, SEM, AFM and EDS tests. The composition of elements at different depths of the thin film was also investigated. It was confirmed that CZTSSe thin film with high sulfur element content on the surface and low at the bottom were obtained after PSS treatment. The electrical performance of the CZTSSe solar cells was measured by Hall test, EQE and J–V. The results showed that the power conversion efficiency (PCE) of the CZTSSe thin film without PSS treatment was only 7.62%, while the PCE of the CZTSSe thin film after PSS treatment increased to 10.11%.

研究领域: 材料科学 · 光伏技术 · 半导体薄膜
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Solar RRL · 2023 ·Vol. 7 ·期 24 ·2300838 · IF 7.9

Improvement of Performance of Cu2ZnSn(S, Se)4 Solar Cells by Low-Temperature Annealing of B-Doped CdS

Ding Ma,Mengge Li,Bin Yao,Yongfeng Li,Zhanhui Ding,Jiayong Zhang,Chunkai Wang,Yuting Sun,Yue Liu,Xiaofei Sun,Yan Zhu

It is known that high carrier recombination at the p–n junction interface and low carrier separation ability (CSA) are two main problems resulting in low power conversion efficiency (PCE) of the Cu 2 ZnSn(S,Se) 4 (CZTSSe) solar cell. To resolve these problems, one CZTSSe solar cell is prepared through substituting B-doped CdS for CdS in a solar cell with the conventional structure of Ag/ITO/ZnO/CdS/CZTSSe/Mo/SLG and annealing B-doped CdS/CZTSSe/Mo/SLG prior to deposition of ZnO, ITO, and Ag electrode. By optimizing the B doping content in the CdS and annealing temperature and time of the B-doped CdS/CZTSSe, lattice mismatch between CdS and CZTSSe is decreased and width of depletion region is increased, leading to reduction in interfacial recombination, enhancement in CSA and intensity of incident light passing through the B-doped CdS, and so increase in PCE from 7.89% of CZTSSe solar cell using CdS as buffer layer to 10.62%. A mechanism of the increment of the PCE induced by B doping and annealing is suggested. This work proposes a method of increasing PCE of CZTSSe solar cell and advances a deeper understanding of the mechanisms behind various parameters in CZTSSe solar cells through theoretical analysis and calculations.

研究领域: 材料科学 · 光伏技术 · 半导体物理
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Advanced Energy Materials · 2024 · IF 24.4

An Effective Precursor-Solutioned Strategy for Developing Cu2ZnSn(S, Se)4 Thin Film Toward High Efficiency Solar Cell

Ang Liang,Yue Jian,Yun Zhao,Shuo Chen,Jun Zhao,Zhuanghao Zheng,Jingting Luo,Hongli Ma,Xianghua Zhang,Zhenghua Su,Guangxing Liang

Enhancing the efficiency of Cu 2 ZnSn (S, Se) 4 (CZTSSe) thin-film solar cells requires the development of well-crystallized light-absorbing layers. A deep understanding of the role of precursor solution chemistry in film nucleation and crystal growth processes is essential. Insights into these processes enable the development of innovative strategies to enhance absorber quality, minimize detrimental bulk defects, and ultimately improve device performance. This study elucidates the condensation reactions between thiourea and metal cations, as well as the alcoholysis of 2-methoxyethanol (MOE), at different concentrations of precursor solutions. The primary focus of this study is implementing a simple and environmentally friendly innovative spin-coating strategy, aimed at optimizing Cu 2 ZnSnS 4 (CZTS) precursor films and adjusting the Se content within the film bulk to promote grain growth during selenization. This strategy effectively improves absorber morphology while suppressing the formation of deep-level defects, thereby enhancing carrier transport in both interfacial and bulk regions of the absorber layer. Consequently, CZTSSe absorbers with enhanced crystallinity and reduced defects are synthesized, resulting in a solar cell with an impressive efficiency of 14.10%. These findings underscore the potential for creating highly efficient kesterite CZTSSe solar cells through the manipulation of precursor solution chemistry using environmentally friendly solvents.

