Deposition Of Titanium Nitride Films Research Articles

Duplex treatment on AISI D2 tool steel: plasma nitriding and reactive deposition of TiN and TiAlN films via magnetron sputtering

In this work, titanium nitride (TiN) and titanium aluminum nitride (TiAIN) films have been obtained via triode magnetron sputtering. The films were deposited using a direct current source on plasma nitrided AISI D2 tool steel (duplex treatment), non-nitrided steel, and silicon. The nitrided layer was characterized by scanning electron microscopy (SEM), Vickers microhardness, and X-ray diffraction (XRD). The films were characterized by SEM and XRD. The mechanical properties of the coatings were determined using the instrumented indentation technique (IIT) and the adhesion of the film to the substrate was qualitatively evaluated using the Rockwell C test. Both films presented no significant variation in hardness (H) and elastic modulus (E). However, compared to the films obtained in non-nitrided steel, the duplex treatment improvided the film-substrate adhesion. The improvement in adhesion can be attributed to the preliminary plasma nitriding treatment and the compressive loads acting on the nitrided surface.

Optical, electrical, and structural properties of single-phase Ti2 − xN films deposited by cathodic cage

Cathodic cage, operating in the plasma nitriding mode, has been widely applied to improve the mechanical properties of steel surfaces. This paper investigated the use of this method for the deposition of titanium nitride films on a glass substrate, demonstrating its promising application in nanostructured materials with good electrical and optical properties. 300 nm thick films were grown varying the N2/H2 gas ratio for a fixed working pressure of 1 Torr and a cage temperature of 460 °C. The formation of a single-phase tetragonal δ'-Ti2 − xN structure was shown possible by means of controlling the N2/H2 gas ratio flux. The Ti2 − xN films have shown modified electrical and optical properties, such as a different charge carrier density, resistivity, transmittance, and gap energy.

Remote plasma-enhanced atomic layer deposition of metallic TiN films with low work function and high uniformity

Thermal stability of metal/n-GaN contact is critical for its applications in microelectronic and optoelectronic devices. Metal Ti is generally used to make Ohmic contact on n-GaN after high temperature annealing, and the key factor is to form TiN at the interface. To reduce the processing temperature and improve the reliability, metallic titanium nitride (TiN) thin film has been proposed to substitute traditional metals (such as Ti) in the contact structures, due to its low work function and high blocking effect. For this novel approach, the first step is to fabricate high quality TiN films. Here, the authors adopted remote plasma-enhanced atomic layer deposition method to deposit TiN films under well-controlled conditions. Stoichiometric TiN films (Ti:N ∼ 1:1) with low oxygen contamination (<5%) have been deposited uniformly on 2 in. substrates in a large temperature range of 250–400 °C. The work function of TiN films is quite low (∼3.7 ± 0.1 eV) compared to metal Ti (∼4.33 eV), and almost independent to the growth temperature and substrates. Strong Fermi edge and high conductivity indicate excellent metallic property of the TiN films. This study of TiN film growth paves the way to establish a low temperature process and improve the thermal stability of Ohmic contacts for wide band gap semiconductor-based devices.

Synergetic effect for improved deposition of titanium nitride films

It is known that cathodic arc deposition (CAD) has been widely used in industry for high quality thin film coatings. An extremely high current density (~1012 A/m2) was created to evaporate and ionize the target material rapidly. However, the CAD also produces macroparticles or droplets along with the deposition process leading to the degradation of the film properties. Magnetic filters with different designs were therefore adopted to reduce the macro particles or droplets. However, the macroparticles still cannot be fully eliminated. Lately, a newly developed PVD process known as high power impulse magnetron sputtering (HiPIMS) was found to have the capability of yielding highly ionized flux of both gas and sputtered materials by applying a high power in short pulses to the target. High plasma density in the order of 1017 to 1019 m−3, which is three orders of magnitude higher than that of the conventional dc magnetron sputter (dcMS), can therefore be achieved from the large fluxes of energetic ions in a HiPIMS process. As a result, a smoother and denser thin film with better adhesion to the substrate can be obtained, leading to enhanced mechanical, electrical, and optical properties. However, it was also found the deposition rate of the HiPIMS process was much slower than that of the conventional dcMS and CAD process. Therefore, a hybridized deposition system combining CAD and HiPIMS was studied in this paper. Titanium nitride (TiN) films were deposited to investigate their microstructures, physical, chemical, and mechanical properties. The macroparticles were reduced in the HiPIMS system while thin films with enhanced hardness was obtained in the CAD system.

