The Study on the surface modification of metals by the new nitride or oxide thin films and their spectroscopic evaluation

我们利用光谱仪和比色分析以及常用的分析仪器研究了氮和/或氧含量对TiN和ZrN薄膜性能的影响。通过色度坐标、x、y和刺激值y来评价膜的颜色，主要结论如下：(1)ZrN涂层的颜色对氮流即氮分压的敏感性高于TiN涂层。(2)在较高的压力（0.3）下溅射ZrN涂层也能获得亮丽的金色Pa。另一方面，TiN涂层的亮金色仅在0.15 Pa的较低压力下制成。(3) TiN涂层中的氧含量随氩气流量（氩气分压）的增加而增加。这种趋势对应于光反射率和电阻率对氩气流速的依赖性。这些结果可以从膜的形态和氮氧浓度来解释。此外，我们还研究了添加Si对ZrN薄膜结构和力学性能的影响。对其结构和力学性能的研究表明：(1)随着Si含量的增加，薄膜的硬度先升高，在3%左右达到最大值，然后降低到低于Zr-N二元薄膜的硬度。(2)含硅约3%的最硬薄膜由20 ~ 25 nm范围内的大晶体组成。(3)加入硅后ZrSiN薄膜硬度的增加不能用晶体尺寸来解释。(4)含3 at% Si的Zr-Si-N膜有可能成为具有更高硬度和金色的新型装饰涂层。

We have investigated the influence of nitrogen and/or oxygen content on the properties of TiN and ZrN thin films using spectrometer and colorimetric analysis as well as usual analytical instruments. The color of the films was evaluated by means of chromaticity coordinate, x and y, and the stimulus value Y. The major conclusions are as follows : (1) The color of ZrN coatings are more sensitive to nitrogen flow, namely to nitrogen partial pressure, than that of TiN coatings. (2) The bright gold-color of ZrN coatings can be obtained by the sputtering even at higher pressure of o.3 Pa. On the other hand, the bright gold color for TiN coatings is made only at the lower pressure of 0.15 Pa. (3) The oxygen content in TiN coatings increases with increasing the argon flow rate (the argon partial pressure). This tendency corresponds to the dependences of luminous reflectance and resistivity on the argon flow rate. These results can be explained from the morphology of the films and the nitrogen and oxygen concentrations.Furthermore, we have studied the influence of Si addition on the structure and the mechanical properties of ZrN thin films. A study of their structure and mechanical properties has provided as follows : (1) With increasing Si content, the hardness of the films increases initially, attaining a maximum hardness at approximately 3%, and then decreases to lower hardness than that of Zr-N binary films. (2) The hardest film containing about 3% Si consists of large crystals in the range of 20 to 25 nm. (3) The increment in hardness of ZrSiN films by silicon addition cannot be explained by the crystal size. (4) Zr-Si-N films containing 3 at% of Si have a possibility of the new decorative coatings with higher hardness and golden color.