Functionalization of nanocrystalline porous silicon surfaces with aryllithium reagents: Formation of silicon-carbon bonds by cleavage of silicon-silicon bonds
Functionalization of nanocrystalline porous silicon surfaces with aryllithium reagents: Formation of silicon-carbon bonds by cleavage of silicon-silicon bonds
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DOI：
10.1021/ja9734511
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发表时间：
1998-03-18
影响因子：
15
通讯作者：
Sailor, MJ
中科院分区：
文献类型：
--
作者：
Song, JH;Sailor, MJ
纳米晶（“多孔”）硅与苯基锂和苯乙炔锂的反应导致硅表面与苯基和苯乙炔部分的官能化？分别反应通过在表面Si-Si键上添加芳基锂试剂进行，产生Si-芳基键和Si-Li物质。高活性的Si-Li表面物种容易被水水解，导致显著的表面氧化。表面结合的锂也可以被替换为H或酰基物种通过添加三氟乙酸？乙酰氯、庚酰氯或4-丁基苯甲酰氯。这些后一种处理显著降低了多孔硅表面的空气氧化速率。所使用的纳米晶硅样品显示出由量子限制效应引起的可见光致发光。用苯基锂官能化保留了一些光致发光。而苯乙炔锂反应导致硅纳米晶体的光致发光几乎完全丧失。
Reaction of nanocrystalline ("porous") silicon with phenyllithium and lithium phenylacetylide results in functionalization of the silicon surface with phenyl and phenylacetylene moieties? respectively. The reaction proceeds by addition of the aryllithium reagent across a surface Si-Si bond, resulting in a Si-aryl bond and Si-Li species. The highly reactive Si-Li surface species is readily hydrolyzed by water, resulting in significant surface oxidation. The surface-bound Li can also be replaced with H or acyl species by addition of trifluoroacetic acid? acetyl chloride, heptanoyl chloride, or 4-butylbenzoyl chloride. These latter treatments significantly reduce the rate of air oxidation of the porous silicon surface. The nanocrystalline silicon samples used display visible photoluminescence arising from quantum confinement effects. Functionalization with phenyllithium preserves some of the photoluminescence. while the lithium phenylacetylide reaction results in almost complete loss of photoluminescence from the silicon nanocrystallites.