Titanium Carbide Films Research Articles

Comparative assessment and experimental analysis of atomic coordination and mechanical properties of sputter deposited Ti-rich TiN, TiC, and TiCN thin films

In the present work, Titanium nitride (TiN)150 nm, Titanium on Titanium nitride (TiN75 nm/Ti75 nm), Titanium on Titanium carbonitride (TiCN75 nm/Ti75 nm), and Titanium on Titanium carbide (TiC75 nm/Ti75 nm) films were deposited on Si (100), quartz, and glass substrates through dc-magnetron sputtering. Vacuum annelation was carried at 600ºC for 1 hr to form TiN (m-TiN), Ti-rich TiN (b-TiN), Ti-rich TiC (b-TiC) and Ti-rich TiCN (b-TiCN) films. b-TiCN showed less optical absorbance and band gap compared to b-TiN and b-TiC films and more detrimental types of defects, which might lead to the degradation of mechanical properties in b-TiCN film. The shifting of the Ti-N core orbital towards higher binding energy showed the higher bond strength of the b-TiN film. The ITA/ITO ratio increased from 0.8 to 2.37 for b-TiC to b-TiN films, signifying the deterioration in medium-range order. The defect parameter, ID/IG, increased from 0.63 to 0.71, indicating that b-TiCN has higher defects than b-TiC films. The valence band spectra revealed that b-TiN and b-TiC valence bands are present above the Fermi level but below in the case of b-TiCN films. X-ray absorption spectroscopy confirmed that the Ti L, N K, and C K-edge were observed at 462.38, 404.53, and 287.33 eV, respectively. The highest Young’s modulus and hardness were 97.43 and 18.47 GPa, respectively, measured by a Berkovich nanoindenter for b-TiN thin films.

Investigations of TiC and SiC films synthesized by DC magnetron sputtering and thermal annealing

In this research article, two-dimensional thin films of titanium, hierarchical titanium-carbon, titanium carbide, hierarchical silicon-carbon, and silicon carbide films were synthesized on the plates of AISI 304 stainless steel and glass slides, individually, using DC magnetron sputtering techniques. During the sputtering process, the creation of stable plasma was affected by the vacuum level, DC potential, plasma current, and Argon gas. The results showed that the coatings of titanium, titanium-carbon, and titanium carbide modified the optical properties of stainless steel. Additionally, titanium carbide coatings displayed a shiny gold appearance with a hardness of 1500 HV. Besides this, X-ray diffraction studies revealed a hexagonal Ti in the metallic films and C60, and diamond-like structures dispersed on its surface after the carbon coating. The spherical particulates of Ti and C60/diamond-like carbon particulates anchored on its surface were observed using scanning electron microscope analysis. The structural analysis indicated C vacant sites, which are available for ionic/electronic charge diffusion, thereby rendering these structures suitable for making Li storage batteries as electrode material.

Electrochemical Performance of Biocompatible TiC Films Deposited through Nonreactive RF Magnetron Sputtering for Neural Interfacing.

The efficacy of neural electrode stimulation and recording hinges significantly on the choice of a neural electrode interface material. Transition metal carbides (TMCs), particularly titanium carbide (TiC), have demonstrated exceptional chemical stability and high electrical conductivity. Yet, the fabrication of TiC thin films and their potential application as neural electrode interfaces remains relatively unexplored. Herein, we present a systematic examination of TiC thin films synthesized through nonreactive radio frequency (RF) magnetron sputtering. TiC films were optimized toward high areal capacitance, low impedance, and stable electrochemical cyclability. We varied the RF power and deposition pressure to pinpoint the optimal properties, focusing on the deposition rate, surface roughness, crystallinity, and elemental composition to achieve high areal capacitance and low impedance. The best-performing TiC film showed an areal capacitance of 475 μF/cm2 with a capacitance retention of 93% after 5000 cycles. In addition, the electrochemical performance of the optimum film under varying scanning rates demonstrated a stable electrochemical performance even under dynamic and fast-changing stimulation conditions. Furthermore, the in vitro cell culture for 3 weeks revealed excellent biocompatibility, promoting cell growth compared with a control substrate. This work presents a novel contribution, highlighting the potential of sputtered TiC thin films as robust neural electrode interface materials.

