TY - JOUR
T1 - Solution-liquid-solid growth of indium phosphide fibers from organometallic precursors
T2 - Elucidation of molecular and nonmolecular components of the pathway
AU - Trentler, Timothy J.
AU - Goel, Subhash C.
AU - Hickman, Kathleen M.
AU - Viano, Ann M.
AU - Chiang, Michael Y.
AU - Beatty, Alicia M.
AU - Gibbons, Patrick C.
AU - Buhro, William E.
PY - 1997
Y1 - 1997
N2 - Methanolysis of {t-Bu2In[μ-P(SiMe3)2]}2 (1) in aromatic solvents gives polycrystalline InP fibers (dimensions 10-100 nm x 50-1000 nm) at 111-203°C. The chemical pathway consists of a molecular component, in which precursor substituents are eliminated, and a nonmolecular component, in which the InP crystal lattices are assembled. The two components working in concert comprise the solution-liquid-solid (SLS) mechanism. The molecular component proceeds through a sequence of isolated and fully characterized intermediates: 1 → [t-Bu2In(μ-OMe)]2 (2) → [t-Bu2In(μ-PHSiMe3)]2 (3) → 2 → [t-Bu2In(μ-PH2)]3 (4). Complex 4, which is alternatively prepared from t-Bu3In and PH3, undergoes alkane elimination, the last steps of which are catalyzed by the protic reagent MeOH, PhSH, Et2NH, or PhCO2H. In the subsequent nonmolecular component of the pathway, the resulting (InP)(n) fragments dissolve into a dispersion of molten In droplets, and recrystallize as the InP fibers. Important criteria are identified for crystal growth of covalent nonmolecular solids from (organic) solution. The outcomes of other solution-phase semiconductor syntheses are rationalized according to the functioning of molecular and nonmolecular pathway components of the kind identified here.
AB - Methanolysis of {t-Bu2In[μ-P(SiMe3)2]}2 (1) in aromatic solvents gives polycrystalline InP fibers (dimensions 10-100 nm x 50-1000 nm) at 111-203°C. The chemical pathway consists of a molecular component, in which precursor substituents are eliminated, and a nonmolecular component, in which the InP crystal lattices are assembled. The two components working in concert comprise the solution-liquid-solid (SLS) mechanism. The molecular component proceeds through a sequence of isolated and fully characterized intermediates: 1 → [t-Bu2In(μ-OMe)]2 (2) → [t-Bu2In(μ-PHSiMe3)]2 (3) → 2 → [t-Bu2In(μ-PH2)]3 (4). Complex 4, which is alternatively prepared from t-Bu3In and PH3, undergoes alkane elimination, the last steps of which are catalyzed by the protic reagent MeOH, PhSH, Et2NH, or PhCO2H. In the subsequent nonmolecular component of the pathway, the resulting (InP)(n) fragments dissolve into a dispersion of molten In droplets, and recrystallize as the InP fibers. Important criteria are identified for crystal growth of covalent nonmolecular solids from (organic) solution. The outcomes of other solution-phase semiconductor syntheses are rationalized according to the functioning of molecular and nonmolecular pathway components of the kind identified here.
UR - https://www.scopus.com/pages/publications/0030992465
U2 - 10.1021/ja9640859
DO - 10.1021/ja9640859
M3 - Article
AN - SCOPUS:0030992465
SN - 0002-7863
VL - 119
SP - 2172
EP - 2181
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 9
ER -