Effect of solid-H<sub>2</sub>S gas reactions on CZTSSe thin film growth and photovoltaic properties of a 12.62% efficiency device

Son, Dae‐Ho; Kim, Seung Hyun; Kim, Se-Yun; Kim, Young‐Ill; Sim, Jun-Hyung; Park, Si-Nae; Jeon, Dong‐Hwan; Hwang, Dae‐Kue; Sung, Shi‐Joon; Kang, Jin‐Kyu; Yang, Kee‐Jeong; Kim, Dae-Hwan

doi:10.1039/c9ta08310c

Cited by 243 publications

(183 citation statements)

References 39 publications

(41 reference statements)

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“…Nearly all the highly efficient CZTSSe solar cells are fabricated from the absorber with Cu‐poor and Zn‐rich compositions. [ 2,3,23 ] Theoretical calculation on kesterite materials reported by Chen et al, [ 14 ] also suggests that Cu‐poor and Zn‐rich conditions are helpful for the reduction of antisite defects. Most of the studies adopt the empirical value with Cu/(Sn + Zn) = 0.8 and Zn/Sn = 1.2 as the optimal composition, whereas some other groups tried to get more insights into the influence of the elemental ratios on the device performance.…”

Section: Introductionsupporting

confidence: 80%

Surprising Efficiency Enhancement of Cu₂ZnSn(S,Se)₄ Solar Cells with Abnormal Zn/Sn Ratios

Huang

et al. 2020

Solar RRL

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The elemental proportion of Cu poor and Zn rich in Cu2ZnSn(S,Se)4 (CZTSSe) is well established for achieving highly efficient CZTSSe solar cells. However, how high Zn/Sn ratio can the complicated CZTSSe thin film tolerate remains a question. Therefore, herein, the well control of Zn/Sn ratio in CZTSSe thin film is obtained by multi‐spin‐coating and tuning the initial Zn/Sn ratio in the Cu–Zn–Sn–S precursor ink from 1.0 to 1.9. It is found that the Zn/Sn on the surface of CZTSSe absorber can self‐regulate to around 1.2 even with Zn/Sn ratio up to 1.9 in the precursor solution. Excess Zn presented as Zn(S,Se) secondary phase not only concentrate near the bottom area, but also widely distribute at the grain boundaries (GBs). In addition, it is found that the Zn(S,Se) secondary phase at GBs can promote current transport as revealed by conductive atomic force microscopy measurement. The surface roughness and grain size of the resulting CZTSSe absorber increased, whereas the MoSe2 thickness was reduced with increasing Zn/Sn ratio. More importantly, the device performance increased from 4.5% to 10.0% with a significant decrease in VOC deficit from 0.73 to 0.58 V when the Zn/Sn ratio increases from 1.0 to 1.5 in the precursor ink.

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Section: Introductionsupporting

confidence: 80%

Surprising Efficiency Enhancement of Cu₂ZnSn(S,Se)₄ Solar Cells with Abnormal Zn/Sn Ratios

Huang

et al. 2020

Solar RRL

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“…These materials exhibit p-type conductivity, a large absorption coefficient (more than 10 4 cm −1 ), and a tunable direct bandgap ranging between 1.0 (CZTSe) and 1.5 eV (CZTS). 1,4,5 However, the reported maximum conversion efficiency of CZTSSe is only 12.6%, 6,7 which is far below the theoretical solar conversion efficiency of Cu 2 ZnSnS 4 (CZTS)-based thin-film solar cells (32.4%). 8 Extensive research to improve the poor efficiency of CZTSSe solar cells has focused on the reduction of the high V OC deficit, which is also related with their low fill factor (FF).…”

mentioning

confidence: 94%

Improved interfacial properties of electrodeposited Cu₂ZnSn(S,Se)₄ thin‐film solar cells by a facile post‐heat treatment process

Hwang

Park

Cheon

et al. 2020

Progress in Photovoltaics

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Cu 2 ZnSn(S,Se) 4 (CZTSSe) thin-film solar cells offer various advantages including excellent optical and electrical properties, nontoxic and earth-abundant raw materials, and a simple fabrication process. However, these devices suffer from a high deficit of the open-circuit voltage (V OC), mainly caused by interface recombination, which increases with increasing surface roughness. In this study, to achieve a high V OC and enhance the overall device performance, an additional heat treatment process was introduced during the fabrication of co-electrodeposited rough CZTSSe solar cells, and its effect on the photovoltaic properties was systematically investigated using various characterization techniques including diode analysis, transient photovoltage decay measurement, evaluation of the temperature dependency of the open-circuit voltage, current-voltage and drive-level capacitance profile analysis, and electrochemical impedance spectroscopy. At the optimized post-heat treatment (PHT) temperature of 200 C, a significant increase in the conversion efficiency (as high as 32%, from 7.11% to 9.40%) was observed owing to the change in the interfacial materials properties (i.e., higher conductivity and reduced interfacial nonradiative recombination), which in turn is a consequence of the diffusion of the Cd ions and the expansion of the Cu-poor/Zn-rich phase. The PHT-applied CZTSSe device exhibited a high conversion efficiency close to the record-high one reported for electrodeposited CZTSSe thin-film solar cells. These findings confirm the

