Investigation on the Mechanism of Radical Intermediate Formation and Moderate Oxidation of Spiro-OMeTAD by the Synergistic Effect of Multisubstituted Polyoxometalates in Perovskite Solar Cells

• Published in: ACS applied materials & interfaces Vol. 14; no. 15; pp. 17610 - 17620
• Main Authors: Hu, Boyuan, Jian Zhang, Yang, Yulin, Wang, Jiaqi, Wang, Wei, Li, Jiao, Liu, Shihui, Xia, Debin, Lin, Kaifeng, Dong, Yayu, Fan, Ruiqing
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 20.04.2022
• Subjects: Functional Inorganic Materials and Devices; perovskite solar cell; heteroatom-substituted polyoxometalates; controllable oxidation; mechanism; interfacial charge transfer
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.1c24337

Conventional oxidation of 2,2′,7,7′-tetrakis­[N,N-di­(4-methoxyphenyl)­amino]-9,9′-spirobifluorene (Spiro-OMeTAD) by air would bring various drawbacks for perovskite solar cells (PSCs), such as low power conversion efficiency (PCE) and poor stability. Here, a series of heteroatom-substituted Keggin-type polyoxometalates (POMs), H4PMo11VO40 (PMo11V), H5PMo10V2O40 (PMo10V2), and H6PMo9V3O40 (PMo9V3) are prepared and applied as p-type dopants to realize quantitative and controllable oxidation of Spiro-OMeTAD under an inert condition. The possible mechanism and electron donor regions in the oxidation of Spiro-OMeTAD are investigated using two-dimensional nuclear magnetic resonance (NMR) spectra and the relationship between POM structures and the oxidation degree of Spiro-OMeTAD is proposed. In addition, the synergistic effect of heteroatoms makes V2-substituted PMo10V2 exhibit appropriate oxidation of Spiro-OMeTAD and promoted the highest efficient hole extraction as well as the decreased charge recombination. Therefore, the champion device doped with PMo10V2 shows a PCE of 20.41% and a superior open circuit voltage (V oc) of 1.133 V, surpassing that of the pristine device (18.61%). This work presents a fresh perspective to the controllable oxidation of Spiro-OMeTAD employing economical inorganic POM dopants, which would promote the commercialization of PSCs.