评Veprek的nc-TiN/a-Si3N4模型和其“超过金刚石硬度”的实验基础

doi:10.15541/jim20140313

摘要/Abstract

摘要：

由于报道获得了超过金刚石的硬度, TiN/Si₃N₄纳米复合薄膜成为十多年来超硬材料和薄膜材料的重要热点。本文从实验基础方面对这类薄膜的Veprek模型和“超高硬度”进行了评述。在微结构方面, Veprek提出的非晶Si₃N₄包裹TiN纳米晶的结构模型(即nc-TiN/a-Si₃N₄)缺乏足够的实验依据, 直接观察表明: 高硬度薄膜中的TiN晶粒并非等轴晶,而是纳米直径的柱状晶。就Si₃N₄界面相来说也并非以1个单分子层(~0.3 nm)的非晶态存在, 而是厚度约3个分子层(~0.7 nm)的晶体态, 更重要的是Si₃N₄界面相与相邻的TiN晶体形成了共格结构。在制备技术方面, 十余年来始终没有人在这类材料中重复出Veprek超过金刚石硬度的结果, Veprek不仅将其归咎于缺乏足够高的沉积温度和氮分压, 甚至归咎于薄膜中存在不可避免的微量氧, 但也缺乏足够的直接证据。在超高硬度的样品方面, Veprek所报道超过金刚石硬度(最高达138.9 GPa)的样品不但未经任何他人检测确认, 而且现在这些样品已经不存在了。

关键词: TiN/Si3N4薄膜, 超高硬度, 微结构

Abstract:

Since hardness exceeding that of diamond was reported by Vepreke, TiN/Si₃N₄ nanocomposite film has attracted much attention from the scientific community and resulted in a ballooning number of publications over the past 15 years. This paper commented on the Veprek's microstructure model and “superhardness” of this kind of films from experimental fundamental aspects. In term of the microstructure, the model of nc-TiN/a-Si₃N₄ proposed by Veprek, in which equiaxed nanocrystalline TiN (nc-TiN) were embedded in an amorphous Si₃N₄(a-Si₃N₄) matrix, was short of sufficient experimental evidence. Direct transmission electron micrographs observations showed that the TiN nanocrystals still had a columnar morphology instead of equiaxed morphology. Si₃N₄ interface tissue had a thickness of about 0.5-0.7 nm and existed in the crystalline state. Low-energy coherent interfaces are formed between Si₃N₄ and neighbouring elongated TiN grains. As far as the preparation technology, the hardness exceed diamond has not been repeated by others in this material up to now. Veprek attributed it not only to the lack of a sufficiently high temperature and partial pressure of nitrogen, but also to the unavoidable oxygen in preparation. However, those critical conditions were imposable to satisfy in technology. For the samples, although Veprek declared their films received the hardness exceed diamond (up to 138.9 GPa), they have not confirmed by any others, and moreover, these samples have disappeared now.

Key words: TiN/Si3N4 films, super hardness, microstructure

中图分类号:

TQ174

李戈扬. 评Veprek的nc-TiN/a-Si₃N₄模型和其“超过金刚石硬度”的实验基础[J]. 无机材料学报, 2015, 30(1): 1-8.

LI Ge-Yang. Comment on Experiment Fundament of Veprek’s nc-TiN/a-Si₃N₄ Model and Its “Exceed Diamond Hardness”[J]. Journal of Inorganic Materials, 2015, 30(1): 1-8.

图/表 7

图1 纳米复合薄膜非晶包裹纳米晶结构及微裂纹受阻的示意图[21]

Fig. 1 Illustration of nanostructure and limited growth of a nanocrack in nanocrystalline/amorphous composite films[21]

图2 ~5at% Si的TiN/Si3N4复合膜截面的低倍(a)和高倍(b)TEM照片[26]

Fig. 2 Low magnification (a) and high magnification (b) cross- sectional TEM images of ~5at% Si nanocomposite film[26]

图3 TiN/Si3N4纳米多层膜的截面HRTEM照片(a)和硬度随Si3N4层厚的变化(b)[29]

Fig. 3 Cross-sectional HRTEM image of TiN/Si3N4 multilayers (a) and hardness of TiN/Si3N4 vs thickness of Si3N4 (b)[29]

图4 纳米复合膜的微结构的Hultman模型[33]

Fig. 4 Hultman microstructural model of nanocomposite films[33],Si3N4 tissue is amorphous (lSi3N4>0.7 nm)(a) and part of tissue forms epitaxial pseudo-crystal (lSi3N4≤0.5-0.7 nm)(b)

图5 TiN/Si3N4纳米复合膜的HRTEM像[26]

Fig. 5 A typical HRTEM plane-view image of nanocomposite coatings [26]

图6 Veprek提出的复合薄膜中残余氧原子对结构影响的示意图[50]

Fig. 6 Illustrations of a planar TiN/Si3N4 interface in pure (a) and oxygen contaminated (b) systems[50]

图7 Veprek两次提供的超高硬度纳米复合薄膜压痕

Fig. 7 Two indentation SEM images of ultra-hardness composite films provided by Veprek. The hardness is only 51 GPa[58] compares with the claimed 138.4 GPa[8] (a) and the hardness is over 100 GPa[27] (b) computed by the scale on the SEM images

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评Veprek的nc-TiN/a-Si₃N₄模型和其“超过金刚石硬度”的实验基础

Comment on Experiment Fundament of Veprek’s nc-TiN/a-Si₃N₄ Model and Its “Exceed Diamond Hardness”

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