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Nanomaterials · 2022 ·Vol. 12 ·期 22 ·3994 · IF 5.719

Optimization of the Selenization Temperature on the Mn-Substituted Cu2ZnSn(S,Se)4 Thin Films and Its Impact on the Performance of Solar Cells

Zhanwu Wang,Yingrui Sui,Meiling Ma,Tianyue Wang

Cu2ZnSn(S,Se)4(CZTSSe) films are considered to be promising materials in the advancement of thin-film solar cells. In such films, the amounts of S and Se control the bandgap. Therefore, it is crucial to control the concentration of S/Se to improve efficiency. In this study, Cu2MnxZn1−xSnS4(CMZTS) films were fabricated using the sol-gel method and treated in a Se environment. The films were post-annealed in a Se atmosphere at various temperature ranges from 300 °C to 550 °C at intervals of 200 °C for 15 min to obtain Cu2MnxZn1−xSn(S,Se)4(CMZTSSe). The elemental properties, surface morphology, and electro-optical properties of the CMZTSSe films were investigated in detail. The bandgap of the CMZTSSe films was adjustable in the scope of 1.11–1.22 eV. The structural propeties and phase purity of the CMZTSSe films were analyzed by X-ray diffraction and Raman analysis. High-quality CMZTSSe films with large grains could be acquired by suitably changing the selenization temperature. Under the optimized selenization conditions, the efficiency of the fabricated CMZTSSe device reached 3.08%.Keywords:Cu2ZnSn(S,Se)4film;Mn-doping;solar cells;properties;selenization temperature

研究领域: 材料科学 · 能源技术
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Advanced Materials Interfaces · 2021 ·Vol. 8 ·期 18 ·2100971 · IF 6.147

Bifacial Cu2ZnSn(S,Se)4 Thin Film Solar Cell Based on Molecular Ink and Rapid Thermal Processing

Saqib Nawaz Khan,Sijie Ge,Ening Gu,Santhosh Kumar Karunakaran,Wentao Yang,Ruijiang Hong,Yaohua Mai,Xianzhong Lin,Guowei Yang

The use of transparent conducting oxides (TCO) as a back contact for Cu 2 ZnSn(S,Se) 4 (CZTSSe) thin film solar cell enables light absorption from both front and rear sides and allows for the fabrication of semi-transparent photovoltaic devices. However, the CZTSSe solar cell based on TCO substrate suffers from high parasitic losses owing to the long post-annealing time at elevated temperature required for high-quality absorber. This work aims to overcome this issue by carefully tailoring the annealing conditions to obtain high-performance solar cell. Rapid thermal processing is used to instantaneously generate high Se vapor pressure at target temperature and shorten the annealing time. The crystalline quality, morphology, and particularly the photovoltaic performance of the resulting CZTSSe thin film are systematically investigated. It is found that the increase of annealing temperature and time improves the crystalline quality but unfortunately deteriorates the device performance owing to increasing parasitic losses. Increasing the amount of Se allows to get highly crystalline absorber within 7 min of annealing, yielding a total area 5.56% efficient CZTSSe solar cell with front illumination resulting from reducing parasitic losses. This work provides a simple approach to preserve the back contact without using a complex interfacial layer.

CAS / MDL: 67-68-5
研究领域: 材料科学 · 光伏技术
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Sustainable Energy & Fuels · 2023 ·Vol. 8 ·期 3 ·604-609 · IF 5.6

Differential effects of MoO3 and MoO2 sacrificial layers on the J–V performance of Cu2ZnSn(S,Se)4 solar cells

Jinhui Zhang,Chuanhe Ma,Haixuan Gao,Jinchun Jiang,Hailong Wang

An over-thick MoSe2 layer and numerous voids at the absorbing layer inside and backside lead to a relatively low Jsc and PCE of CZTSSe solar cells. In previous studies, MoO2 and MoO3 sacrificial layers have been commonly used to eliminate those voids and reduce the thickness of MoSe2 layers. However, there is still no clarity about which one is more effective. In this work, we prepared MoO2 and MoO3 sacrificial layers on the surface of Mo-coated SLG substrates by air annealing and ammonia (NH3·H2O) etching, respectively. J–V testing shows that both MoO2 and MoO3 can effectively improve the Jsc and PCE of CZTSSe solar cells, wherein MoO3 is more effective. Comparative analysis shows that the electrical mechanism of Jsc and PCE improvement lies in the significant reduction of device series resistance (Rs). SEM images and XRD pattern results indicate that the reason for Rs decreasing is void elimination and MoSe2 layer thickness reduction from 600 nm to 270 nm after applying MoO3. With the aid of the MoO3 sacrificial layer, the PCE of the CZTSSe device increases from 7.51% to 9.58% (total area 0.21 cm2) without the MgF2 anti-reflection layer.