Substrate-insensitive atomic layer deposition of plasmonic titanium nitride films

The plasmonic properties of titanium nitride (TiN) films depend on the type of substrate when using typical deposition methods such as sputtering. Here we show atomic layer deposition (ALD) of TiN films with very weak dependence of plasmonic properties on the substrate, which also suggests the prediction and evaluation of plasmonic performance of TiN nanostructures on arbitrary substrates under a given deposition condition. Our results also observe that substrates with more nitrogen-terminated (N-terminated) surfaces will have significant impact on the deposition rate as well as the film plasmonic properties. We further illustrate that the plasmonic properties of ALD TiN films can be tailored by simply adjusting the deposition and/or post-deposition annealing temperatures. Such characteristics and the capability of conformal coating make ALD TiN films on templates ideal for applications that require the fabrication of complex 3D plasmonic nanostructures.

Cathodic cage plasma deposition of TiN and TiO2 thin films on silicon substrates

Cathodic cage plasma deposition (CCPD) was used for growing titanium nitride (TiN) and titanium dioxide (TiO2) thin films on silicon substrates. The main advantages of the CCPD technique are the uniformity, tridimensionality, and high rate of the film deposition that occurs at higher pressures, lower temperatures, and lower treatment times than those used in conventional nitriding treatments. In this work, the influence of the temperature and gas atmosphere upon the characteristics of the deposited films was investigated. The TiN and TiO2 thin films were characterized by x-ray diffraction, scanning electron microscopy, and Raman spectroscopy to analyze their chemical, structural, and morphological characteristics, and the combination of these results indicates that the low-cost CCPD technique can be used to produce even and highly crystalline TiN and TiO2 films.

Microhardness of TiN-TiNi composite produced by ion-plasma deposition

The microhardness of TiN-TiNi composite produced by ion-plasma deposition of titanium-nitride film on the surface of TiNi alloy is investigated. The microhardness of thin surface layers may be analytically determined on the basis of a recuperated indenter impression. The proposed conditions for the deposition of a protective TiN coating on the surface of TiNi alloy produce a barrier layer whose hardness is close to that of the base. This product meets the requirements for the medical use of titanium-nickelide components.

Deposition of Titanium Nitride Film on Mg-Li Alloys by DC Reactive Magnetron Sputtering

A number of studies have shown that TiN film is correlated with corrosion resistance. In this study, we used a reactive direct current magnetron sputtering system to prepare TiN coating on Mg-Li alloys at low temperature. The intermediate TiN layer of thickness was about 1.6 μm from Ti target (99.99% purity). The structures of the resulting nanocatalysts were investigated, using X-ray diffraction analysis (XRD). The surface morphology of the coating was observed by Atomic Force Microscope (AFM). In the corrosive compare experiment the samples of Mg-Li alloys with and without titanium nitride film were put in solution with 5% NaCl respectively. We fund that the Mg-Li alloys with TiN coating has a lower rate of liberation of hydrogen, and the eroded surface morphology was examined by Scanning Electron Microscopy (SEM), it prove that the TiN deposition on the surface of Mg-Li alloys has improved the corrosion resistance performance.

Study on Low Temperature Deposition of TiN Films and their Tribological Properties

The low temperature deposition principle of magnetron sputtering was discussed. Reactive magnetron sputtering technique was used to gain titanium nitride (TiN) thin films on W18Cr4V high-speed steel substrates at low temperature. A series of experiments had been conducted to study the properties of TiN films. The experimental results showed that at the low temperature(<140 °C), magnetic sputtering can be used for the deposition of TiN film with compact, uniform and high nano-hardness, and their tribological properties were excellent, which co-determined by the film structure of low temperature magnetron sputtering and the counter-parts of rubbing pairs.

