Structural characteristics and mechanical properties of Ti(Cr) films produced on Si substrate

A series of nanogranular Ti₉₀Cr₁₀ thin films have been fabricated by pulsed-laser deposition on Si substrates at different temperatures. The crystal structure and mechanical properties of these films were investigated. The X-ray diffraction and transmission electron microscope images with selected area diffraction showed that the structure of as-prepared films is dependent on film thickness and deposition temperature. It was found that the Ti₉₀Cr₁₀ films consisted of fine hexagonal close packed microstructure with columnar grains, while body close-packed cubic structure of Cr films are composed of irregular grains, meanwhile, a chromium disilicide (CrSi₂) layer formed in the interface between the substrate and Cr films which deposited at temperature of greater than 600 °C. The crystalline and columnar grains improved with an increase of the thickness of the films and an optimum microstructure is obtained under the present experimental condition of about 50 nm thickness and deposited temperature of 500 °C for Ti₉₀Cr₁₀ films. Deposited at 300 °C, the Ti₉₀Cr₁₀ films have hardness of 12.7 GPa and elastic modulus of 174.6 GPa. Improved to 600 °C the sample shows higher hardness of 13.1 GPa and higher elastic modulus of 183.2 GPa. Using Benjamin-Weaver model, adhesion shearing force can be calculated as 34.9 MPa for 300 °C Ti₉₀Cr₁₀ film while higher value of 44.4 MPa for higher temperature of 600 °C.     

Influence of N2 partial pressure on mechanical properties of (Ti,Al)N films deposited by reactive magnetron sputtering

The influence of the nitrogen partial pressure on the mechanical properties of (Ti,Al)N films deposited by DC reactive magnetron sputtering using a Ti-Al mosaic target at a substrate bias of −100 V is investigated. Nanoindentation tests reveal that with increasing N₂ partial pressure, the film hardness and elastic modulus increase initially and then decrease afterwards. The maximum hardness and elastic modulus are 43.4 GPa and 430.8 GPa, respectively. The trend is believed to stem from the variations in the grain size and preferential orientation of the crystals in the (Ti,Al)N films fabricated at varying N₂ partial pressure. The phenomenon is confirmed by results acquired using glancing angle X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS).     

Properties of aluminum oxide thin films deposited by pulsed laser deposition and plasma enhanced chemical vapor deposition

The chemical, structural, mechanical and optical properties of thin aluminum oxide films deposited at room temperature (RT) and 800 °C on (100) Si and Si-SiO₂ substrates by pulsed laser deposition and plasma enhanced chemical vapor deposition are investigated and compared. All films are smooth and near stoichiometric aluminum oxide. RT films are amorphous, whereas γ type nano-crystallized structures are pointed out for films deposited at 800 °C. A dielectric constant of ∼ 9 is obtained for films deposited at room temperature and 11-13 for films deposited at 800 °C. Young modulus and hardness are in the range 116-254 GPa and 6.4-28.8 GPa respectively. In both cases, the results show that the deposited films have very interesting properties opening applications in mechanical, dielectric and optical fields.     

Hardness enhancement and oxidation resistance of nanocrystalline TiN/MoxC multilayer films

In this paper the influence of the layer's microstructure on the hardness enhancement in multilayer nanocrystalline films and the oxidation resistance are studied. The TiN/Mo_xC multilayer films at different modulation period, and Mo_xC and TiN monolayer films were deposited on the (0 0 1) silicon wafers and molybdenum sheets by rf and dc magnetron sputtering. The monolayer TiN films with a thickness of about 2 μm are of pure face-center cubic TiN phase, while the monolayer Mo_xC films consist of two phases, one of which is body-center cubic Mo and the other is hexagonal Mo₂C as determined by XRD. The coarse columnar grains of about 200 nm in the monolayer TiN films become much smaller or disappear in the multilayer films. The hardness enhancement of the multilayer films takes place at the modulation period of 320 nm, which can reach to 26 GPa and is much higher than the values of Mo_xC and TiN monolayer films. This enhancement in hardness can be explained as the decrease in the size and/or disappearance of columnar grains in the TiN layer. The Young's modulus in the temperature range from 100 to 400 °C increases with decreasing modulation period. It is found that about 100 nm thick TiN films can increase largely the oxidation resistance of Mo_xC films.     

