硫化物靶与单质靶制备Cu2ZnSnS4薄膜的比较研究

doi:10.15541/jim20180304

摘要/Abstract

摘要：

为了验证磁控溅射硫化物靶替代单质靶制备Cu₂ZnSnS₄(CZTS)薄膜及太阳电池的可行性与优越性, 采用多周期磁控溅射ZnS-Sn-CuS和Zn-Sn-Cu制备CZTS薄膜, 并分析了使用不同溅射靶材对薄膜晶体结构、相纯度、表面粗糙度、化学组分、表面、截面形貌及光电特性的影响。按SLG/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Ni-Al结构制成完整的电池器件并测量了J-V曲线。结果显示采用ZnS-Sn-CuS靶制备的CZTS薄膜太阳电池开路电压为611 mV, 短路电流密度为21.28 mA/cm ², 光电转换效率达5.11%; 而以单质靶为基础制备的太阳电池开路电压为594 mV, 短路电流密度为18.56 mA/cm ², 光电转换效率为4.13%。这归因于采用ZnS-Sn-CuS制备的CZTS薄膜相比于单质靶更加平整致密, 纵向生长更好。证明了采用硫化物靶制备CZTS薄膜及太阳电池相较于单质靶的优越性。

关键词: 铜锌锡硫薄膜, 太阳电池, 二元硫化物靶, 金属单质靶

Abstract:

To verify feasibility and superiority of preparing Cu₂ZnSnS₄ (CZTS) thin films and solar cells by sputtering chalcogenide targets instead of single targets, two kinds of CZTS thin films were synthesized via multi-period sputtering ZnS-Sn-CuS and Zn-Sn-Cu, respectively. Influence of different sputtering targets on crystal structure, phase purity, surface roughness, chemical composition, surface and cross-sectional morphology, and optical-electrical properties of CZTS thin films were investigated in detail. Subsequently, the complete devices were fabricated according to SLG/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Ni-Al and J-V characteristics of cells were measured. The results show that the solar cell made of ZnS-Sn-CuS precursor owns an open-circuit voltage of 611 mV, short-circuit current density of 21.28 mA/cm ² and efficiency of 5.11% while the solar cell based on single targets shows an open-circuit voltage of 594 mV, short-circuit current density of 18.56 mA/cm ² and an efficiency of 4.13%. It is attributed to the fact that the CZTS thin films prepared by ZnS-Sn-CuS have smoother, denser surface and better longitudinal growth compared with those prepared by single targets. The result confirms the superiority of the CZTS thin film and solar cells prepared using the chalcogenide targets over those from single targets.

Key words: Cu₂ZnSnS₄ thin films, solar cells, binary sulfide target, single metal target

中图分类号:

TN304

徐信, 王书荣, 马逊, 杨帅, 李耀斌, 杨洪斌. 硫化物靶与单质靶制备Cu₂ZnSnS₄薄膜的比较研究[J]. 无机材料学报, 2019, 34(5): 529-534.

Xin XU, Shu-Rong WANG, Xun MA, Shuai YANG, Yao-Bin LI, Hong-Bin YANG. Comparative Study of Cu₂ZnSnS₄ Thin Films Prepared by Chalcogenide and Single Targets[J]. Journal of Inorganic Materials, 2019, 34(5): 529-534.

图/表 10

图1 不同预制层制备的CZTS薄膜的XRD图谱

Fig. 1 XRD patterns of the CZTS thin films obtained with different precursors

图2 不同预制层制备的CZTS薄膜的拉曼图谱

Fig. 2 Raman spectra of the CZTS thin films obtained with different precursors

图3 不同预制层制备的(a, c)CZTS1和(b, d)CZTS2薄膜的SEM照片 (a-b): ×20000; (c-d): ×50000

Fig. 3 SEM images of (a, c) CZTS1 and (b, d) CZTS2 thin films obtained via different precursors

表1 CZTS1和CZTS2薄膜组分及元素比例

Table 1 Chemical composition of CZTS1 and CZTS2 thin film

Sample	Cu/at%	Zn/at%	Sn/at%	S/at%	Cu/(Zn+Sn)	Zn/Sn
CZTS1	20.52	13.47	11.24	54.75	0.83	1.2
CZTS2	21.63	13.31	10.75	54.31	0.90	1.23

图4 (a~c) CZTS1和(d~f) CZTS2的原子力显微镜图

Fig. 4 AFM images of (a-c) CZTS1 and (d-f) CZTS2 thin films

图5 CZTS1*与CZTS2*的(a)光吸收系数光谱图及(b)带隙图

Fig. 5 (a) Optical absorption coefficient and (b) plots of ($\alpha$hv)2 vs. photon energy (hv) of CZTS1* and CZTS2*

表2 CZTS1*与CZTS2*的电学性能参数

Table 2 Electrical properties of CZTS1* and CZTS2*

Sample	Mobility /(cm²·V^-1·s^-1)	Charge carrier concentration/cm³	Resistivity /(Ω·cm)
CZTS1*	5.65	8.58×10¹⁷	0.94
CZTS2*	4.36	6.88×10¹⁸	1.07

图6 薄膜太阳电池Cell-1和Cell-2的截面SEM照片

Fig. 6 Cross sectional SEM images of Cell-1 and Cell-2

图7 Cell-1与Cell-2的J-V曲线

Fig. 7 J-V curves of the Cell-1 and Cell-2

表3 Cell-1与Cell-2的电池参数

Table 3 Parameters of cell-1 and Cell-2

Cell	V_oc/mV	J_sc/ (mA·cm^-2)	η/%	FF/%	R_S/ (Ω·cm^-2)	R_sh/ (Ω·cm^-2)
Cell-1	611	21.28	5.11	39	12.7	151.8
Cell-2	594	18.56	4.13	37	14.4	135.1

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硫化物靶与单质靶制备Cu₂ZnSnS₄薄膜的比较研究

Comparative Study of Cu₂ZnSnS₄ Thin Films Prepared by Chalcogenide and Single Targets

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