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“…Besides the hydrazine-based method, the sputtering method also produced highly efficient CZTSSe devices, 12.6% for a small cell size and 11.3% for a larger cell size (1.176 cm 2 ), as shown in Fig. 2d [60]. Obviously, the highest efficiency was achieved in CZTSSe absorber with low S content (E g ≈1.1 eV).…”

Section: Development Status and Main Problemmentioning

confidence: 92%

“…Performance parameters including short-circuit current density (J SC ), open-circuit voltage (V OC ) and fill factor (FF) of the reported CZTSSe solar cells with efficiencies above 11% are summarized and shown in Fig. 2a-d [13,28,[47][48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63]. These devices were prepared by different processes, including non-vacuum (i.e., hydrazine-based and non-hydrazine spin coating) and vacuum (i.e., coevaporation, and sputtering) methods.…”

Section: Development Status and Main Problemmentioning

confidence: 99%

Underlying mechanism of the efficiency loss in CZTSSe solar cells: Disorder and deep defects

Duan

Shi

et al. 2020

Sci. China Mater.

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Although Cu 2 ZnSn(S x , Se 1−x) 4 (CZTSSe) is a promising candidate for thin-film photovoltaics, its cell performance is currently limited by the large voltage loss. Although a series of studies on the efficiency loss mechanism of CZTSSe solar cell have been carried out in the past few years, no convincing understanding has been obtained until now. In this review, the current findings regarding the underlying mechanism of the efficiency loss in CZTSSe solar cells are systematically summarized and analyzed. The properties of atomic disorder and deep defects in CZTSSe materials and their effects on device performance are discussed. The synergistic effect is proposed to help understand the defect-related charge loss in the absorber. Furthermore, the experimental methods of defect identification and defect control are presented, in an attempt to identify the killer defects that can be responsible for the ultra-short minority lifetime of CZTSSe material. By comprehensively and dialectically understanding these defect properties of the CZTSSe solar cell, we believe breakthrough in the cell efficiency will come soon with our concentrated effort.

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Effect of solid-H₂S gas reactions on CZTSSe thin film growth and photovoltaic properties of a 12.62% efficiency device

Abstract: 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.

Cited by 243 publications

References 39 publications

Surprising Efficiency Enhancement of Cu₂ZnSn(S,Se)₄ Solar Cells with Abnormal Zn/Sn Ratios

Surprising Efficiency Enhancement of Cu₂ZnSn(S,Se)₄ Solar Cells with Abnormal Zn/Sn Ratios

Improved interfacial properties of electrodeposited Cu₂ZnSn(S,Se)₄ thin‐film solar cells by a facile post‐heat treatment process

Underlying mechanism of the efficiency loss in CZTSSe solar cells: Disorder and deep defects

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Effect of solid-H2S gas reactions on CZTSSe thin film growth and photovoltaic properties of a 12.62% efficiency device

Abstract: 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.

Cited by 243 publications

References 39 publications

Surprising Efficiency Enhancement of Cu2ZnSn(S,Se)4 Solar Cells with Abnormal Zn/Sn Ratios

Surprising Efficiency Enhancement of Cu2ZnSn(S,Se)4 Solar Cells with Abnormal Zn/Sn Ratios

Improved interfacial properties of electrodeposited Cu2ZnSn(S,Se)4 thin‐film solar cells by a facile post‐heat treatment process

Underlying mechanism of the efficiency loss in CZTSSe solar cells: Disorder and deep defects

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Effect of solid-H₂S gas reactions on CZTSSe thin film growth and photovoltaic properties of a 12.62% efficiency device

Surprising Efficiency Enhancement of Cu₂ZnSn(S,Se)₄ Solar Cells with Abnormal Zn/Sn Ratios

Surprising Efficiency Enhancement of Cu₂ZnSn(S,Se)₄ Solar Cells with Abnormal Zn/Sn Ratios

Improved interfacial properties of electrodeposited Cu₂ZnSn(S,Se)₄ thin‐film solar cells by a facile post‐heat treatment process