Solution−Liquid−Solid Growth of Indium Phosphide Fibers from Organometallic Precursors: Elucidation of Molecular and Nonmolecular Components of the Pathway

Abstract

Methanolysis of {t-Bu2In[μ-P(SiMe3)2]}2 (1) in aromatic solvents gives polycrystalline InP fibers (dimensions 10−100 nm × 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.