Comparative study of titanium carbide films deposited by plasma-enhanced and conventional magnetron sputtering at various methane flow rates

Titanium carbide (TiCx) films were deposited by reactively sputtering Ti target with varied methane (CH4) flow rates using an unbalanced magnetron sputtering equipment operating in conventional (CMS) and plasma-enhanced (PEMS) mode. The microstructure and properties of the TiCx films were mainly scrutinized with X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, nano indentation, and ball-on-disk tribo-test. As the CH4 flow rate is increased from 4 to 16 sccm, x in the TiCx films deposited by PEMS and CMS is gradually increased from 0.28 to 0.96 and 0.28 to 0.73, respectively; and the concentration of TiC phase in the films rises. A densified microstructure with strong preferred growth is observed in the PEMS-deposited films, while a loose columnar microstructure with almost random growth exists in the CMS-deposited films. When the CH4 flow rate is increased, the hardness of the films deposited by PEMS is firstly increased and then decreased, and reaches a maximum value of 29.6 GPa; but that of CMS-TiCx film is fluctuated below 10.6 GPa. The friction coefficient of TiCx-coated samples against pure aluminum is gradually increased with increasing CH4 flow rate from 4 to 14 sccm, accompanied by a reduction of the aluminum adhesion. The wear rate of the TiCx-coated samples as a function of the CH4 flow rate is firstly decreased and then increased. The lowest wear rate of the PEMS-prepared samples is 7.2 × 10−16 m3/(N·m) obtained at a CH4 flow rate of 14 sccm, while that of the CMS-prepared samples is 9.3 × 10−15 m3/(N·m) obtained at 12 sccm. Therefore, PEMS is a promising method to prepare TiCx films with a good combination of the mechanical properties and wear-resistance against pure aluminum.

Elastic constants of titanium carbide films using surface Brillouin scattering

Surface Brillouin scattering (SBS) from surface phonons has been used for determining the dispersion curves of guided acoustic modes propagating along titanium carbide (TiC) films. Dispersion curves have been obtained by varying both the layer thickness and the angle of incidence. Elastic stiffnesses for the TiC on silicon and TiC on silicon carbide systems were determined from a least-squares fitting procedure of the velocity dispersion curves and used to simulate the respective SBS spectra. For each system there is good agreement between measured and calculated SBS spectra.

Deposition of titanium carbide catalytic films on vanadium foils by ion beam sputtering for hydrogen separation and purification

Titanium carbide (TiC) catalytic films were deposited on vanadium (V) foils by ion beam sputtering (IBS) technique for hydrogen purification. The effect of sputtering temperature in the IBS process on the phase structure and catalytic property of the TiC catalytic films and the hydrogen permeation performance of TiC/V composite membranes was investigated. The carbon vacancy density of TiC films increases with the sputtering temperature, resulting in increasing catalytic property of TiC films and hydrogen permeation performance of TiC/V composite membranes. At sputtering temperature of 400 °C, the TiC/V composite membranes exhibit highest hydrogen permeability (∼9.5 × 10−8 mol H2 m−1 s−1 Pa−0.5) at 650 °C and excellent stability during the thermal cycles at 450–650 °C.

Effect of Microstructural and Tribological Behaviors of Sputtered Titanium Carbide Thin Film on Copper Substrate

Titanium carbide (TiC) thin films were deposited by radio frequency magnetron sputtering (RFMS) onto a copper substrate by using Argon (Ar) gas plasma at a gas flow rate of 10.0 sccm. The effect of time and temperature at a constant RF power on the structural and tribological properties were respectively investigated by atomic force spectroscopy (AFM), X-ray Diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, optical microscopy (OM), scanning electron microscopy (SEM) and tribological measurements. All films were tested to have crystal structures with the preferential plane (111) and dominant plane (200) grain orientations. Thus, plane (111) has phase identification of Cu(Cu16Ti)0.23 for some samples, whereas plane (200) has a phase identification of Cu(Cu0.997Ti0.003) and Cu(Cu0.923Ti0.077) for other samples. The lowest thin film roughness of 19.797 nm was observed in the sample, with RF power, sputtering time, and a temperature of 200 W, for two hours and 80 °C, respectively. The FTIR spectra of TiC films formed under different sputtering times (2-3 h) and temperatures (80 °C-100 °C) on Cu substrates at a constant sputtering power of 200 W in the range of 5000-500 cm-1. The peaks at 540 cm-1, 780 cm-1, and 1250 cm-1 are presented in the FTIR spectra and the formation of a Ti-C bond was observed. On the other hand, a sample was revealed to have the lowest wear volume of 5.1 × 10-3 mm3 while another sample was obtained with the highest wear volume of 9.3 × 10-3 mm3.