研究领域: 材料科学 · 太阳能 · 光伏技术
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JOURNAL OF ALLOYS AND COMPOUNDS · 2024 · IF 5.8

Realization of grain growth and suppressed bulk defects for efficient solution-processed Cu2ZnSn (S, Se)4 solar cells via co-doping strategy

Chang Miao,Meiling Ma,Yingrui Sui,Yue Cui,Zhanwu Wang,Lili Yang,Fengyou Wang,Xiaoyan Liu,Bin Yao

Environmentally benign and earth-abundant constituent’s kieserite Cu 2 ZnSn (S, Se) 4 (Cotises) is considered as a hopeful photovoltaic material. Unfortunately, the severe tail state caused by various harmful deep defects in CZTSSe absorber prevents further development of its device efficiency. Here, we report firstly that the Co was incorporated into CZTSSe films to form the Cu 2 Co x Zn 1-x Sn (S, Se) 4 (CCZTSSe) films using a two-step annealing and solution-processing technique method. Through optimized the Co/(Co+Zn) ratio, the CCZTSSe film has excellent good surface morphology and single-phase composition. Appropriate amount of Co elements replacing Zn elements in CZTSSe films can effectively reduce the degree of Cu-Zn disorder, thus inhibiting [2Cu Zn +Sn Zn ] defect clusters and Cu Zn defects. The detrimental deep defects located in the film were effectively passivated to reduce electrostatic potential fluctuations, resulting in relief of the trailing state. Therefore, a champion device having an efficiency of 7.50 % with a fill factor (FF) of 61.00 % was achieved from CCZTSSe with 3 % Co content. This work provides new insights into the impacts of Co doping in CZTSSe by a solution processed method and offers a deeper comprehension of the origin of the efficiency enhancement of CCZTSSe devices.

研究领域: 材料科学 · 能源技术 · 半导体物理
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CHEMISTRY OF MATERIALS · 2014 · IF 8.535

Versatile and Low-Toxic Solution Approach to Binary, Ternary, and Quaternary Metal Sulfide Thin Films and Its Application in Cu2ZnSn(S,Se)4 Solar Cells

Qingwen Tian,Gang Wang,Wangen Zhao,Yanyan Chen,Yanchun Yang,Lijian Huang,Daocheng Pan

We developed a versatile and environmentally friendly solution approach for the fabrication of a variety of metal sulfide nanocrystal thin films. Metal oxides, metal hydroxides, metal chlorides, metal acetates, and metal acetylacetonates can be used as the starting materials and dissolved in thioglycolic acid and ethanolamine, forming many types of metal–organic precursor solutions. High quality CdS, SnS, CuInS2, CuSbS2, Cu2ZnSnS4, Cu(In0.7Ga0.3)S2, and luminescent Ag-doped ZnxCd1–xS nanocrystal thin films have been successfully prepared by spin-coating their corresponding metal precursor solutions. Cu2ZnSn(S,Se)4 thin film solar cell with a power conversion efficiency of 6.83% has been realized by this versatile method.

研究领域: 材料科学 · 能源技术
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Journal of Materials Chemistry A · 2022 ·Vol. 10 ·期 42 ·22791-22802 · IF 14.511

Ag, Ti dual-cation substitution in Cu2ZnSn(S,Se)4 induced growth promotion and defect suppression for high-efficiency solar cells

Xing-Ye Chen,Muhammad Ishaq,Nafees Ahmad,Rong Tang,Zhuang-Hao Zheng,Ju-Guang Hu,Zheng-Hua Su,Ping Fan,Guang-Xing Liang,Shuo Chen

The existence of various detrimental defects inside the absorber layer is a major obstacle limiting the performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells. Cationic substitution is a viable strategy for overcoming this challenge and has drawn tremendous research attention. In this work, a dual-cation substituted CZTSSe involving Ag and Ti to separately occupy partial Cu and Sn lattice sites is proposed. Under 6% Ag and 1% Ti dual-cation substitution, the champion CZTSSe device delivers a highly interesting efficiency of 12.73%, accompanied by an outstanding VOC of 530 mV. Further investigation demonstrates that Ag introduction can improve the density and crystallinity of CZTSSe thin films while decreasing the concentration of CuZn acceptor defects. Further Ti substitution can effectively eliminate fine grains and reduce the defect density of CuSn and [2CuZn + SnZn] defects, as well as the core level defects. This work explores the synergistic effect of Ag, Ti dual-cation substitution in CZTSSe solar cells for the first time, and the clarified device performance improvement mechanism opens up promising possibilities for the bright development of CZTSSe thin-film photovoltaic technology.

