| A synthetic route to indium fluoroalkoxide complexes was developed and fluorine-doped indium oxide films were prepared from one of the new complexes by chemical vapor deposition.; The reaction of indium amide complexes with fluorinated alcohols was found to be a convenient synthetic route to indium fluoroalkoxide complexes. In[N-t-Bu(SiMe3)]3 reacted with (CF3)Me2COH to give the dimer [In{lcub}mu-OCMe 2(CF3){rcub}{lcub}OCMe2(CF3){rcub}2] 2. In contrast, reactions involving the more acidic alcohols (CF 3)2MeCOH and (CF3)2CHOH yielded products containing t-BuNH2, which was derived from the amide ligands of the starting material. Reactions of (CF3) 2MeCOH and (CF3)2CHOH with In(tmp)3 (tmp = the anion derived from 2,2,6,6-tetramethylpiperidine) and In(NEt 2)3 gave In[OCH(CF3)2]3(Htmp), [H2tmp][In{lcub}OCR(CF3)2{rcub}4] (R = H or Me), and mer-In[OCMe(CF3)2]3(py) 3.; Polycrystalline indium oxide films were deposited at 400--550°C in a low-pressure chemical vapor deposition process from In[OCMe(CF3 )2]3(H2N-t-Bu) and O2 precursors. The films deposited at ≤500°C contained 2--3 atom % fluorine while the film deposited at 550°C had no detectable fluorine incorporation. Films deposited on quartz (∼3600-A thickness) showed >85% transmittance in the 400--800 nm region, and resistivities of 2.56 x 10 --1--2.02 x 10--2 O cm were measured for the as-deposited films. The observed transmittance is in the range reported previously for doped and undoped In2O3, while the resistivity values are higher than those reported for tin, fluorine or sulfur-doped indium oxide.; The work on the synthesis of indium fluoroalkoxide complexes prompted an examination of the synthesis of related aluminum and gallium fluoroalkoxide complexes. Aluminum and gallium fluoroalkoxide complexes of formula M(ORf) 3(HNMe2) [M = Al, Rf = CH(CF3)2, CMe 2(CF3) or CMe(CF3)2; M = Ga, Rf = CMe 2(CF3) or CMe(CF3)2] were prepared by reacting the corresponding metal dimethylamide complexes with fluorinated alcohols.; An attempt was made to prepare gallium hydrido-thiolate complexes for possible use as precursors to gallium sulfide films. Reactions of GaH 3L (L = NMe3 or quinuclidine) with 1 or 2 equivalents of t-BuSH and GaH3--xClx(quin) with 1 or 2 equivalents of LiS-t-Bu produced mixtures of products. GaH(S- t-Bu)2(NMe3) and GaH2(S- t-Bu)(quin) were isolated as crystalline solids from the product mixtures. The complexes Ga(S-t-Bu)3L (L = NMe 3 or quinuclidine) were synthesized from GaH3L and a slight excess of t-BuSH. |
