Kinetical Aspects of the LPCVD of Titanium Nitride from Titanium Tetrachloride and Ammonia

Abstract

normalTiN was deposited from the reactant gases TiCl4 , NH3 , and H2 , with Ar as a carrier gas. The depositions were carried out in a cold wall CVD reactor at a total deposition pressure of 20.0 Pa (150 mtorr). The deposition rate and film properties were studied as a function of the deposition temperature and the partial pressure of the reactant gases. A rate equation for normalTiN has been determined r=1.3×10−5exp)(−7500/T·PH20·PNH31.3·PTiCl4−0.5 No influence of H2 on the deposition rate and film composition was detected. Even without H2 , deposition occurred in a gas mixture of TiCl4 , NH3 , and Ar. This suggests that H2 does not play a role in the normalTiN deposition reaction mechanism. The reaction order for NH3 and TiCl4 can only be explained qualitatively because of the existence of a normalTiN deposition reaction and a parallel complex forming reaction in the gas phase. These two reactions take place simultaneously and competitively. The complex forming reactions in the gas phase influence the reactant partial pressures. Until now this influence has not been known quantitatively. Therefore, a detailed reaction mechanism of the normalTiN deposition could not be extracted from our results. An activation energy of 61 kJ/mol has been determined. At increasing deposition temperature and at higher values of the PNH3/PTiCl4 ratio, lower values of electrical resistivity were observed. This resistivity variation is found to be caused by the impurity content (Cl and O) in the normalTiN films, which varies with the process parameters.

Correlation Between the Electrical Properties and the Morphology of Low-Pressure MOCVD Titanium Oxynitride Thin Films Grown at Various Temperatures

“…[3,4] Moreover, the presence of oxygen in titanium nitride films leads to a promising functional range of materials, TiN x O y , already used as solar selective absorbers, [5] or transparent windows for infrared detectors. [6,7] However, few works have been published on the growth, structure, and properties of these titanium oxynitride films.…”

RBS and PIXE analysis of chlorine contamination in ALD-Grown TiN films on silicon

“…Conformal TiN layers can be grown by Chemical Vapor Deposition (CVD) or atomic layer deposition (ALD) using TiCl 4 and NH 3 as precursors [11,12]. For CVD-grown samples, the chlorine incorporation into the TiN material was shown to lead to a higher resistivity [11].…”

Assessment of Carbon Contamination in Titanium Nitride Films Deposited from the Reaction of Titanium (IV) Ciiloride and Amines

“…Previously, titanium nitride thin films have been deposited by atmospheric pressure chemical vapor deposition (APCVD) through the reaction of nitrogen and titanium tetrachloride at high temperatures,[11 ammonia with titanium tetrachloride, [2] or with tetrakis(dialkylamino)-titanium compounds [3]. Low pressure chemical vapor deposition (LPCVD) of titanium nitride films has been achieved by the reaction of titanium tetrachloride with ammonia [4,5]. The plasma enhanced chemical vapor deposition (PECVD) of titanium nitride films has been achieved from the reaction of titanium tetrachloride with nitrogen gas or with ammonia.…”