Cao Yan-Qiang, Zhang Wei, Xu Lina, Liu Chang, Zhu Lin, Wang Lai-Guo, Wu Di, Li Ai-Dong, Fang Guoyong
National Laboratory of Solid State Microstructures, Jiangsu Key Laboratory of Artificial Functional Materials, Materials Science and Engineering Department, College of Engineering and Applied Sciences, Collaborative Innovation Center of Advanced Microstructures , Nanjing University , No. 22 Hankou Road , Gulou District, Nanjing , Jiangsu 210093 , P. R. China.
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering , Wenzhou University , No. 276 Xueyuanzhong Road , Wenzhou , Zhejiang 325035 , P. R. China.
Langmuir. 2019 Feb 26;35(8):3020-3030. doi: 10.1021/acs.langmuir.8b04137. Epub 2019 Feb 15.
Ti-based maleic acid (MA) hybrid films were successfully fabricated by molecular layer deposition (MLD) using organic precursor MA and inorganic precursor TiCl. The effect of deposition temperature on the growth rate, composition, and bonding mode of hybrid thin films has been investigated systematically. With increasing temperature from 140 to 280 °C, the growth rate decreases from 1.42 to 0.16 Å per MLD cycle with basically unchanged composition ratio of C:O:Ti in the films. Fourier transform infrared spectra indicate that all hybrid films show preference for bidentate bonding mode. Further analyses of X-ray photoelectron spectroscopy and in situ quartz crystal microbalance elucidate that as-deposited MLD Ti-MA hybrid films consist of inorganic Ti-O-Ti units and organic-inorganic Ti-MA units. In addition, the density functional theory calculation was performed to investigate the possible reaction mechanism of the TiCl-MA MLD process, which is well consistent with experimental results. More importantly, upon comparison with the TiCl-fumaric acid MLD system, it is demonstrated that the cis- and trans-configurations of butenedioic acid influence the MLD growth, bonding mode, stability, and charging ability of MLD hybrid films. Ti-MA hybrid films exhibit better stability and charging ability than Ti-FA hybrid films, benefiting from the inorganic Ti-O-Ti units in the hybrid films.
通过使用有机前驱体马来酸（MA）和无机前驱体TiCl，采用分子层沉积（MLD）成功制备了基于Ti的马来酸（MA）混合薄膜。系统研究了沉积温度对混合薄膜生长速率、组成和键合模式的影响。随着温度从140℃升高到280℃，生长速率从每MLD循环1.42 Å降低到0.16 Å，薄膜中C:O:Ti的组成比基本不变。傅里叶变换红外光谱表明，所有混合薄膜都倾向于双齿键合模式。X射线光电子能谱和原位石英晶体微天平的进一步分析表明，沉积态的MLD Ti-MA混合薄膜由无机Ti-O-Ti单元和有机-无机Ti-MA单元组成。此外，进行了密度泛函理论计算以研究TiCl-MA MLD过程的可能反应机理，其与实验结果非常一致。更重要的是，与TiCl-富马酸MLD体系相比，证明了丁烯二酸的顺式和反式构型影响MLD混合薄膜的MLD生长、键合模式、稳定性和充电能力。Ti-MA混合薄膜比Ti-FA混合薄膜表现出更好的稳定性和充电能力，这得益于混合薄膜中的无机Ti-O-Ti单元。
