Daoyong Zhang,Shizhong Sun,Xinyu Li,Xiang Li,Xin Liu,Qiulian Li,Hua Liao,Shurong Wang
In this paper, Cu 2 ZnSn(S x Se 1− x ) 4 (CZTSSe) thin-films with a front-graded band gap were prepared by plasma sulfurization. The method of selenization followed by low-temperature plasma sulfurization was adopted to effectively control the uneven diffusion of S in the absorption layer. By investigating and analyzing the grazing incidence X-ray diffraction, Raman spectroscopy, and PL spectra, the CZTSSe absorption layer with an S-rich top and S-poor bottom layer could be obtained by plasma sulfurization. The inhomogeneous distribution of S led to the formation of band gap gradients. Based on that, the band gap near the top of the absorption layer was determined to be 1.13 eV and the bottom band gap was 1.03 eV. Approximately 300 nm thick sulfur-rich CZTSSe films were found near the surface favoring an increase in the band gap at the interface, which could be attributed to a high open circuit voltage (V oc ). The establishment of the band gap gradient formed a barrier towards the motion of holes towards the interface and increased the effective interfacial recombination band gap, both of which significantly reduced the interfacial recombination. Finally, the CZTSSe thin-film solar cells with a band gap gradient were prepared by plasma sulfurization exhibited a power conversion efficiency (PCE) of 8.11%. Compared with CZTSSe thin-film solar cells without post plasma sulfurization, which had a PCE of 6.98%, the V oc of the CZTSSe solar cell improved considerably from 471.37 mV to 513.93 mV; however, it had little effect on short-circuit current density (J sc ).
In the pursuit of high-performance electrochromic materials, in this paper, six donor-acceptor type with different gradient band gaps electrochromic conjugated polymers, named PBTz-T, PBTz-TT, PBTz-DT, PTBTO8-T, PTBTO8-TT, and PTBTO8-DT, were synthesized via direct (hetero) arylation polymerization, employing two benzothiadiazole derivatives with varying electron-accepting capabilities and three thiophene derivatives with different electron-donating capacities. The structures, optical, electrochemical, and electrochromic properties of the six polymers were investigated. As the number of fused thiophene increases, enhancing the electron-donating ability, a growth trend of electrochemical stability is observed for all polymers. Meanwhile, enhance electron-accepting capabilities of acceptors (from benzotriazole to benzothiadiazole) significantly lower the electronic band gap and improve electrochemical stability. PBTz-DT boasts a bleaching time of 0.3 s, outperforming most reported electrochromic polymers. PBTz-T, at 530 nm, exhibits exceptionally high coloration efficiency, reaching 916 cm 2 C⁻ 1 , and demonstrates higher electron utilization and lower energy consumption, making it an excellent candidate for high-performance electrochromic devices. This work compared studies the relationship of gradient band gaps of electrochromic conjugated polymers and their electrochemical and electrochromic performance, offers new insights into enhancing the electrochemical stability and synthesizing high coloration efficiency electrochromic materials.
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