TiN／Si_3N_4纳米晶复合膜的微结构和强化机制

Microstructure and Mechanical Properties of TiN/Si_3N_4 Nanocomposite Films

采用高分辨透射电子显微镜对高硬度的TiN／Si3N4纳米晶复合膜的观察发现,这类薄膜的微结构与Veprek提出的nc-TiN／a-Si3N4模型有很大不同;复合膜中的TiN晶粒为平均直径约10nm的柱状晶,存在于柱晶之间的Si3N4界面相厚度为0．5-0．7nm,呈现晶体态,并与TiN形成共格界面．进一步采用二维结构的TiN／Si3N4纳米多层膜的模拟研究表明,Si3N4层在厚度约<0．7nm时因TiN层晶体结构的模板作用而晶化,并与TiN层形成共格外延生长结构,多层膜相应产生硬度升高的超硬效应．由于TiN晶体层模板效应的短程性,Si3N4层随厚度微小增加到1．0nm后即转变为非晶态,其与TiN的共格界面因而遭到破坏,多层膜的硬度也随之迅速降低．基于以上结果,本文对TiN／Si3N4纳米晶复合膜的强化机制提出了一种不同于nc-TiN／a-Si3N4模型的新解释．

A microstructure investigation of TiN/Si3N4 nanocomposite films with high hardness was performed by means of high-resolution transmission electron microscope, and a result far from the ncTiN/a-Si3N4 model was presented. Instead of the isotropic one, TiN was pronounced nanocrystalline columnar grains with dimensions of 〈 10nm in width and 〉 100nm in length. Immiscible Si3N4 interfacial phases between TiN nanocolumns with a thickness of about 0.5-0.7nm existed in nanocrystalline structure and formed coherent interfaces with adjacent TiN nanocrystals. A succedent simulation employing two-dimensional TiN/Si3N4 nanomultilayers also implied that due to the template effect of crystalline TiN layers, sputter-deposited amorphous Si3N4 was forced to crystallize and grow epitaxially with TiN layers when its thickness was less than 0.7nm, accompanied by a significant enhancement in film＇s hardness. Due to the short-range nature of the template effect of TiN layers, the crystalline Si3N4 gradually transformed into amorphous when its thickness exceeded 1.0nm and the coherent interfaces were destroyed as a consequence, with a simultaneous film＇s hardness decline. By comparing the microstructure and corresponding hardness response of TiN/Si3N4 nanocomposite films with that of the nanomultilayered ones, a new explanation on hardening mechanism of TiN/Si3N4 nanocomposites was proposed.