While searching for bismuth precursors for thin film preparation by atomic layer deposition (ALD) three bismuth alkoxides Bi(Ot Bu)3 (1), Bi(OCMe2 iPr)3 (2), Bi(OCi Pr3 )3 (3), bismuth b-diketonate, Bi(thd)3 (4), and bismuth carboxylate, Bi(O2Ct Bu)3 (5), were synthesized and evaluated. The compounds were characterized by CHN, NMR,MS, and TGA/SDTA. Earlier unknown crystal structures of compounds 1 and 3 were solved. Compound 1 forms dimeric and loose polymeric structures in the solid state while 3 is strictly monomeric. For compound 2 crystals suitable for complete structure solution could not be grown. Crystallization trials of 2 from hexane and toluene resulted in oxygen bridged tetramer [Bi2 O(OCMe2 iPr)4 ]2 (6). Compound 4 has dimeric structure and compound 5 forms loose tetramers as reported earlier. The structure of toluene solvated crystal [Bi(O2Ct Bu)3 ]4 ·2MeC6 H5 (7)was solved. All compounds studied showed relatively good volatility and thermal stability. They were all tested in ALD deposition experiments, in which compound 2 was found to be the most suitable for ALDgrowthofBi2 O3 . It exhibited a clear improvement over Bi precursors studied earlier.
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