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三元SiH₄ - C₃H₆ - NH₃体系中的气相离子化学。

Gas-phase ion chemistry in the ternary SiH4-C3H6-NH3 system.

作者信息

Calderan Stefania, Carbone Paola, Operti Lorenza, Rabezzana Roberto, Vaglio Gian Angelo

机构信息

Dipartimento di Chimica Generale e Organica Applicata, Università di Torino, Corso Massimo D'Azeglio 48, 10125 Turin, Italy.

出版信息

J Mass Spectrom. 2002 Dec;37(12):1205-12. doi: 10.1002/jms.379.

Abstract

The gas-phase ion chemistry of propene-ammonia and silane-propene-ammonia mixtures was studied by ion trap mass spectrometry. As far as the binary mixture is concerned, the effect of different molar ratios of the reactants on the trend of ion species formed was evaluated, the ion-molecule reaction processes were identified and the rate constants for the main processes were measured. The results were compared with the collisional rate constants to determine the reaction efficiencies. In the ternary silane-propene-ammonia mixture the mechanisms of formation of Si(m)C(n)N(p)H(q)(+) clusters were elucidated and the rate constants of the most important steps were measured. For some species, selected by double isolation (MS/MS), the low abundance of the ions allowed us to determine the reaction paths but not the rate constants. Ternary ions are mainly formed by reactions of Si(m)C(n)H(q)(+) ions with ammonia, whereas a minor contribution comes from reactions of Si(m)N(p)H(q)(+) ions with propene. On the other hand, the C(n)N(p)H(q)(+) ions showed a very low reactivity and no step leading to ternary ion species was identified. The formation of hydrogenated ternary ions with Si, C and N has a basic importance in relation to their possible role as precursors of amorphous silicon carbides doped with nitrogen obtained by deposition from silane-propene-ammonia mixtures properly activated.

摘要

采用离子阱质谱法研究了丙烯 - 氨以及硅烷 - 丙烯 - 氨混合物的气相离子化学。就二元混合物而言,评估了反应物不同摩尔比对所形成离子种类趋势的影响,确定了离子 - 分子反应过程,并测量了主要过程的速率常数。将结果与碰撞速率常数进行比较以确定反应效率。在三元硅烷 - 丙烯 - 氨混合物中,阐明了Si(m)C(n)N(p)H(q)(+)簇的形成机制,并测量了最重要步骤的速率常数。对于通过双重分离(MS/MS)选择的一些物种,离子丰度较低,这使我们能够确定反应路径,但无法确定速率常数。三元离子主要由Si(m)C(n)H(q)(+)离子与氨的反应形成,而次要贡献来自Si(m)N(p)H(q)(+)离子与丙烯的反应。另一方面,C(n)N(p)H(q)(+)离子显示出非常低的反应活性,未发现导致三元离子物种的步骤。含硅、碳和氮的氢化三元离子的形成对于它们作为通过适当活化的硅烷 - 丙烯 - 氨混合物沉积获得的掺氮非晶碳化硅前驱体的可能作用具有根本重要性。

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