新型杂环硅烷自组装纳米膜制备与铜薄膜沉积研究

Fabrication of the excellent copper diffusion barrier has become a hot topic in the copper interconnection technology of the new generation ultra large scale integrated circuit(ULSI).Refractory metal and their nitrides have been mainly studied as inhibition barriers for their excellent thermal stability and electrical properties. However, the miniaturization of the integrated circuits was inhibited by their complex preparation process, high cost and the large thickness. The self-assembled nanofilm is expected to replace the traditional diffusion barrier layers for its super-thin and ordered properties..In our previous research,the novel high reactive dithiol heterocyclic silane was synthesized based on the triazine structure for their excellent thermal stability and molecular condensation. In this proposal, the functional heterocyclic silane self-assembled nanofilm will be prepared on silicon wafer surface and forming mechanism will be investigated. The copper film will be deposited and the condition, mophologies，electrical properties and failure time of the self-assembled nanofilm as diffusion barrier layer will be studied, elucidating the regulation mechanism between the novel dithiol heterocyclic silane self-assembled nanofilm and copper deposition. It is expected that the research would provide a new approch to obtain the excellent barrier layer, and also give theoretical and practice basis for realizing the miniaturization of the semiconductor integrated circuits.

)：.良好的铜扩散阻挡层的制备是新一代超大规模集成电路铜互连工艺中的一个热点课题。难熔金属及其氮化物由于其良好的热稳定性和电性能，一直是阻挡层材料的研究重点。然而它们制备工艺复杂、成本高、厚度大，阻碍了集成电路的微小化。自组装纳米膜具有超薄且有序性等特征，有望成为传统扩散阻挡层的替代材料。.申请人前期研究从分子结构设计入手，选用热稳定性好且富有分子凝聚性的三氮杂嗪环为基本结构，合成了新型高反应性双巯基杂环硅烷。本课题拟进一步在硅基底表面制备该杂环硅烷自组装纳米膜并探究其成膜规律；同时在该纳米膜表面沉积铜层，对铜薄膜的沉积条件、表面相貌及自组装膜作为阻挡层的电性质和失效时间等进行研究；揭示该新型双巯基杂环硅烷自组装纳米膜对铜薄膜沉积的调控机制。为获取良好稳定性的优质扩散阻挡层提供新途径及实现半导体集成电路微小化提供理论和实验基础。

树脂材料表面金属化可以使其兼具树脂和金属的优点，在电子产品、工艺美术品、灯具、乐器以及珠宝等方面应用广泛。对树脂表面进行粗化前处理，能够在其表面形成最佳的粗糙度，以便化学镀铜顺利进行，是树脂表面金属化的关键因素之一。目前已知的化学镀铜粗化工艺多为铬酸、聚丙烯酸、高锰酸钾等处理，其处理效果较好，但过程复杂操作不便并对环境具有一定的污染，严重制约了其广泛应用。因此，寻找一种无污染、操作简单的化学镀铜工艺方法势在必行。在本研究项目中，把电晕与自组装技术应用于化学镀铜的前处理中，在树脂表面成功地自组装了三嗪杂环硅烷有机薄膜，随后进行化学镀铜、电镀铜。通过正交试验得出了三嗪杂环硅烷薄膜的最佳自组装条件、化学镀铜条件与电镀铜条件。另外，硅烷类自组装膜的修饰作用，可以很大程度上促进化学镀铜的沉积，并通过化学键或者配位键和镀铜层连接，增大镀铜层的粘结力，本研究对比了三种不同端基的硅烷膜的镀铜效果，确定了最佳的自组装薄膜。借助接触角仪，SEM，XRD，电化学工作站和盐水浸泡实验、划格实验等实验仪器和方法对化学镀铜层进行表征和研究。研究结果表明：与碱液粗化处理和打磨粗化处理相比，电晕放电粗化处理可以更有有效地活化树脂表面，增加树脂表面的粗糙度，使其表面润湿性提高；经三嗪杂环硅烷自组装薄膜修饰的树脂表面化学镀铜后铜层与基底结合牢固且铜层致密有光泽。三种不同自组装薄膜修饰后的化学镀铜层，其微观结构的晶型均呈现比较强的Cu（111）倾向，三嗪杂环硅烷自组装薄膜修饰的化学镀铜层的电子迁移阻抗性能最好。.