研究领域: 材料科学 · 光伏技术 · 半导体物理
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Solar RRL · 2022 ·Vol. 6 ·期 6 ·2101032 · IF 9.173

Rational Design of Heterojunction Interface for Cu2ZnSn(S,Se)4 Solar Cells to Exceed 12% Efficiency

Junjie Fu,Qingwen Tian,Yachao Du,Qianqian Chang,Yanping Guo,Shengjie Yuan,Zhi Zheng,Sixin Wu,Shengzhong (Frank) Liu

The photovoltaic performance of the kesterite Cu 2 ZnSn(S,Se) 4 solar cells is still far below its predecessor CuInGaSe 2 . One major reason is its severe interface nonradiative recombination at the mismatched Cu 2 ZnSn(S,Se) 4 /CdS heterojunction interface, leading to a large open-circuit voltage loss. Herein, a distinctive indium-incorporation (DI) strategy is developed to deposit an In 1− x Cd x S buffer layer for optimizing the heterojunction interface. The results reveal that adopting this DI method can effectively inhibit the formation of an undesirable secondary phase, and indium can be more easily doped into the bulk lattice of CdS to form additional beneficial shallow donor In Cd defects, which significantly improve the electrical properties of the CdS layer and the quality of the heterojunction interface. Besides, the energy band alignment is adjusted to facilitate the extraction and transfer of interfacial charges, and thus reducing the nonradiative charge recombination at the front Cu 2 ZnSn(S,Se) 4 /CdS heterojunction interface. Consequently, the combination of the above enhances the power conversion efficiency from 10.2% to 12.4%, one of the highest for this type of cells, which corresponds to an open-circuit voltage deficit ( V oc,def ) reduction to as low as 0.54 V. The strategy provides a rational design for optimizing the heterojunction interface of Cu 2 ZnSn(S,Se) 4 solar cells to reduce voltage loss and achieve high efficiency.

研究领域: 材料科学 · 光伏技术 · 可再生能源
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ACS Applied Energy Materials · 2018 · IF 0

Tuning the Se Content in Cu2ZnSn(S, Se)4 Absorber to Achieve 9.7% Solar Cell Efficiency from a Thiol/Amine-Based Solution Process

Junjie Fu,Jie Fu,Qingwen Tian,Houlin Wang,Fengming Zhao,Jun Kong,Xiangyun Zhao,Sixin Wu

The Se content in a Cu2ZnSn(S, Se)4 absorber layer has a significant impact on the electronic properties, but it is rather challenging to control the Se/(S + Se) ratio due to a complicated selenization process. Here, a low-toxicity thiol/amine-based solution process was developed to tune the Se content in a Cu2ZnSn(S, Se)4 absorber layer to an optimal value by ingeniously controlling the SeO2 in the precursor solution. We demonstrated that the crystal growth and the band gap of Cu2ZnSn(S, Se)4 thin films are affected by the Se/(S + Se) ratio. By this approach, the open-circuit voltage deficit (Voc,def) of the device was effectively decreased, and the short-circuit density (Jsc) and fill factor (FF) were remarkably improved; thus, the power conversion efficiency of the Cu2ZnSn(S, Se)4 solar cells was successfully increased from 5.6% to 9.7% for the optimal band gap (Eg = 1.13 eV).

研究领域: 材料科学 · 太阳能电池技术
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Advanced Science · 2023 · IF 15.1

Defect Synergistic Regulations of Li&Na Co-Doped Flexible Cu2ZnSn(S,Se)4 Solar Cells Achieving over 10% Certified Efficiency

Quanzhen Sun,Chen Shi,Weihao Xie,Yifan Li,Caixia Zhang,Jionghua Wu,Qiao Zheng,Hui Deng,Shuying Cheng

Ion doping is an effective strategy for achieving high-performance flexible Cu 2 ZnSn(S,Se) 4 (CZTSSe) solar cells by defect regulations. Here, a Li&Na co-doped strategy is applied to synergistically regulate defects in CZTSSe bulks. The quality absorbers with the uniformly distributed Li and Na elements are obtained using the solution method, where the acetates (LiAc and NaAc) are as additives. The concentration of the harmful Cu Zn anti-site defects is decreased by 8.13% after Li incorporation, and that of the benign Na Zn defects is increased by 36.91% after Na incorporation. Synergistic Li&Na co-doping enhances the carrier concentration and reduces the interfacial defects concentration by one order of magnitude. As a result, the flexible CZTSSe solar cell achieves a power conversion efficiency ( PCE ) of 10.53% with certified 10.12%. Because of the high PCE and the homogeneous property, the Li&Na co-doped device is fabricated to a large area (2.38 cm 2 ) and obtains 9.41% PCE . The co-doping investigation to synergistically regulate defects provides a new perspective for efficient flexible CZTSSe solar cells.