Synthesis of high-quality ultrathin titanium carbide nanosheets and films through immiscibility approach

Two-dimensional (2D) transition metal carbides (TMCs) have been explored widely in energy storage and catalysis fields. However, it is challenging to fabricate high-quality 2D titanium carbide (TiCx) nanosheets with surface functional groups free, uniform size and thickness, and defects free. Here, we demonstrate a simple method to fabricate high-quality ultrathin TiCx nanosheets through an immiscibility approach by using chemical vapor deposition (CVD). Ultrathin Ti film (100 nm) was deposited on Cu foil as the substrate which makes Ti atoms immiscible on Cu foil. Ti atoms were transferred to the Cu substrate surface and reacted with CH4 to form ultrathin TiCx at high temperatures. The size (600 nm) and thickness (4 nm) of the obtained TiCx nanosheets are uniform. Additionally, ultrathin TiCx films werer obtained. This work provides a novel method to produce high-quality TMCs nanosheets and films in a simple and efficient way.

Flexible, lightweight and multi-level superimposed titanium carbide films for enhanced electromagnetic interference shielding

The progressive development of next-generation flexible and portable electronics highly requires electromagnetic interference (EMI) shielding layers with a trade-off among high shielding effectiveness (SE), lightweight and flexible nature. Herein, a multiscale layered structure optimization strategy is proposed to enhance EMI shielding performance through orderly superimposing individual free-standing Ti3C2 (F-Ti3C2) film with an ultrathin thickness of ∼ 4 μm. Compared to a bulk F-Ti3C2 film (64.6 dB) with the same weight of 150 mg, the multi-level superimposed Ti3C2 films with six individual layers (S-Ti3C2-6) show much higher EMI shielding performance (84.7 dB). Furthermore, the increment in the gap distance between the adjacent F-Ti3C2 films can also increase the EMI SE from 51.1 dB (d = 0 mm) to 74.9 dB (d = 1.5 mm). The underlying mechanism can be attributed to the synergistic effect of multiple internal reflections between Ti3C2 nanosheets and multiple-wave interference between adjacent F-Ti3C2 films. Furthermore, the multi-layered design strategy can be extended to other EMI materials including polypyrrole and graphite, etc. The demonstration of Ti3C2 coatings to block EM waves proves their considerable advantages over commercial shielding packages. This work provides a novel methodology to design EMI shielding layers for the practical applications.

Epitaxial TiCx(001) layers: Phase formation and physical properties vs C-to-Ti ratio

Titanium carbide films are deposited onto MgO(001) by reactive magnetron sputtering in Ar/CH4 mixtures at 1100 °C with a varying CH4 fraction fCH4 = 0.4–8%, yielding C-to-Ti ratios x = 0.08–1.8. The microstructure is dominated by an epitaxial rock-salt structure TiCx(001) matrix which contains secondary hcp Ti and graphitic/a-C:H for x ≤ 0.24 and x ≥ 1.5, respectively. First-principles calculations indicate negligible interstitial C in the cubic phase, a large equilibrium phase-field x = 0.5–1 for the cubic structure which is extended to x < 0.5 by entropic stabilization, and a predicted C-solubility in hcp Ti of x = 0.06 at 1100 °C. The measured relaxed lattice constant increases from ao = 0.4304 nm for TiC0.5 to 0.4325 nm for TiC1.0, in excellent agreement with predictions. However, dao/dx for x < 0.5 and x > 1.0 is much smaller than predicted for C vacancies and interstitials in rock-salt TiCx, respectively, confirming secondary phase formation and indicating a minimum x = 0.46 in the cubic phase. The hardness and elastic modulus of phase-pure TiCx(001) increases from H = 24 GPa and E = 304 GPa for TiC0.5 to H = 31 GPa and E = 462 GPa for TiC1.0, which is attributed to an increasing bonding ionicity. H and E decrease with x < 0.5 and x > 1.0 due to secondary phase softening which is well described by an effective medium with homogenous stress. The electrical resistivities for TiC0.5 and TiC1.0 are 168 and 83 μΩ cm at 298 K, and 158 and 72 μΩ cm at 77 K, indicating electron scattering at random anion vacancies for x = 0.5 but also dominant defect scattering for stoichiometric TiC1.0.

