| A series of new organometallic precursors and/or reactions have been investigated for the facile production of main group compound semiconductors at relatively low temperature. The common feature among the organometallic compounds used in this study is that they all contain the benzyl ligand, Bn = CH2C6H5. Novel dual source reactions between benzylated organometallic compounds, and elemental sulfur or selenium produce the underrepresented Group 14/16 and Group 15/16 solid-state binary semiconductors as well as the corresponding Sn(SxSe1-x) and (Bi xSb1-x)2S3 solid solutions. In addition, new single-source precursors that produce germanium sulfide, selenide, tin telluride, and bismuth sulfide under mild conditions have been synthesized.;By judicious choice of the precursor and the reaction conditions, synthetic control over the size and microstructure of Bi2S3 particles is achieved. Decomposition of (BnS)3Bi at mild temperatures forms small (∼1 mum) aggregates of nearly spherical botryoidal particles or 6 mum diameter spherical particles composed of radiating acicular crystallites. The reaction of Bn3Bi with sulfur produces small spherical crystallites 200--300 nm in size; rod-like crystallites 500--700 nm in width and 4--5 mum in length; or dense, prismatic rods ∼1 mum in length and 500 nm wide.;Two new chemical vapor deposition (CVD) sources of the technologically important elements antimony and bismuth have been identified. Bn3Sb and Bn3Bi were shown to grow films of these elements under low-pressure conditions (LPCVD). Depositions on glass and Si(100) substrates were performed. Resulting films are of high purity, good adherence, and highly crystalline as determined by X-ray powder diffraction (XRPD). The films also exhibit a high degree of texture. The texture of Sb films could be controlled by varying the distance of the deposition substrate to that of the precursor. Bi films were highly oriented in the (012) crystallographic direction, where most deposition methods produce c-axis (003), oriented films. Both precursors are safer, easier to handle, and pyrolyze more efficiently at lower temperatures than the industry standards, (CH3)3M (M = Sb, Bi). Additionally, the use of Bn3Sb in the synthesis and CVD of InSb has been demonstrated. |
