Group 13 Chalcogenides: Molecules and Materials

该奖项由化学部特别项目办公室颁发，以支持莱斯大学安德鲁·巴伦博士的继续研究。这项研究将集中在13-16族材料的化学气相沉积过程中前体分子结构的作用，以及新的13族硫族化合物的合成和反应活性。在发现稳定的笼状结构中间体可以形成亚稳态固相后，将研究在气相中保留笼状结构的条件。为此，将建立一个气溶胶-CVD系统，该系统将消除气相分解。具体地说，将合成环状和笼状的镓和铟、硫化物、硒和碲化物的有机金属络合物，并在设计的条件下进行分解，以保持前驱体的结构完整性，并用俄歇能谱、XPS、透射电子显微镜、扫描电子显微镜、X射线衍射仪和电子衍射仪对新相进行表征。随后将对相生长的机理进行研究，并对分解产物进行飞行时间质谱分析和基质分离。其他研究将调查使用硫化镓笼子作为扩展中间相结构的分子构建块，以及使用笼状硫化镓结构作为齐格勒聚合中铝氧烷的模型。13-16族硫族化合物的基础化学不如相应的氧化物发达。这项研究将确定在化合物半导体、催化剂和多孔沸石类材料中应用的新固相设计和合成的结构和动力学要求。

This award is made in the Office of Special Projects of the Chemistry Division in support of the continuing research of Dr. Andrew Barron at Rice University. The research will focus on the role of precursor molecular structure during chemical vapor deposition of Group 13-16 materials and the synthesis and reactivity of new Group 13-chalcogenide compounds. Having discovered that metastable solid phases can be formed from stable cage structure intermediates, conditions will be investigated which retain the cage structure in the gas phase. To this end, an aerosol-CVD system will be built which will eliminate gas phase decomposition. Specifically, cyclic and cage organometallic complexes of gallium and indium, sufides, selenides and tellurides will be synthesized and decomposed under conditions designed to preserve the structural integrity of the precursors, New phases will be characterized by Auger spectroscopy, XPS, TEM, SEM, x-ray diffraction and electron diffraction. Mechanistic studies of phase growth will be followed by time-of-flight mass spectrometry and matrix isolation of the decomposition products. Other studies will investigate the use of gallium-sulfide cages as molecular building blocks for extended mesophase structures and the use of caged gallium sulfide structures as models for alumoxanes in Ziegler polymerization. The fundamental chemistry of Group 13-16 chalcogenides is less well developed than the corresponding oxides This research will define the structural and kinetic requirements for the design and synthesis of new solid phases for applications in compound semiconductors, catalysis, and porous zeolite-like materials.