SOLUTION-LIQUID-SOLID GROWTH OF INDIUM-PHOSPHIDE FIBERS FROM ORGANOMETALLIC PRECURSORS - ELUCIDATION OF MOLECULAR AND NONMOLECULAR COMPONENTS OF THE PATHWAY

Citation
Tj. Trentler et al., SOLUTION-LIQUID-SOLID GROWTH OF INDIUM-PHOSPHIDE FIBERS FROM ORGANOMETALLIC PRECURSORS - ELUCIDATION OF MOLECULAR AND NONMOLECULAR COMPONENTS OF THE PATHWAY, Journal of the American Chemical Society, 119(9), 1997, pp. 2172-2181
Citations number
52
Categorie Soggetti
Chemistry
ISSN journal
00027863
Volume
119
Issue
9
Year of publication
1997
Pages
2172 - 2181
Database
ISI
SICI code
0002-7863(1997)119:9<2172:SGOIFF>2.0.ZU;2-F
Abstract
Methanolysis of {t-Bu(2)In[mu-P(SiMe(3))(2)]}(2) (1) in aromatic solve nts gives polycrystalline InP fibers (dimensions 10-100 nm x 50-1000 n m) at 111-203 degrees C. The chemical pathway consists of a molecular component, in which precursor substituents are eliminated, and a nonmo lecular component, in which the InP crystal lattices are assembled. Th e 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-Bu(2)In(mu -OMe)](2) (2) --> [t-Bu(2)In(mu-PHSiMe(3))](2) (3) --> 2 --> [t-Bu(2)I n(mu-PH2)](3) (4). Complex 4, which is alternatively prepared from t-B u(3)In and PH3, undergoes alkane elimination, the last steps of which are catalyzed by the protic reagent MeOH, PhSH, Et(2)NH, or PhCO(2)H. 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) sol ution. The outcomes of other solution-phase semiconductor syntheses ar e rationalized according to the functioning of molecular and nonmolecu lar pathway components of the kind identified here.