Interfacial catalysis in and initial reaction mechanism of Al2O3films fabricated by atomic layer deposition using non-hydrolytic sol-gel chemistry.
Atomic layer deposition (ALD) is a powerful nanofabrication technique that can precisely control the composition, structure, and thickness of thin films at the atomic scale, and is widely used in the fields of electronic displays, microelectronics, catalysis, coatings, and energy storage and conversion. ALD of metal oxide thin films can be completed using metal alkoxides as the oxygen source, which is similar to the non-hydrolytic sol-gel (NHSG) technique. Density functional theory calculations show that metal alkoxides, such as Al(OiPr)3and Al(OEt)3, can directly form M-O bonds through strong chemisorption on the surface. Meanwhile, alkyl groups can be eliminated through the formation of alkyl halides and alkenes, which can be catalyzed by interfacial interactions between alkyl groups and the surface. Such noncovalent catalysis resulting from interfacial interaction can be termed as interfacial catalysis. This can be characterized by the difference between the interfacial interaction energies of the transition state and the corresponding intermediate based on natural bond analysis. We expect that such interfacial catalysis can be used in precursor designs, improvement of ALD of oxides and as a new characterization method for other interfacial catalysis and noncovalent catalysis processes.
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China. fanggy@wzu.edu.cn.
Lina
http://orcid.org/0000-0002-0455-3839
L
Xu
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China. fanggy@wzu.edu.cn and National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China.
Guoyong
http://orcid.org/0000-0001-6817-3790
G
Fang
National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China.
Yanqiang
Y
Cao
National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China.
Aidong
A
Li