Characterization of magnetron co-sputtered W-doped C-based films

In this paper, W-doped C-based coatings were deposited on steel and silicon substrates by RF magnetron sputtering, using W and C targets, varying the cathode power applied to the W target and the substrate bias. The chemical composition was varied by placing the substrates in a row facing the C and W targets. W content in the films increased from 1 to 2 at.% over the C target to ∼ 73 at.% over the W target. The coatings with W content lower than ∼ 12 at.% and ∼ 23 at.%, for biased and unbiased conditions, respectively, showed X-ray amorphous structures, although carbide nanocrystals must exist as shown by the detection of the WC_1−x phase in films with higher W content. C-rich films were very dense and developed a columnar morphology with increasing W content. An improvement in the hardness (from 10 GPa, up to 25 GPa) of the films was achieved either when negative substrate bias was used in the deposition, or when the WC_1−x phase was detected by X-ray diffraction. The adhesion of the coatings is very low with spontaneous spallation of those deposited with negative substrate bias higher than 45 V. Varieties in cathode power (90 W or 120 W) applied to the W target showed no observable influence on the characteristics of the films.     

Influence of the annealing in nitrogen atmosphere on the XRD, EDX, SEM and electrical properties of chemical bath deposited CdSe thin films

The influence of annealing in nitrogen atmosphere on the structure, optical and electrical properties of cadmium selenide (CdSe) thin films deposited by chemical bath deposition (CBD) onto glass substrates was studied. The samples were annealed in nitrogen atmosphere at various temperatures. A transition from metastable nanocrystalline cubic to stable polycrystalline hexagonal phase has been observed after annealing. The as-deposited CdSe thin films grow in the nanocrystalline cubic phase with optical band gap 1.93 eV. The electrical resistivity of the thin films has been measured in order of 10⁶ Ω cm. The activation energy of the samples has been found to be 0.26–0.19 eV at low temperature region, and 0.36–0.56 eV at high temperature region. It was also found that the activation energy and the resistivity of the films decrease with the increasing annealing temperature.     

Structural, optical and electrical properties of undoped polycrystalline hematite thin films produced using filtered arc deposition

Thin films of α-Fe₂O₃ (hematite) were deposited using filtered arc deposition. The structural, optical and electrical properties of the films have been characterized. High-purity hematite films were produced, free from other iron oxide phases and impurities. The films exhibit preferred orientation, with the c-axis of the hexagonal structure aligned perpendicular to the substrate. The films have an upper uncertainty bound of the porosity of 15%, with a microindentation hardness of 17.5 ± 1 GPa and elastic modulus of 1235 ± 5 GPa. The indirect and direct band gap energies were found to be approximately 1.9 eV and 2.7 eV, respectively. The refractive index, and the extinction and absorption coefficients were determined from total reflectance and direct transmittance measurements. The thin films exhibit a high resistivity (≥ 10⁵ Ω cm) which indicates pure α-Fe₂O₃. An activation energy of 0.7 eV was calculated from an Arrhenius plot of the conductivity.     

A study of the nanostructure and hardness of electron beam evaporated TiAlBN Coatings

TiAlBN coatings have been deposited by electron beam (EB) evaporation from a single TiAlBN material source onto AISI 316 stainless steel substrates at a temperature of 450 °C and substrate bias of − 100 V. The stoichiometry and nanostructure have been studied by X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy. The hardness and elastic modulus were determined by nanoindentation. Five coatings have been deposited, three from hot-pressed TiAlBN material and two from hot isostatically pressed (HIPped) material. The coatings deposited from the hot-pressed material exhibited a nanocomposite nc-(Ti,Al)N/a-BN/a-(Ti,Al)B₂ structure, the relative phase fraction being consistent with that predicted by the equilibrium Ti-B-N phase diagram. Nanoindentation hardness values were in the range of 22 to 32 GPa. Using the HIPped material, coating (Ti,Al)B_0.29N_0.46 was found to have a phase composition of 72-79 mol.% nc-(Ti,Al)(N,B)_1 − x+ 21-28 mol.% amorphous titanium boride and a hardness of 32 GPa. The second coating, (Ti,Al)B_0.66N_0.25, was X-ray amorphous with a nitride+boride multiphase composition and a hardness of 26 GPa. The nanostructure and structure-property relationships of all coatings are discussed in detail. Comparisons are made between the single-EB coatings deposited in this work and previously deposited twin-EB coatings. Twin-EB deposition gives rise to lower adatom mobilities, leading to (111) (Ti,Al)N preferential orientation, smaller grain sizes, less dense coatings and lower hardnesses.     