Flexible, Lightweight and Multi-Level Superimposed Titanium Carbide Films for Enhanced Electromagnetic Interference Shielding

Flexible, Lightweight and Multi-Level Superimposed Titanium Carbide Films for Enhanced Electromagnetic Interference Shielding

Effect of Annealing Temperature on Microstructure and Resistivity of TiC Thin Films

Titanium carbide (TiC) thin films were prepared by non-reactive simultaneous double magnetron sputtering. After deposition, all samples were annealed at different temperatures under high-vacuum conditions. This paper mainly discusses the influence of deposition methods and annealing temperatures on microstructure, surface topography, bonding states and electrical resistivity of TiC films. XRD (X-ray diffraction) results show that TiC thin films can still form crystals without annealing, and the crystallinity of thin films is improved after annealing. The estimated grain size of the TiC films varies from 8.5 nm to 14.7 nm with annealing temperature. It can be seen from SEM (scanning electron microscope) images that surfaces of the films are composed of irregular particles, and when the temperature reaches to 800 °C, the shape of the particles becomes spherical. Growth rate of film is about 30.8 nm/min. Oxygen-related peaks were observed in XPS (X-ray photoelectron spectroscopy) spectra, which is due to the absorption of oxygen atoms on the surface of the film when exposed to air. Raman spectra confirm the formation of TiC crystals and amorphous states of carbon. Resistivity of TiC films decreases monotonically from 666.73 to 86.01 μΩ·cm with the increase in annealing temperature. In brief, the TiC thin films prepared in this study show good crystallinity, thermal stability and low resistivity, which can meet the requirements of metal gate applications.

Multidimensional carbon template preparation of 3D multilayered TiC nanoflakes for high performance symmetric supercapacitor

Titanium carbide (TiC)-based electrodes are attractive in supercapacitor due to their ultra-high density and pseudocapacitive charge storage mechanism. However, TiC films with horizontal alignment of flakes or random nanostructures limit the high rate of charge transfer and hinder the migration of ions to redox active sites. In this work, the TiC nanotubes and three-dimensional interconnected nanoflakes are synthesized by electrodeposition and carbothermal treatment of carbon nanotube (CNT) film and graphite, respectively. To study the capacitance mechanism of TiC nanotube-interconnected branch (NTIB) films, the in-situ Raman spectrums of the TiC-NTIB negative electrode during the charge/discharge processes in H2SO4 show that hydronium is bonded to the terminal O during discharge, and debonding occurs during charging. The integrated TiC NTIB electrode is capable of operating at rates faster than that of carbon, conductive polymers or transition metal oxides, but still delivers a specific capacitance of 273 F g−1 at 10 A g−1 after repeating 2000 cycles at current densities of 1, 3, 5 and 10 A g−1. The symmetric supercapacitor composed of the TiC NTIB electrodes delivers an energy density of 64.4 Wh kg−1 (at 892.3 W kg−1) and a power density of 9.5 kW kg−1 (at 55.6 Wh kg−1), and a good cycle stability (≈86.7% retention after 15,000 cycles).

Ultrasensitive and reversible room-temperature resistive humidity sensor based on layered two-dimensional titanium carbide

The nanostructured two-dimensional (2D) materials for humidity sensing applications have become increasingly attractive. However, 2D materials have negative aspects of easily stacking and agglomerating multilayers. Here, a novel resistive-type humidity sensor utilizing multi-layer titanium carbide (Ti3C2Tx) films as sensitive material is demonstrated. The humidity sensor exhibits an ultrasensitive and reversible sensing performance in a wide relative humidity range. Furthermore, the ultrafast response and recovery properties are achieved at room temperature. The Fourier transform infrared spectroscopy is used to investigate the adsorption of water vapor on Ti3C2Tx surfaces. A rapid capillary condensation of water vapor on the unique accordion-like microstructures and the hierarchical nanostructures of hydroxyl-riched Ti3C2Tx surface are supposed to be responsible for the super adsorption capability for water vapor. The electrostatic field induced by adsorbed water molecules is proposed to explain the resistance change of the titanium carbide humidity sensor. This work highlights the unique advantages of humidity sensor with layered 2D materials of Ti3C2Tx MXenes, including ultrasensitive, good reversibility and fast recovery at room temperature.