Laser chemical vapor deposition of titanium nitride films with tetrakis (diethylamido) titanium and ammonia system

Wide-area and thick titanium nitride (TiN x ) films were prepared on Al 2O 3 substrate by laser chemical vapor deposition (LCVD) using tetrakis (diethylamido) titanium (TDEAT) and ammonia (NH 3) as source materials. Effects of laser power ( P L) and pre-heating temperature ( T pre) on the composition, microstructure and deposition rate of TiN x films were investigated. (111) and (200) oriented TiN x films in a single phase were obtained. The lattice parameter and N to Ti ratio of the TiN x films slightly increased with increasing P L and was close to stoichiometric at P L > 150 W. TiN x films had a cauliflower-like surface and columnar cross section. The deposition rate of TiN x films increased from 42 to 90 µm/h at a depositing area of 10 mm by 10 mm substrate, decreasing with increasing P L and T pre. The highest volume deposition rate of TiN x films was about 10 2 to 10 5 times greater than those of previous LCVD using Nd:YAG laser, argon ion laser and excimer laser.

Chemisorption of Tetrakis(dimethylamido)titanium on Si(100)-2 × 1: C−H and C−N Bond Reactivity Leading to Low-Temperature Decomposition Pathways

Tetrakis(dimethylamido)titanium, Ti[N(CH3)2]4 or TDMAT, is a metal alkylamide precursor often used in the deposition of titanium nitride films. The mechanisms of decomposition of TDMAT upon its adsorption on the Si(100)-2 × 1 surface are investigated by infrared (IR) spectroscopy, temperature-programmed desorption (TPD), and density functional methods. Two experimental observations, the formation of Si−H bonds at temperatures as low as 220 K and methane desorption at temperatures below 400 K, indicate the scission of C−H and C−N bonds. The unusual low-temperature reactivity of these bonds is explained in terms of bond activation due to the zwitterionic character of the silicon−silicon dimers of the Si(100)-2 × 1 surface. Silicon surface atoms with predominantly nucleophilic character are able to attract hydrogen atoms, forming Si−H bonds. Silicon surface atoms with electrophilic character are able to form N−Si dative bonds that weaken the C−N bond, favoring its scission. Density functional calculations support this model, finding that the C−H scission is favored thermodynamically and kinetically provided that the TDMAT molecule has already undergone dissociative adsorption via N−Ti bond scission. Several decomposition pathways are considered, and in all cases the surface products are stabilized upon the formation of Si−C bonds, which agrees with the formation of an interface with high carbon content when metalorganic precursors are employed. The repercussion of these facile mechanisms of decomposition on the first stages of film deposition is discussed.

Optimization of plasma parameters for high rate deposition of titanium nitride films as protective coating on bell-metal by reactive sputtering in cylindrical magnetron device

Nano-structured titanium nitride (TiN) thin film coating is deposited by reactive sputtering in cylindrical magnetron device in argon and nitrogen gas mixtures at low temperature. This method of deposition using DC cylindrical magnetron configuration provides high uniform yield of film coating over large substrate area of different shapes desirous for various technological applications. The influence of nitrogen gas on the properties of TiN thin film as suitable surface protective coating on bell-metal has been studied. Structural morphological study of the deposited thin film carried out by employing X-ray diffraction exhibits a strong (2 0 0) lattice texture corresponding to TiN in single phase. The surface morphology of the film coating is studied using scanning electron microscope and atomic force microscope techniques. The optimized condition for the deposition of good quality TiN film coating is found to be at Ar:N 2 gas partial pressure ratio of 1:1. This coating of TiN serves a dual purpose of providing an anti-corrosive and hard protective layer over the bell-metal surface which is used for various commercial applications. The TiN film's radiant golden colour at proper deposition condition makes it a very suitable candidate for decorative applications.

