Control of the layer number of organic thin films in the electrochemical polymerization of triazine dithiols and its properties

研究了6-取代基-1，3，5-三氮-2，4-二硫代单钠盐(RTD)在金属表面电化学聚合的成膜条件和薄膜的结构。从RTD浓度与电流密度的关系可知，在速率决定步骤为扩散过程的条件下形成非晶态有机薄膜，在速率决定步骤为单电子转移过程的条件下形成晶态薄膜。有机薄膜的形貌结构取决于RTD中取代基团的化学结构。在短烷基链的取代基中形成非晶态有机薄膜，在长烷基链的基团中形成结晶膜。此外，当烷基链为一条时，形成非晶膜，当烷基链为两条时，形成结晶膜。根据电流效率和聚合时间可以计算出膜的层数。RTD取代基团中含有不饱和基团，可制得不溶于有机溶剂的三维有机薄膜。二辛氨基-1，3，5-三氮-2，4-二硫醇在电化学聚合过程中的生成速率呈线性递增规律，表明聚合反应的速率控制步骤为电子转移过程。这种有机膜类似于Y型LB膜，但取代基中含有不饱和基团的三氮杂二硫醇形成了X型LB膜。这种薄膜是制作聚光器和非线性光学器件的有效薄膜。一些RTD的晶体结构分析表明，聚合物薄膜在一定的电势范围内开启电流，这是由于电子给体和受主部分的分离。这些特性将被开发为有机半导体、电容器和电阻器等电子设备。

The formation conditions of thin films in the electrochemical polymerization of 6-substituted groups-1,3,5-triazine-2,4-dithiol mono sodium salts (RTD) on metals and the structure of thin films were investigated. From the relation between RTD concentration and current density, amorphous organic thin films are formed in the conditions as a rate-determination step is a diffusion process and crystalline films are done in the conditions as a rate-determination step is a one-electron transfer process. Morphology structure of the organic thin films depends upon the chemical structure of substituted groups in RTD. Amorphous organic thin films are formed in the substituted groups of short alkyl chains, and crystalline films in the groups of long alkyl chains. Furthermore, amorphous films are formed when alkyl chains is one, and crystalline films when alkyl chains two. The number of layer can be calculated from current efficiency and polymerization time. RTD containing unsaturated groups in the substituted groups gave three dimensional organic thin films insoluble in organic solvents. Formation rate in the electrochemical polymerization of dioctylamino-1,3,5-triazine-2,4-dithiols increased according to a linear low, suggesting the rate-determining step to be electron transfer process. This organic film is similar to a Y-type LB film but triazine dithiols containing unsaturated groups in the substituted group give a X-type LB film. This films are effective one for producing condensers and non-linear optical devices. Crystal structure analysis for some RTD indicate that polymer films turn on an electric current over a certain potential as be separated in the parts of electron donor and acceptor. The properties will be developed as electric devices such as organic semiconductors, condensers and resistors.