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

我们用光谱仪和比色法以及常用的分析仪器研究了氮和氧含量对TiN和ZrN薄膜性能的影响。用色度坐标、x、y和刺激值Y来评价薄膜的颜色。主要结论如下：(1)氮化锆膜的颜色对氮气流量，即氮气分压比TiN膜的颜色更敏感。(2)即使在较高的气压(0.3Pa.)下，溅射也能获得亮金色的ZrN涂层。另一方面，TiN涂层只有在0.15帕的低气压下才能获得明亮的金色。(3)TiN涂层中的氧含量随着Ar流量(Ar分压)的增加而增加。这一趋势对应于发光反射率和电阻率随Ar流量的依赖关系。这些结果可以从薄膜的形貌和氮氧浓度来解释。此外，我们还研究了Si的添加对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，薄膜的硬度开始增加，在约3%时达到最大值，然后下降到低于Zr-N二元薄膜的硬度。(2)含硅约3%的最硬薄膜由20~25 nm的大晶体组成。(3)硅的加入对薄膜硬度的提高不能用晶体尺寸来解释。(4)含硅量为3at%的Zr-Si-N薄膜有可能成为具有更高硬度和金黄色的新型装饰涂层。

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.