研究领域: 材料科学 · 太阳能 · 半导体物理
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Sustainable Energy & Fuels · 2019 ·Vol. 4 ·期 4 ·1621-1629 · IF 4.912

Heterovalent Ga3+ doping in solution-processed Cu2ZnSn(S,Se)4 solar cells for better optoelectronic performance

Yachao Du,Qingwen Tian,Jin Huang,Yuechao Zhao,Xiaohuan Chang,Afei Zhang,Sixin Wu

Additional elements in Cu2ZnSn(S,Se)4 (CZTSSe) absorber layers present a viable strategy to improve the performance of thin film solar cells. In this study, heterovalent cation doping by partially substituting metal cations with Ga3+ is explored by constructing a sandwich-like configuration. We demonstrated that a low doping level of Ga3+ can be successfully incorporated into the host lattice of CZTSSe to form a homogeneous Cu2ZnSn(Ga) (S,Se)4 (CZTGSSe) alloy material. Characterization was performed using SEM, EDS, XRD, Raman spectroscopy, and XPS, which showed that the material fabricated by this heterovalent cation doping method expressed high phase purity, appropriate valence components, and suitable optical bandgap, which are vital for high performance solar cells. As a result, the champion device achieves stabilized efficiency as high as 10.80%, improved by nearly 28% compared with only 8.43% for the reference device.

研究领域: 材料科学 · 太阳能 · 半导体物理
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SEMICONDUCTOR SCIENCE AND TECHNOLOGY · 2025 ·Vol. 40 ·期 3 ·035006 · IF 2.1

Improving the quality of back contact interface in Cu2ZnSn(S,Se)4 solar cells by inserting a thin Mg(OH)2 intermediate layer

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

Modifying the back contact interface plays a key role in improving the efficiency of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Aiming at the phase decomposition and carrier recombination issues in the CZTSSe/Mo back contact interface, an ultra-thin Mg(OH)2 intermediate layer was introduced between the Mo substrate and the CZTSSe absorber layer. The Mg(OH)2 intermediate layer effectively suppressed the interface phase decomposition reactions and inhibited the generation of interface secondary phases. Meanwhile, during the high-temperature selenization process, the Mg2+ doped into CZTSSe at the back contact interface, reducing the defects and band offset at the CZTSSe/Mo interface. The performance of the device was improved, with a significant increase in efficiency compared to the control device. This work highlights the modification effect of Mg(OH)2 for improving back contact and also provides an easy-handling method to achieve high-performance CZTSSe solar cells.

研究领域: 材料科学 · 能源技术
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Small Methods · 2024 · IF 10.7

Segmented Control of Selenization Environment for High-Quality Cu2ZnSn(S,Se)4 Films Toward Efficient Kesterite Solar Cells

Yue Jian,Litao Han,Xiangrui Kong,Tianliang Xie,Dongxing Kou,Wenhui Zhou,Zhengji Zhou,Shengjie Yuan,Yuena Meng,Yafang Qi,Guangxing Liang,Xianghua Zhang,Zhi Zheng,Sixin Wu

High-crystalline-quality absorbers with fewer defects are crucial for further improvement of open-circuit voltage ( V OC ) and efficiency of Cu 2 ZnSn(S,Se) 4 (CZTSSe) solar cells. However, the preparation of high-quality CZTSSe absorbers remains challenging due to the uncontrollability of the selenization reaction and the complexity of the required selenization environment for film growth. Herein, a novel segmented control strategy for the selenization environment, specifically targeting the evaporation area of Se, to regulate the selenization reactions and improve the absorber quality is proposed. The large evaporation area of Se in the initial stage of the selenization provides a great evaporation and diffusion flux for Se, which facilitates rapid phase transition reactions and enables the attainment of a single-layer thin film. The reduced evaporation area of Se in the later stage creates a soft-selenization environment for grain growth, effectively suppressing the loss of Sn and promoting element homogenization. Consequently, the mitigation of Sn-related deep-level defects on the surface and in the bulk induced by element imbalance is simultaneously achieved. This leads to a significant improvement in nonradiative recombination suppression and carrier collection enhancement, thereby enhancing the V OC . As a result, the CZTSSe device delivers an impressive efficiency of 13.77% with a low V OC deficit.

研究领域: 材料科学 · 太阳能 · 光伏技术
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