Deposition of titanium nitride films onto silicon by an ion beam assisted deposition method

Titanium nitride (TiN) films were deposited onto silicon wafers using an ion beam assisted deposition (IBAD) method with an electron cyclotron resonance (ECR) ion source for ionizing the nitrogen (N 2) gas under a condition of high nitrogen ion to titanium neutral ratio. The deposition rate of the TiN films was strongly dependent on the evaporation rate, d Ti, of Ti metal and decreased with increasing nitrogen ion current. The deposition rate can be approximated as d= βd Ti ϕ N2/{1/ k+ ϕ N2}− αI, where β, k and α are proportional constants, ϕ N2 is the sum rate of neutral and ionized nitrogen impinging onto the substrate, and I is the nitrogen ion current.

Electron impact ionization of the TiClx (x=1 – 3) free radicals

Titanium tetrachloride (TiCl4) is used for the plasma-assisted chemical vapor deposition of titanium nitride films. We studied the electron impact ionization of TiClx (x = 1 – 3) free radicals, which are abundant constitutents in TiCl4-containing processing plasmas, for electron energies from threshold to 100 eV. Absolute partial cross sections for the formation of all singly charged molecular ions were measured using the fast-beam technique. Dissociative ionization was found to be the dominant process for TiCl3 whereas the formation of the respective parent ions plays a more important role for TiCl2 and TiCl. Total single ionization cross sections for the three radicals could not be determined with reasonable accuracy because of problems in the determination of the cross sections for the formation of the atomic ions Ti+ and Cl+ for the three targets and, as a consequence, no comparison of the measured cross sections with calculated total single ionization cross sections is possible.

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

We propose a new chemical vapor deposition (CVD) process, the flow modulation chemical vapor deposition (FMCVD) process, to obtain high quality titanium nitride (TiN) films at low deposition temperature in a single CVD chamber. FMCVD uses sequential deposition and reduction processes, such as the deposition of TiN films followed by chlorine reduction. This cycle was repeated to achieve sufficient film thickness. By decreasing the thickness in one cycle, the residual chlorine concentration and the resistivity of the films decreased. Using FMCVD process, we could achieve low resistivity (250 µΩcm), low residual chlorine concentration (2 at.%) with uniform step coverage at low deposition temperature (380°C).

Effect of Ion Bombardment during Chemical Vapor Deposition of TiN Films

Titanium nitride (TiN) films were deposited using tetrakis(dimethylamido)titanium (TDMAT) as a precursor. During film growth, N‐ and Ar‐ion beams with an energy of 120 eV were supplied in order to improve the film quality. The films deposited using a N‐ion beam showed a resistivity of about 320 μΩ cm and density of . The use of the N‐ion beam, however, drastically degraded the step coverage of the film (below 5% at the 0.5 × 1.5 μm contact). The films deposited using an Ar‐ion beam showed a resistivity of about 800 μΩ cm and density of . The step coverage measured at the same contact was around 30%. For comparison, the thermally decomposed film showed a resistivity of about 5800 μΩ cm and density of . Finally, the diffusion barrier properties of 50 nm thick TiN films for Cu were investigated by the etch‐pit test. The films deposited using N‐ and Ar‐ion beam failed after annealing at 600 and 650°C for 1 h, respectively, while thermally decomposed films failed at temperatures as low as 500°C. It is thought that the improvements of the diffusion barrier performance of the films deposited using a N‐ and Ar‐ion beam are the consequence of the film densification resulting from ion bombardment during film growth. © 2000 The Electrochemical Society. All rights reserved.

Low temperature chemical vapor deposition of titanium nitride films from tetrakis(ethylmethylamido)titanium and ammonia

Titanium nitride films were deposited from tetrakis(ethylmethylamido)titanium and ammonia at 250–350°C and 0.7–2 Torr by thermal chemical vapor deposition. The effect of process parameters such as deposition temperature, precursor temperature, carrier gas flow, and ammonia flow on the film properties was studied, the apparent activation energy of film growth was calculated and the film composition was determined. The film step coverage was better than for films grown from tetrakis(dimethylamido)titanium and ammonia.

