非水解溶胶-凝胶碳热还原氮化法制备TiN薄膜研究

Synthesis of TiN films via carbonthermal reduction nitridation process based on non-hydrolytic sol-gel method

以四氯化钛和无水乙醇为前驱体原料,按C/Ti摩尔比为12:1引入聚乙烯吡咯烷酮(PVP,分子量为1 300 000)作为碳源,采用非水解溶胶-凝胶碳热还原氮化技术,在流量为30ml/min高纯N2中,经1300℃碳热还原氮化5h,在石英基片上制备出具有金黄色光泽的TiN薄膜。利用XRD、RAMAN和FE-SEM表征TiN薄膜物相组成及显微结构,结果表明:薄膜为具有NaCl型面心立方结构的δ-TiN晶相,薄膜中TiN晶体在其最小应变能晶面(111)择优生长,部分晶粒呈棱角分明的三棱椎状,晶界清晰,薄膜厚度在200nm左右。镀有TiN薄膜的石英基片,在可见光范围内透过率峰值为13%,在近红外区域的反射率接近70%。

Titanium tetrachloride and anhydrous ethanol were used as raw materials and polyvinylpyrrolidone （PVP, molecular weight was 1 300 000） was used as carbon source. The TiN films were prepared by carbonthermal reduction nitridation process based on non-hydrolytic sol-gel method. When the C/Ti molar ratio was 12：1, the flow rate of high-purity N2 was 30 ml/min, the the synthesis temperture was 1 300℃ and the soaking time was 5h, the golden color TiN films could be synthetized on the quartz glass substrate. The phase compositions and microstructures of the TiN films were investigated by XRD, RAMAN and FE-SEM. The result shows that the crystalline phase of thin film was 8-TIN with sodium chloride-type face-centered cubic structure. The TiN crystal showed preferred orientation growth significantly in （111） with the minimum strain energy. Some of TiN crystal appeared angular three pyramid shape and the grain boundary was clear. The thickness of TiN films was about 200 nm. The ultraviolet visible transmittance of TiN film was around 13%, its infrared reflectance was higher than 70% in the near-infrared range.