Paul Philipp Wellmann, Fabian Pieck, Ralf Tonner-Zech
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引用次数: 0
Abstract
We investigate the blocking layer formation of the trimethoxypropylsilane small molecule inhibitor (SMI), its blocking mechanisms, and all relevant blocking layer disintegration reactions on SiO2 in the area-selective atomic layer deposition of Al2O3 with density functional theory-based methods. The choice of amorphous silica (a-SiO2) surface models proves to be essential for obtaining the correct SMI chemistry. We demonstrate that complete blocking of reactive sites is possible here and deduce an upper SMI density limit of the resulting blocking layer that is limited by Pauli repulsion. The SMI adsorption process can nevertheless leave unreacted silanol groups, which could be remedied by using a second monodentate SMI. The SMI layer is inert against neither common aluminum precursors nor the co-reactant water as our comprehensive analysis of the various blocking layer disintegration reactions for different SMI layer densities shows. We report a new blocking mechanism of the SMI layer and propose to differentiate what is discussed as the “steric blocking” effect into the known “adsorption prevention” effect and the newly found “reactivity reduction” effect. For trimethylaluminum (TMA), an additional favorable SMI layer decomposition mechanism is found compared to that of the bulkier triethylaluminum (TEA), which could explain the lower selectivity of TMA found experimentally. Our computational work offers some principles and ideas for future experiments to improve selectivity in area-selective atomic layer deposition processes.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.