Feasibility of novel (H3C)(n)X(SiH3)(3-n) compounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations
2015 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 44, no 7, 3356-3366 p.Article in journal (Refereed) Published
We employ ab initio calculations to predict the equilibrium structure, stability, reactivity, and Raman scattering properties of sixteen different (H3C)(n)X(SiH3)(3-n) compounds (X = B, Al, Ga, In) with n = 0-3. Among this methylsilylmetal family, only the (H3C)(3)X members, i.e., trimethylboron (TMB), trimethylaluminum (TMA), trimethylgallium (TMG), and trimethylindium (TMI), are currently well-studied. The remaining twelve compounds proposed here open up a two-dimensional array of new possibilities for precursors in various deposition processes, and evoke potential applications in the chemical synthesis of other compounds. We infer that within the (H3C)(n)X(SiH3)(3-n) family, the compounds with fewer silyl groups (and consequently with more methyl groups) are less reactive and more stable. This trend is verified from the calculated cohesive energy, Gibbs free energy of formation, bond strength, and global chemical indices. Furthermore, we propose sequential reaction routes for the synthesis of (H3C)(n)X(SiH3)(3-n) by substitution of methyl by silyl groups, where the silicon source is the silane gas. The corresponding reaction barriers for these chemical transformations lie in the usual energy range typical for MOCVD processes. We also report the Raman spectra and light scattering properties of the newly proposed (H3C)(n)X(SiH3)(3-n) compounds, in comparison with available data of known members of this family. Thus, our computational experiment provides useful information for a systematic understanding of the stability/reactivity and for the identification of these compounds.
Place, publisher, year, edition, pages
Royal Society of Chemistry , 2015. Vol. 44, no 7, 3356-3366 p.
IdentifiersURN: urn:nbn:se:liu:diva-115338DOI: 10.1039/c4dt03406fISI: 000349403100048PubMedID: 25599815OAI: oai:DiVA.org:liu-115338DiVA: diva2:795009
Funding Agencies|Swedish Foundation for International Cooperation in Research and Higher Education (STINT) [YR2009-7017]; Swedish Research Council (VR) [348-2014-4249]; Linkoping Linnaeus Initiative on Novel Functionalized Materials (VR); Swedish Foundation for Strategic Research (SSF) Synergy on Functional Carbides and Advanced Surface Engineering (FUNCASE) [RMA-110029]; Swedish Governmental Agency for Innovation Systems (VINNOVA); Swedish Research Council (VR); Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq); Fundacao de Ampar a Pesquisa do Estado da Bahia (FAPESB); Coordenacao de Aperfeicoamento de Pessoal de Novel Superior (CAPES)2015-03-132015-03-132015-03-26