Pulsed laser deposition of titanium nitride films on sapphire

We successfully deposited high-quality TiN films on c-plane sapphire by using the pulsed laser deposition technique. TiN grew on sapphire with two in-plane epitaxial relationships: (111)TiN//(0001)sapphire and [101]TiN//[1100]sapphire or (111)TiN// (0001)sapphire and [101]TiN//[1100]sapphire. The TiN unit cell showed a ±30° in-plane rotation for sapphire. The misfit between the TiN film and the sapphire substrate was calculated by using the near coincidence site lattice approach. The deposited films were analyzed by x-ray diffraction, transmission electron microscopy, atomic force microscopy, Rutherford backscattering or channeling spectrometry, electrical, and spectrophotometric measurements. The dependence of the film's crystalline quality on the deposition temperature has been investigated. The full width half-maximum of the rocking curve of the TiN 111 peak was 0.2–0.3°. The minimum ion channeling was 5%, and the room temperature resistivity was as low as 13 μω cm.

Low-temperature deposition of titanium nitride films from dialkylhydrazine-based precursors

The deposition of titanium nitride films from single-source precursors bearing alkylhydrazine-derived ligands is reported. The complex [Ti 2Cl 4(NN(CH 3) 2) 2(NH 2N(CH 3) 2) 2] sublimes at 140–150°C (0.1 mmHg) and affords titanium nitride films in a chemical vapor deposition reactor at substrate temperatures of ⩾400°C. By contrast, structurally related single-source precursors containing alkylamine- or ammonia-derived ligands deposit titanium (IV) nitride chloride films at 400°C in the same reactor, and only afford titanium nitride films at ⩾475°C. The hydrazide(1−) complex [TiCl 2(N(CH 3)N(CH 3) 2) 2] sublimes at 130°C (0.1 mmHg) and affords titanium nitride films at 600°C. At substrate temperatures of ⩽550°C, poorly adherent blue-colored coatings were obtained. The atmospheric pressure chemical vapor deposition reaction of titanium tetrachloride and 1,1-dimethylhydrazine affords titanium nitride films at >500°C, but gives titanium (IV) nitride chloride films at ⩽500°C. Characterization of the films obtained from the depositions is described. The results demonstrate that ligands derived from 1,1-dialkylhydrazines can be powerful reducing sources for high valent early transition metals, depending on the ligand coordination mode, and can lead to a significant reduction in deposition temperatures compared to traditional nitrogen sources in cases where a high valent metal source compound must be reduced to a lower oxidation state.

Ion Beam Induced Metallorganic Chemical Vapor Deposition of Titanium Nitride Films as a Diffusion Barrier Between Cu and Si

ABSTRACTWe have deposited TiN films by using ion-beam-induced chemical-vapor-deposition (IBICVD). Tetrakis-dimethyl-amido-titanium (TDMAT) was used as a precursor. N2 and Ar gas were used to generate the plasma and the ions in the plasma were extracted by using two electrically isolated grids. The energy of ion beam was about 115–127 eV. The use of N-ion beam significantly lowers the resistivity and carbon content of TiN film (∼320 μΩ-cm, 15 at.%), compared with the thermally decomposed film (∼6000 μΩ-cm, 36 at.%). The use of Ar ion beam also considerably lowers the resistivity of films (∼800 μΩ-cm), but does not reduce the carbon content. The step coverage of the thermally-decomposed film was about 70 %, while the step coverages of the films deposited using N2 and Ar ion beams were about 0 and 30 %, respectively, in 0.5 μm x 1.5 μm contacts. The etch-pit test showed that 50-nm-thick films deposited by using N2 and Ar ion beams prevent the diffusion of Cu into the Si substrate up to annealings at 550 °C and 600 °C for 1 hour, while the thermally decomposed film fails at 500 °C.