Abstract

Atomic layer deposition (ALD) of titanium nitride (TiN) is carried out by the alternate surface reactions of titanium tetrachloride (TiCl₄) and hydrazine (N₂H₄) at temperatures ranging from 150 to 350°C. The film deposition process is monitored in situ by quartz piezoelectric microweighing (QPM) and Fourier transform infrared spectroscopy (FTIRS). The QPM data detects the self-limiting character of the surface reactions between TiCl₄ and N₂H₄, as well as the linearity of the film growth with the number of cycles at 200 and 225°C. The growth constant of the TiN_x film is found to be 0.36 Å/cycle at the optimum growth temperature of 275°C. The roughness and density of the 116.3-Å-thick film deposited at this temperature are determined to be 7.2 Å and 87.5% (of the TiN volume’s density), respectively. The X-ray photoelectron spectroscopy (XPS) analysis of these films shows the content of chlorine impurities to be below the instrument’s sensitivity limit (<0.2 аt %) and the oxygen content to be near 14 at %. The X-ray diffraction measurements indicate the cubic polycrystalline structure of these films. The FTIRS method is used for surface deposition chemistry at 200 and 275°C. The possibility of depositing titanium-aluminum nitride (TiAl_xN_y) films by ALD with trimethylaluminum (TMA) as a precursor is also shown. Films deposited at 275°С are found to contain oxygen and chlorine impurities near 3 and 4 at %, respectively.

中文翻译：

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使用TiCl 4和N 2 H 4沉积TiN x的热原子层

摘要

氮化钛（TiN）的原子层沉积（ALD）通过四氯化钛（TiCl ₄）和肼（N ₂ H ₄）的交替表面反应在150至350°C的温度范围内进行。通过石英压电微称量（QPM）和傅里叶变换红外光谱（FTIRS）原位监测膜沉积过程。QPM数据可检测TiCl ₄和N ₂ H ₄之间的表面反应的自限性，以及随着200和225°C循环次数的薄膜生长线性。TiN _x的生长常数发现在275°C的最佳生长温度下，薄膜的周期为0.36Å/循环。测得在此温度下沉积的116.3-Å厚膜的粗糙度和密度分别为7.2Å和87.5％（占TiN体积的密度）。这些薄膜的X射线光电子能谱（XPS）分析显示，氯杂质的含量低于仪器的灵敏度极限（<0.2原子％），氧含量接近14 at％。X射线衍射测量表明这些膜的立方多晶结构。FTIRS方法用于200和275°C的表面沉积化学。沉积钛铝氮化物（TiAl _x N _y还显示了以三甲基铝（TMA）为前体的ALD薄膜。发现在275°C的温度下沉积的薄膜分别含有3和4 at％的氧和氯杂质。