Growth Of Titanium Nitride Research Articles

Initial Growth Process of TiN Films in Ultrahigh-Vacuum Rapid Thermal Chemical Vapor Deposition

We have investigated an initial stage of titanium nitride (TiN) growth on SiO2 substrates by ultrahigh-vacuum chemical vapor deposition with TiCl4 and NH3 as source materials. The behaviors of nucleation and grain growth of TiN have been clarified by atomic force microscopy and transmission electron microscopy. It was found that TiN film formation at an initial stage consists of three stages, which are characteristic of the lateral and subsequent vertical growth processes of grains. Deposition time dependence of the lateral growth of TiN grains clearly indicates that a process at 550°C is limited by the surface reaction, irrespective of the TiCl4 flow rate and a pretreatment for the substrates before the deposition. The pretreatment affects in the generation of additional nucleation sites on the SiO2 surface but does not affect the mechanisms of nucleation and grain growth.

Manufacture and properties of AlON–TiN particulate composites

Abstract The mechanical properties and microstructure of different content of Titanium nitride (TiN) particulates added Aluminum oxynitride (AlON) ceramic composites were studied by using DSC, SEM, TEM, XRD techniques. AlON and TiN were the only main phases in this dense material. No reaction was noticed between the AlON matrix and TiN particles. The TiN particles can delay the decompostion temperature of AlON’s. The mechanical properties increases with an increasing TiN content. The extensive microcracking commonly existing around the very large TiN grains, due to the high thermal expansion mismatch between AlON and TiN, was considered to have brought about positive effects on the strength of the composites materials and on toughening. The mechanical properties increases with an increasing sintering temperature, due to compactness of the composites, then degraded because of enormous grain growth of AlON and TiN. Finally, possible processes were discussed for the improvement of the properties of AlON–TiN composites.

Nucleation study of titanium nitride onto steel using 15N(p,αγ) 12C resonant nuclear reaction

In this research, titanium nitride is deposited by reactive DC magnetron sputtering with two original constraints due to the expected industrial application as roll to roll decorative coating of steel: the samples should be grounded and could not be heated during deposition. The growth of titanium nitride on low-carbon steel has been studied using the 15N(p,αγ) 12C resonant nuclear reaction analysis for 429 keV protons. Using gas flow of isotope 15N enriched nitrogen during deposition, it is possible to detect nitride layer of about 0.3 ML (MonoLayer) calculated thickness with the help of the above very sharp nuclear reaction. Films from 0.3 ML to bulk-like thicknesses deposited on low-carbon steel have been analysed. The spectra obtained were deconvoluted to obtain the straggled energy width and the height proportional to the depth of nitride layer and to the 15N coverage, respectively. It is then possible to observe the nitride growth onto steel substrates: an island nucleation is followed by coalescence and finally by a continuous growth. These three nucleation steps suggest an island growth mode, the basis of the well-known columnar structure for sputtered titanium nitride on steel.

Treatment of Ti–Si contact in hydronitrogen plasma

Phase transformations have been investigated that occur in Ti–Si contact subjected to processing with hydronitrogen plasma. Regularities of formation and growth of titanium nitride have been studied as a function of plasma irradiation parameters. Treatment of the Ti–Si system with hydronitrogen plasma makes it possible to form TiN films on silicon and results in formation of TiSi 2 at the interface, thus leading to changes in electrical and physical characteristics of the contact.

TiN growth on Si by hybrid radical beam PLD

High-quality (good crystallinity and stoichiometry) titanium nitride (TiN) thin films were grown on Si(100) substrates by pulsed laser deposition (PLD) using a high-purity titanium target (99.99%) and nitrogen radical beam. The crystallinity, chemical composition, and depth profiles of the grown films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectroscopy (RBS), respectively. The XRD pattern indicated that the preferred growth of TiN(200) with an orientation parallel to the Si(100) direction was obtained and the nitrogen radical drastically improved crystallinity compared with that grown in ambient nitrogen gas. RBS spectra indicated that the combination of PLD and the nitrogen radical beam suppressed silicidation at the interface between the Si substrate and TiN thin film during growth. The XPS analysis revealed that this method achieved the synthesis of stoichiometric TiN films.

Structural transitions and phase transitions in titanium thin films under irradiation by a nitrogen-hydrogen plasma

Structural and phase transitions in titanium films under nitrogen-hydrogen plasma treatment are investigated. Regularities in the formation and growth of titanium nitride are established as functions of the plasma irradiation parameters. The electrical resistivity of the irradiated films is determined.