A comparative investigation of hetero-epitaxial TiC thin films deposited by magnetron sputtering using either hybrid DCMS/HiPIMS or reactive DCMS process

A hybrid direct current magnetron sputtering/high-power impulse magnetron sputtering (DCMS/HiPIMS) technique was used to improve the structural and electrical properties of single-crystal titanium carbide (TiC) thin films. The hetero-epitaxial TiC films, ~ 60 nm thick, were grown on MgO (001) substrates at temperatures ranging from 200 °C to 800 °C, by co-sputtering of Ti and C targets powered by DCMS and HiPIMS, respectively. Films’ composition and the structural, morphological, and electrical properties were comparatively investigated to those of a set of samples deposited at same temperatures by reactive-DCMS (R-DCMS) in Ar/CH4 atmosphere. The composition and the FWHM of rocking curves of the films deposited by R-DCMS varied from TiC0.84 to TiC0.94 and from 1.38° to 0.64°, respectively, as the growth temperature increased. TiC0.94 - TiC0.96 layers were deposited by hybrid DCMS/HiPIMS method at temperatures higher than 400 °C, fully strained over their full thickness, with FWHM of rocking curves of about 0.13°. Electrical resistivity values measured for these films were of about 155 µΩ cm, significantly close to those corresponding to bulk TiC0.95 single crystals. The resistivity of R-DCMS films is higher by 6% to 23% in comparison with that of the DCMS/HiPIMS grown samples, depending on the growth temperature.

RETRACTED: Influence of sputtering parameters on the structural and mechanical properties of TiC thin film coating

Abstract Titanium carbide (TiC) nanostructured thin films coating were deposited on a commercially pure titanium (CpTi) substrate to enhance the surface properties using Radio Frequency (RF) Magnetron Sputtering coating technique. The sputtering time, power and temperature were varied during the process to study the influence of the sputtering parameters on the evolving properties of the thin films. The surface morphology of the films was studied using Field emission scanning electron microscope FESEM. Atomic force microscope was used to analyse the surface topography. The mechanical properties of the film were measured using nanoindentation. The structural properties were characterized using Grazing incidence X-ray diffraction, X-ray Photoelectron spectroscopy and Raman spectroscopy. The microstructure results of the planar view revealed the film microstructural evolution with varying sputtering parameters. The XRD analyses confirmed the presence of nanostructured TiC film with (1 1 0) preferential growth diffractogram. Absence of Raman active vibrational diffraction peaks was noticed for films with continuous and defect-free microstructure produced at RF power of 200 W. The Young modulus and hardness varied with the sputtering parameters with the highest hardness value attained at 250 W.

Preparation of Ti2C MXene phase by ion beam sputtering and ion irradiation

Thin titanium carbide films were prepared by ion beam sputtering of titanium and graphite targets followed by thermal annealing at 600 °C in vacuum and irradiation by Ar+ ions up to a fluence of 1015 ions/cm2. The stoichiometry of the films was analyzed by RBS and NRA methods, it was found to be Ti2.2C. The crystalline structure of the films was analyzed by STEM and EELS microscopic methods: before irradiation it was mostly amorphous with crystalline parts and visible network of micro-voids, crystallization and formation of laminar structure was observed after irradiation. The irradiated part showed corrugated surface morphology and a dense network of nano-openings. The thickness of the films increased from ca 67 nm to ca 83 nm. Obviously, the effect of the ion irradiation promoted the recrystallization and self-organization of the structure, resulting in the nano-laminar phase of Ti2C.

Bidirectional properties of TiC, TiN and TiNC thin films deposited by radio frequency magnetron sputtering.

Titanium nitride (TiN), titanium carbide (TiC) and titanium carbonitride (TiNC) thin films show promising practical applications due to their photoelectric properties and corrosion behaviour. In this work, we investigated the factors which may affect the optical properties and the corrosion behaviour of these coatings. The titanium coatings were carried out by sputtering using the target of Ti6Al4V (purity 99.96%) with different N2, CH4 and Ar partial pressures. XRD, FTIR, Raman and SEM with EDX studies show the formation of titanium nitride, titanium carbide coatings. Uv-vis spectroscopy was carried out to estimate the optical properties using the numerical Swanepoel method. Potentiodynamic polarization studies in Hank's solution show that the corrosion resistance is found to be in the order of C-TiN(2) > C-TiN(1) > TiN > TiC. A high protective efficiency was determined (60%) when comparing TiNC(2) and TiC corrosion current densities, which confirms the lower corrosion velocity and the higher passivation stability of the coatings composed with TiN and TiC phases. Electrochemical impedance spectroscopy studies show that the Rct increases in the following order: TiC < TiN < C-TiN(1) < C-TiN(2), highlighting the fact that C-TiN(2) coating has the higher corrosion resistance.

Study on high performance titanium by using mixture of titanium carbide and titanium dioxide film

Study on high performance titanium by using mixture of titanium carbide and titanium dioxide film

Improving the properties of 2D titanium carbide films by thermal treatment

A two-stage thermal treatment process at low temperature (300 °C) has been proposed to improve the conductivity, environmental stability and flexibility of the Ti3C2Txfilm simultaneously.