Abstract
In this work, the Cu2MnxZn1−xSn(S,Se)4 (0 ≤ x ≤ 1) (CMZTSSe) alloy films were fabricated by a sol-gel method. Meanwhile, the effects of Mn substitution on the structural, morphological, electrical, optical, and device performance were studied systematically. The clear phase transformation from Cu2ZnSn(S,Se)4 (CZTSSe) with kesterite structure to Cu2MnSn(S,Se)4 (CMTSSe) with stannite structure was observed as x = 0.4. The scanning electron microscope (SEM) results show that the Mn can facilitate the grain growth of CMZTSSe alloy films. Since the x was 0.1, the uniform, compact, and smooth film was obtained. The results show that the band gap of the CMZTSSe film with a kesterite structure was incessantly increased in a scope of 1.024–1.054 eV with the increase of x from 0 to 0.3, and the band gap of the CMZTSSe film with stannite structure was incessantly decreased in a scope of 1.047–1.013 eV with the increase of x from 0.4 to 1. Meanwhile, compared to the power conversion efficiency (PCE) of pure CZTSSe device, the PCE of CMZTSSe (x = 0.1) device is improved from 3.61% to 4.90%, and about a maximum enhanced the open-circuit voltage (VOC) of 30 mV is achieved. The improvement is concerned with the enhancement of the grain size and decrease of the Cu instead of Zn (CuZn) anti-site defects. Therefore, it is believed that the adjunction of a small amount of Mn may be an appropriate approach to improve the PCE of CZTSSe solar cells.
Highlights
Cu2ZnSn(S,Se)4 (CZTSSe) has drawn great attention due to tunable band gaps and high absorption coefficient (>104 cm−1) [1,2,3]
Compared to the power conversion efficiency (PCE) of pure CZTSSe device, the PCE of CMZTSSe (x = 0.1) device is improved from 3.61% to 4.90%, and about a maximum enhanced the open-circuit voltage (VOC) of 30 mV is achieved
The highest power conversion efficiency (PCE) of CZTSSe device is 12.6% [4,5], which is significantly lower than the theoretical prediction value and the PCE of Cu(In,Ga)Se2 (CIGS) device [6]
Summary
Cu2ZnSn(S,Se) (CZTSSe) has drawn great attention due to tunable band gaps and high absorption coefficient (>104 cm−1) [1,2,3]. Replacing Cu with Ag in CZTSSe is an efficacious method to decrease the concentration of anti-site defects, which, thereby, improves device performance [13,14,15]. Due to the mismatch of ion radius and high formation energy for Cd and Ag, these doping elements have difficulty in entering the crystal lattice and can only exist on the surface of grain boundaries of CZTSSe [19] According to these issues, the doping of Cd and Ag elements is not the most appropriate, so it is still necessary to establish a suitable cation substitute to decrease cation anti-site defects and improve properties of the CZTSSe absorber layer.
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