Mechanical properties optimization of tungsten nitride thin films grown by reactive sputtering and laser ablation

Transition metal nitrides coatings are used as protective coatings against wear and corrosion. Their mechanical properties can be tailored by tuning the nitrogen content during film synthesis. The relationship between thin film preparation conditions and mechanical properties for tungsten nitride films is not as well understood as other transition metal nitrides, like titanium nitride. We report the synthesis of tungsten nitride films grown by reactive sputtering and laser ablation in the ambient of N₂ or N₂/Ar mixture at various pressures on stainless steel substrates at 400  C. The composition of the films was determined by XPS. The optimal mechanical properties were found by nanoindentation based on the determination of the proper deposition conditions. As nitrogen pressure was increased during processing, the stoichiometry and hardness changed from W₉N to W₄N and 30.8-38.7 GPa, respectively, for films deposited by reactive sputtering, and from W₆N to W₂N and 19.5-27.7 GPa, respectively, for those deposited by laser ablation.     

Structure, mechanical and tribological properties of diamond-like carbon films on aluminum alloy by arc ion plating

The low hardness and poor tribological performance of aluminum alloys restrict their engineering applications. However, protective hard films deposited on aluminum alloys are believed to be effective for overcoming their poor wear properties. In this paper, diamond-like carbon (DLC) films as hard protective film were deposited on 2024 aluminum alloy by arc ion plating. The dependence of the chemical state and microstructure of the films on substrate bias voltage was analyzed by X-ray photoelectron spectroscopy and Raman spectroscopy. The mechanical and tribological properties of the DLC films deposited on aluminum alloy were investigated by nanoindentation and ball-on-disk tribotester, respectively. The results show that the deposited DLC films were very well-adhered to the aluminum alloy substrate, with no cracks or delamination being observed. A maximum sp³ content of about 37% was obtained at −100 V substrate bias, resulting in a hardness of 30 GPa and elastic modulus of 280 GPa. Thus, the surface hardness and wear resistance of 2024 aluminum alloy can be significantly improved by applying a protective DLC film coating. The DLC-coated aluminum alloy showed a stable and relatively low friction coefficient, as well as narrower and shallower wear tracks in comparison with the uncoated aluminum alloy.     

Effect of Nb concentration on the structure,mechanical, optical,and electrical properties of nano-crystalline Ti<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Nb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>N thin films

The structure, mechanical, optical, and electrical properties of Ti_1−x Nb _x N thin films, 0 ≤ x ≤ 1, are reported. The films were deposited onto polycrystalline nuclear grade 316LN stainless steel substrate by radio frequency reactive magnetron sputtering in 100% N₂ plasma. X-ray diffraction results revealed that Nb is soluble in TiN up to x = 0.77. From x = 0.26 to x = 0.77, these films stabilized in rock salt structure with (111) orientation. The hardness and Young’s modulus increased, whereas electrical resistivity decreased with an increase in the Nb concentration in the films. The highest value of hardness and Young’s modulus were 31 and 320 GPa, respectively, for x = 0.77, at which the value of the lowest resistivity of 56 μΩ-cm was measured. The films showed a broad reflectance band, with a minimum in reflectance that shifted to shorter wavelengths as a function of increasing x. The reflectance band extended from the ultraviolet (~250 nm) to the visible region (~750 nm) and the position of the reflectance shifted from 2.33 to 3 eV with an increase in x from 0 to 0.77.     

Effect of substrate on microstructure and mechanical properties of sol–gel prepared (K,Na)NbO3 thin films

Lead-free ferroelectric (K, Na)NbO₃ (KNN) thin films (～200 nm thickness) were prepared using a modified sol–gel method by mixing K and Na acetates with the Nb–tartarate complex, deposited by spin-coating method on Pt/Al₂O₃ and Pt/SiO₂/Si substrates and sintered at 650 °C. Pure perovskite phase of K_0.65Na_0.35NbO₃ in film on silicon were revealed, while film on alumina contained also small amount of secondary pyrochlore Na₂Nb₈O₂₁ phase. Homogenous microstructure of film on Si substrate was smoother with the lower roughness (～7.4 nm) and contained spherical (～50 nm) particles. The mechanical properties of films were characterized by nanoindentation. The modulus and hardness of KNN films were calculated from their composite values of film/substrate systems using discontinuous and modified Bhattacharya model, respectively. The KNN film modulus was higher on alumina substrate (91 GPa) in comparison with silicon substrate (71 GPa) and values of film hardness were the same (4.5 GPa) on both substrates.     