ChemInform Abstract: Acceleration of Electrochemical Titanium Nitride Growth by Addition of LiH in a Molten LiCl—KCl—Li3N System.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Effects of a low-energy ion beam on the growth of titanium nitride layers near the interface of a polyimide

In this letter two different growth methods, reactive evaporation and ion-assisted reactive evaporation, were used to grow titanium nitride films on the polyimide biphenyl tetracarboxylic acid dianhydride-para phenylene diamine. The films were examined with x-ray photoemission spectroscopy and it was found that the chemical properties of the film depend on the distance from the polyimide/titanium nitride interface. While both techniques produced very similar films at distances greater than 5 nm from the interface, only the ion-assisted grown film had a significant amount of nitride near the interface. This is due to the ability of low-energy (100 eV) nitrogen ions to break the initial titanium/polyimide bonds which would otherwise prevent the growth of titanium nitride at the interface.

Acceleration of Electrochemical Titanium Nitride Growth by Addition of LiH in a Molten LiCI-KCl-Li[sub 3]N System

Acceleration of Electrochemical Titanium Nitride Growth by Addition of LiH in a Molten LiCI-KCl-Li[sub 3]N System

Adsorption and desorption kinetics of tetrakis(dimethylamino)titanium and dimethylamine on TiN surfaces

Titanium nitride (TiN) can be deposited using the organometallic precursor tetrakis(dimethylamino)titanium (Ti[N(CH 3) 2] 4) (TDMAT). Deviations from conformal TiN film growth have been observed in trench structures using TDMAT. This nonconformal deposition may be associated with readsorption and site blocking by the dimethylamine (HN(CH 3) 2) (DMA) reaction product. To understand the deviations from conformal TiN deposition in trench structures, the adsorption and desorption kinetics for TDMAT and DMA were measured on a sputter-deposited TiN surface using laser induced thermal desorption (LITD) techniques. The LITD measurements revealed that DMA has a higher sticking coefficient than TDMAT. The sticking coefficients for both TDMAT and DMA were also dependent on surface coverage. The initial sticking coefficient for TDMAT is S 0=0.23 with a coverage-dependence approximated by S( θ)=0.25 exp(−4.7 θ) where θ is the normalized surface coverage. The initial sticking coefficient for DMA is S 0=0.70 and the coverage-dependence is approximated by S( θ)=0.86 exp(−3.7 θ). The observed desorption kinetics of DMA following TDMAT and DMA exposures on TiN were also coverage-dependent. The isothermal desorption measurements could be fit using a simple first-order desorption rate expression, k d= ν dexp[− E d( θ)/ RT] where E( θ) is the coverage-dependent desorption energy, E d( θ)= E 0− E 1 θ. Assuming a desorption preexponential of ν d=1×10 13 s −1, the observed isothermal desorption measurements for DMA desorption following both TDMAT and DMA exposures could be fit using E 0=29.1 kcal mol −1 and E 1=8.2 kcal mol −1. These measured adsorption and desorption kinetics are consistent with DMA readsorption as a major contributor to nonconformal TiN growth in trench structures using TDMAT.

Kinetics of the Formation of Titanium Nitride Layers by Rapid Thermal Low Pressure Chemical Vapor Deposition from TiCl4 ‐ NH 3 ‐ H 2

A kinetic study of the titanium nitride growth by low pressure chemical vapor deposition (LPCVD) from gas‐phase was carried out. Experiments were performed in the temperature range of 600–900°C and in the total pressure range of 20 to 73 Pa. Partial pressures ranges were 0.4 to 2.5 Pa for , 5 to 43 Pa for , and 13 to 28 Pa for The following law of deposition was obtained A model was developed to explain the difference between these results and the published results, and to point out the importance of gas injection configuration on the experimental reaction orders and on the apparent activation energies. When (respectively, ) is injected quite near the substrate, this species is strongly adsorbed on the surface, and the available sites for adsorption (respectively, ) are reduced. Then the reaction order with respect to (respectively, is negative, and the rate‐determining step is the adsorption of (respectively, ). When these two species are injected far from the substrate, the rate‐determining step is the reaction between adsorbed and adsorbed NH or .

Titanium Nitride Thin Films Epitaxially Grown by N-Implantation

The epitaxial growth of titanium nitride (TiN) films, formed by implanting nitrogen ions (N2+) with 62 keV into 100-nm-thick Ti films grown on NaCl substrates held at 250°C, has been studied mainly by transmission electron microscopy. It has been revealed that (001)-oriented TiNy is epitaxially grown by N-implantation into the as-grown (03·5)-oriented hcp-Ti. The nitriding mechanism of epitaxial Ti thin films is discussed.