研究领域: 材料科学 · 能源科学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2024 · IF 5.8

Enhancement of power conversion efficiency of Cu2ZnSn(S,Se)4 Solar Cells by pretreating Mo electrode with H2O2

Yue Liu,Chunkai Wang,Ding Ma,Mengge Li,Yuting Sun,Xiaofei Sun,Yan Zhu,Bin Yao,Yongfeng Li,Zhanhui Ding

It is proved that secondary phases, such as Cu 2 Se, and ZnSe etc., and MoSe 2 layer can form at Cu 2 ZnSn(S,Se) 4 (CZTSSe)/Mo electrode interface, due to that Mo electrode reacts with CZTSSe and Se vapor during selenization process. The secondary phases and MoSe 2 with inappropriate thickness can decrease power conversion efficiency (PCE) of CZTSSe solar cell. In this work, a simple method was proposed to suppress the reaction between CZTSSe and Mo, and to optimize the thickness of MoSe 2 . This was achieved by growing a layer of Mo oxide in situ on the Mo electrode surface through soaking the Mo electrode in H 2 O 2 . The Mo oxide layer consisted of MoO 3 , MoO x and MoO 2 . It could suppress the reaction between Mo and CZTSSe, thus preventing the formation of secondary phases in CZTSSe. By further tuning the soaking time, the thickness and density of the Mo oxide layer were optimized, resulting in an optimized thickness of the MoSe 2 layer and a significant improvement in the contact quality at both the front and back interfaces. This improvement is beneficial for suppressing carrier recombination and reducing contact resistance. Furthermore, the Cu/(Zn+Sn) ratio in CZTSSe was optimized, leading to an expansion of the depletion region width. As a result, the reverse saturation current density and series resistance decrease, while the photogenerated current density increases. This ultimately led to a rise in PCE from 7.66% for CZTSSe solar cells with Mo electrodes that were not soaked to 8.95% for those with Mo electrodes soaked for 20 s.

研究领域: 材料科学 · 能源技术
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APPLIED SURFACE SCIENCE · 2016 · IF 3.15

Fabrication of Cu2ZnSn(S,Se)4 (CZTSSe) absorber films based on solid-phase synthesis and blade coating processes

Ruixin Ma,Fan Yang,Shina Li,Xiaoyong Zhang,Xiang Li,Shiyao Cheng,Zilin Liu

CZTSSe is an important earth abundant collection of materials for the development of low cost and high efficiency thin film solar cells. This work developed a simple non-vacuum-based route to fabricate CZTSSe absorber films. This was demonstrated by first synthesizing Cu 2 ZnSnS 4 (CZTS) nano-crystalline based on solid-phase synthesis. Then a stable colloidal ink composed of CZTS nano-crystalline was blade coated on Mo-coated substrates followed by an annealing process under Ar atmosphere. After CZTS films formation, the films were sintered into CZTSSe absorber films by exposing them under Selenium vapor. The formation of a kesterite type CZTS was confirmed using X-ray diffraction and Raman scattering measurements. The band gap of CZTSSe absorber films was determined to be 1.26   eV, which was appropriate for use as an absorber layer in thin film solar cells. The CZTSSe absorber films showed a good photovoltatic performance, demonstrating this simple approach had great potential for CZTSSe solar cell production.

研究领域: 材料科学 · 光伏技术 · 薄膜技术 · 纳米材料 · 可再生能源
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Nanomaterials · 2022 ·Vol. 12 ·期 17 ·2942 · IF 5.719

Insight into the Effect of Selenization Temperature for Highly Efficient Ni-Doped Cu2ZnSn(S,Se)4 Solar Cells

Fancong Zeng,Yingrui Sui,Meiling Ma,Na Zhao,Tianyue Wang,Zhanwu Wang,Lili Yang,Fengyou Wang,Huanan Li,Bin Yao

Cu2Ni0·05Zn0·95Sn(S,Se)4(CNZTSSe) films were synthesized on Mo-coated glass substrates by the simple sol–gel means combined with the selenization process, and CNZTSSe-based solar cells were successfully prepared. The effects of selenization temperature on the performance and the photoelectric conversion efficiency (PCE) of the solar cells were systematically studied. The results show that the crystallinity of films increases as the selenization temperature raises based on nickel (Ni) doping. When the selenization temperature reached 540 °C, CNZTSSe films with a large grain size and a smooth surface can be obtained. The Se doping level gradually increased, and Se occupied the S position in the lattice as the selenization temperature was increased so that the optical band gap (Eg) of the CNZTSSe film could be adjusted in the range of 1.14 to 1.06 eV. In addition, the Ni doping can inhibit the deep level defect of SnZnand the defect cluster [2CuZn+ SnZn]. It reduces the carrier recombination path. Finally, at the optimal selenization temperature of 540 °C, the open circuit voltage (Voc) of the prepared device reached 344 mV and the PCE reached 5.16%.Keywords:solar cell;selenidation temperature;CNZTSSe;sol gel

研究领域: 材料科学 · 太阳能电池技术
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