Film formation from mixed solutions of 1,3,5-triazine-2,4-dithione and phosphate onto Au, Ag, and Cu substrates
Film formation from mixed solutions of 1,3,5-triazine-2,4-dithione and phosphate onto Au, Ag, and Cu substrates
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DOI：
10.1021/jp711923t
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发表时间：
2008-05-01
影响因子：
3.7
通讯作者：
Kadoma-L, Yoshinori
中科院分区：
文献类型：
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作者：
Yamamoto, Masato;Suzuki, Masako;Kadoma-L, Yoshinori
用红外光谱和拉曼光谱研究了1,3,5-三嗪-2,4-二硫酮衍生物（VBATDT）和磷酸衍生物（M10P）在An、Ag和Cu底物上的混合溶液生成的有机膜的分子结构。分子结构根据混合溶液的浓度、摩尔浓度比、底物和薄膜制备方法而变化。当VBATDT吸附在金属上时，1,3,5-三嗪-2,4-二硫醇（杂环）基作为吸附位点，使环结构由硫酮形式转变为硫醇形式。如果VBATDT与M10P在基板表面附近共存，这两种单体至少可以在金属表面形成四种化学吸附层。一种是含有两个杂环基硫的VBATDT吸附在Au上的单层，其中环的对称轴垂直于表面。第二种是在Ag或Cu衬底上形成的以VBATDT为主的单层，杂环基团倾斜。第三是由VBATDT衍生的聚合物组成的厚膜；该聚合物可由浓缩混合物在Ag和Cu衬底上生成。四是主要由M10P制成的聚合物组成的厚膜；该聚合物可由含有高摩尔比M10P的浓溶液在Cu衬底上制备。讨论了产生这些不同化学吸附层的原因。
Molecular structures of organic films generated from mixed solutions of a 1,3,5-triazine-2,4-dithione derivative (VBATDT) and a phosphate derivative (M10P) onto An, Ag, and Cu substrates were examined by IR and Raman spectroscopy. The molecular structure varies according to the concentration, the molarity ratio of the mixed solution, the substrate, and the method of film preparation. When VBATDT is adsorbed on the metals, the 1,3,5-triazine-2,4-dithiol (heterocyclic) group acts as the adsorption site and changes the ring structure from the thione form to the thiol form. If VBATDT coexists with M10P near the substrate surface, the two kinds of monomers can build, at least, four kinds of chemisorbed layers on the metals. One is the monolayer of VBATDT adsorbed onto Au with two sulfurs in the heterocyclic group, in which the axis of symmetry of the ring is perpendicular to the surface. The second is the monolayer mainly consisting of VBATDT formed on the Ag or Cu substrate with the heterocyclic group tilted. The third is the thick film consisting of the polymer derived from VBATDT; this polymer can be generated on the Ag and Cu substrates from the concentrated mixture. The fourth is the thick film consisting of the polymer made mainly from M10P; this polymer can be prepared on the Cu substrate from the concentrated solution containing a high molarity ratio of M10P. The reasons for these various chemisorbed layers were discussed.