TiNCl formation during low-temperature, low-pressure chemical vapor deposition of TiN

Abstract

We report for the first time the existence of the titanium nitride chloride (TiNCl) compound in low-temperature (400 °C) low-pressure chemical vapor deposition (LPCVD) TiN films deposited using TiCl4/NH3 chemistry. Thin-film x-ray diffraction and Auger electron spectroscopy was used in the film characterization. Physical, chemical, and electrical properties of the resulting low-temperature LPCVD TiN films are discussed.

TiN Films Prepared by Flow Modulation Chemical Vapor Deposition using TiCl4 and NH3

“…It is considered that the major residual chlorine exists at the grain boundaries and can be easily reduced by NH 3 , but minor chlorine is strongly bonded to titanium, and hence is difficult to remove. 12,[17][18][19] It is note worthy that the value for the FM100 sample grown at 380 • C is lower than that for the normal and post-annealed samples deposited at higher temperatures (410 • C, 440 • C). This deposition temperature dependence suggests that FM-CVD appears to be an effective method to obtain TiN films of low resistivity and low chlorine concentration at low deposition temperature.…”

Atom Probe Tomography investigations on grain boundary segregation in polycrystalline Ti(C,N) and Zr(C,N) CVD coatings

“…One plausible cause for such distinct behavior could be segregation of impurities at interfaces. For low temperature CVD processes, chlorine contamination is a concern [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] , which stems from the widely used metal chloride as a precursor in CVD reactions (e.g. TiCl 4 is the most widely used inorganic precursor employed in the CVD of titanium-containing materials (TiN, TiC, TiO 2 , Ti(C,N)) [22]).…”

“…Chlorine contamination related to CVD processes, using metal chloride precursors, is well known and documented for Low Temperature (LT) CVD processes; like Plasma Assisted (PA) [4][5][6][7][8][9][10][11][12][13]23,34] and Low Pressure (LP) CVD [12,[14][15][16][17][18][19][20][21]. However, its effects on MT-CVD process are underestimated or overlooked, given that chlorine content decreases considerably with higher temperatures and at MT-CVD temperature deposition range (700~950°C) the Cl concentration is very low.…”

“…at ~1700 °C, decomposition of TiCl 4 does not exceed 10%) [22]. On the other hand, post-annealing treatment with hydrogen source (H 2 or NH 3 ) was proposed as a solution to reduce the chlorine contamination for TiN coating [19,18,17]. With the increase of temperature, HCl production is kinetically promoted as the reaction rate follows Arrhenius behavior [22].…”

Effect of N2/H2 Plasma Treatment on the Properties of TiN Films Prepared by Chemical Vapor Deposition from TiCl4 and NH3

“…In addition, among the various parameters of the TiCl 4 -based CVD TiN process, the deposition temperature is of primary importance in controlling the Cl concentration in the deposits; the chlorine content was decreased with increasing deposition temperature. [11][12][13][14] Previously, Suzuki et al studied the relationship between Cl concentration and the resistivity, using TiN films which were prepared under vari-sheet resistance measured using a four-point probe and the film thickness. Crystallinity of the deposits was also analyzed using glancing-angle X-ray diffraction (XRD), and transmission electron microscopy (TEM) was used to evaluate the microstructure.…”