Solution-based synthesis of crystalline silicon from liquid silane through laser and chemical annealing.

We report a solution process for the synthesis of crystalline silicon from the liquid silane precursor cyclohexasilane (Si(6)H(12)). Polysilane films were crystallized through thermal and laser annealing, with plasma hydrogenation at atmospheric pressure generating further structural changes in the films. The evolution from amorphous to microcrystalline is characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy and impedance spectroscopy. A four-decade enhancement in the electrical conductivity is attributed to a disorder-order transition in a bonded Si network. Our results demonstrate a potentially attractive approach that employs a solution process coupled with ambient postprocessing to produce crystalline silicon thin films.

An efficient Pd-catalyzed route to silyl esters

[formula: see text] A one-step, highly selective catalytic route to silyl esters is reported. Commercially available silanes with Si-H functionality were converted to silyl or siloxy esters in the presence of Pd(OAc)2 under mild reaction conditions. This protocol was found to be equally applicable for the modification of multiple silicon centers in one framework and lead to the corresponding polysilyl esters in high yields. A comparison of catalytic efficiency of Pd(OAc)2 versus Pd on carbon was also undertaken.

Synthesis and characterization of new cationic hexacoordinate silanes.

The reaction of N,N,N',N"-pentamethyldiethylenetriamine (pmdeta) with HSiCl3 and H2SiCl2 in dry CH2Cl2 affords the novel cationic intermolecular hexacoordinate silanes [pmdeta.HSiCl2]+Cl- (1) and [pmdeta.H2SiCl]+Cl(2), respectively. The addition of N,N,N',N',N"-pentaethyldiethylenetriamine (pedeta) to a solution of HSiCl3 in dry CH2Cl2 gives the redistribution product formulated as the salt [pedeta.H2SiCl]+Cl- (3) and SiC4. Treatment of H2SiCl2 with pedeta and N,N,N',N',N",N"'-hexamethyltriethylenetetramine (hmteta) produces [pedeta.H2SiCl]+Cl(3) and [hmteta.H2SiCl]+C1- (HCl) (4). In 4, the fourth amine is not bonded to silicon. Reactions of 2, 3, and 4 with NaBPh4 give the ion exchange products [pmdeta.H2SiC1]+BPh4- (5), [pedeta.H2SiCl]+BPh4- (6), and [hmteta.H2SiCl]+BPh4- (HCl) (7), respectively. The salts 1, 5, 6, and 7 were characterized by single-crystal X-ray diffraction analysis. Most notable is that the cations in 1, 5, 6, and 7 are slightly distorted octahedra in which two hydrogen atoms are at the trans positions. The reactions of 3 with tmeda and pmdeta afford the intermolecular ligand exchange products tmeda.H2SiCl2 and 2, respectively.