Characterization of highly oriented (110) TiN films grown on epitaxial Ge/Si(001) heterostructures

The characteristics of epitaxial growth of titanium nitride films on Ge/Si(001) have been studied. The growth of titanium nitride and germanium films on (001)Si was carried out in situ in a high vacuum chamber (<10−7 Torr) using a multitarget stage in a pulsed laser deposition system. Electrical resistivity, stoichiometry, crystallinity, and epitaxial relationships as a function of deposition temperature have been studied. Electrical resistivity of the titanium nitride films grown at deposition temperatures in the range of 450 °C–750 °C was measured using a four-point probe. The stoichiometry of these films was investigated using Auger electron spectroscopy and Raman spectroscopy. The crystalline quality and epitaxial nature of TiN films grown at different substrate temperatures were characterized using x-ray diffraction and transmission electron microscopy. Highly oriented titanium nitride films with (110) orientation were obtained on Ge(001) film when the substrate temperature was maintained between 550 °C and 650 °C. The epitaxial growth of the titanium nitride films was found to be a function of two-dimensional or three-dimensional growth mode of germanium film on silicon (001) substrate. Titanium nitride films grown at a substrate temperature of 650 °C exhibited the lowest room temperature resistivity (26 μΩ-cm), highest nitrogen content (close to stoichiometry), and the best epitaxiality with the Ge(001) films on Si(001). The epitaxial relationships for the TiN/Ge/Si(001) heterostructure are found to be [001]TiN‖ [110]Ge‖ [110]Si and [110]TiN‖ [110] Ge‖ [110]Si. To explain the epitaxial growth in a large mismatch system (∼28%) such as TiN/Ge(001), the domain matching mechanism is proposed. Domains of size four (001)TiN by seventeen (220)TiN in the titanium nitride film match closely with domains of size three (220)Ge by sixteen (220)Ge in the germanium film, respectively. The lattice matching epitaxy involving a 4% mismatch between Ge and Si provides a mechanism for epitaxial growth of Ge on Si(001).

A Kinetic Study of Titanium Nitride Chemical Vapor Deposition Using Nitrogen, Hydrogen, and Titanium Tetrachloride

The kinetics of the growth of titanium nitride by hot‐wall atmospheric pressure chemical vapor deposition (CVD) has been studied using titanium tetrachloride , hydrogen , and nitrogen as reactants. The growth rate as a function of reactant concentration at different reaction temperatures is determined. The growth rate dependence in the input concentration changes from a positive to a negative order behavior with increasing reactant concentration, and the observed maximum growth rate shifts to a higher input concentration with increasing reaction temperature. For the growth rate a square root dependence in the concentration is observed in all cases, and for the growth rate a positive order dependence in the concentration is observed which changes from 0.5 to 1.5. A reaction model has been proposed based on isothermal Langmuir adsorption behavior with mutual displacement on titanium sites at the surface, and an indirect mutual displacement on nitrogen sites at the surface. This reaction model consists of a set of elementary gas‐phase, adsorption, and surface reactions which are quasi‐equilibrated, and a rate‐determining step involving the reaction at the surface between an adsorbed species on a nitrogen site, and an adsorbed species on a titanium site. Using this model the experimental and reported growth rate data can be understood as a function of reactant concentration within the temperature region from 1000 to 1273 K.

Single crystal growth of titanium nitride by chemical vapour deposition and measurement of the linear growth rate on a (100) plane

Single crystals of TiN were grown from a gas mixture of TiCl 4, N 2 and H 2 on a tip of molybdenum wire twisted with a tungsten filament heated above 1800°C. Cubic single crystals grew at 1600–2200°C, and etching of TiN took place above 2200°C. Linear growth rates of <100>edges were calculated from sequential micrographs, and attained to a maximum of 110 μm/min at 1900–2000°C and at a gas flow ratio of 2 N 2⧸ TiCl 4 of 0.7–1.0. The crystal growth mechanism at an early stage is suggested to be surface reaction controlled.

Crystal growth of titanium nitride by chemical vapor deposition

The growth of titanium nitride crystals from the TiCl 4-H 2-N 2 system was studied using a flow method. The depositions were done on graphite plates heated externally. Red-brown coatings were formed on the lower temperature zone of the substrate and golden-yellow coatings were formed on the higher temperature zone. Needle crystals grew in the region of the substrate whose temperature was at 1200 °C to 1300 °C; they had diameters of 5–140 μm. The growth rate of needle crystals showed maxima against titanium tetrachloride and nitrogen concentrations. The growth rate was approximately proportional to P H2 1 2 . The maximum growth rate observed was ∼ 3 x 10 -5 cm/sec. The titanium nitride crystals were found to grow preferentially in the direction of [111].