Effects of oxygen or nitrogen doping on the microstructures, bonding, electrical, thermal properties and phase change kinetics of GeSb9 films

This study investigated the phase change kinetics, thermal, structural, electrical properties, and chemical bonding state of 50-nm-thick oxygen or nitrogen doped GeSb₉ films prepared by sputtering. Up to 6.8 at.% O or 8.7 at.% N doping, as measured by secondary ion mass spectrometry, the crystallization temperatures, lattice constants, and the resistivity of both crystalline and amorphous films increased with oxygen or nitrogen concentration , while the grain sizes decreased. Nitrogen atoms bonded to Ge and formed GeN₄ nitrides, and both the GeO₂ and Sb₂O₃ co-existed when oxygen concentration reached 8.5 at.%. Crystallization could be triggered by a laser pulse of duration 12 ns for all films. Both GeSb₉-O and GeSb₉-N films had fast crystallization speed, good thermal stability, and improved resistivity and are therefore potential candidates as active layers for phase-change memory.     

Structural evolution of La-Cr-O thin film: Part II. Elasto-plastic properties by nanoindentation

The goal of this research is to study the elasto-plastic properties of La-Cr-O thin films deposited by RF-magnetron sputtering on stainless steel interconnect materials after annealing at high temperatures in air. Elastic modulus, hardness and yield pressure derived from nanoindentation data are reported for thin films in different structural states. The amorphous film has an estimated elastic modulus of 174 GPa. The moduli of annealed films are calculated to be 150, 185 and 120 GPa after annealing at 500 °C, 600 °C and 800 °C, respectively. The film annealed at 800 °C has the lowest hardness and is dramatically different from the other structural states due to formation of the nanoporosity. The amorphous film and the films annealed at 500 °C and 600 °C both have hardness of 14 GPa, which is close to the value estimated by modeling.     

Synthesis-structure-property relations for Cr-B-N coatings sputter deposited reactively from a Cr-B target with 20 at% B

Cr-B-N films were synthesized by unbalanced magnetron sputtering from a sintered Cr-B target with 20 at% B in an Ar-N₂ discharge at varying N₂ partial pressures (p_N2) of up to 64% of the total pressure (p_Ar+p_N2=0.4 Pa). Coating composition and microstructure were investigated by X-ray diffraction, X-ray photoelectron spectroscopy and wavelength-dispersive electron-probe microanalysis and correlated with mechanical and tribological properties measured by microindentation and dry sliding ball-on-disk tests. For low nitrogen partial pressures (p_N2?22%), the XRD patterns are composed of broad overlapping peaks with low intensity. These films have hardness values of ∼15 GPa and indentation moduli of ∼150 GPa. Increasing p_N2 from 22% to 28% results in an increase of the N content from ∼38 to 50 at% where the films meet the quasi-binary CrN-BN composition. Thereby, an increase of the hardness from ∼15 to 32 GPa is obtained. A further increase in p_N2 up to 64% results in minor changes of the chemical composition, micro and bonding structure as well as mechanical properties. While in ball-on-disk testing early failure was observed for coatings grown at p_N2?22%, higher nitrogen contents in the discharge yielded friction coefficients of ∼0.43 independent of chemical composition, microstructure and mechanical properties.     

Effect of annealing on the composition, structure and mechanical properties of carbon nitride films deposited by middle-frequency magnetron sputtering

Carbon nitride films were deposited by middle-frequency reactive magnetron sputtering and annealed at different temperatures in nitrogen ambient. X-ray photoelectron spectroscopy, Raman scattering, transmission electron microscopy, and nano-indenter were used to characterize the as-deposited and annealed films. The analysis showed that annealing resulted in the dissociation of N and C in the films. The dissociation of C happened after 500 °C and lagged behind that of N. With the increase of annealing temperature, the disorder of sp² C decreased and the films were gradually graphitized. The microstructure changed from amorphous to fullerene-like CN_x with the annealing temperature increasing to 500 °C, and then to nitridized graphite nanocrystals at 600 °C. The graphitization resulted in a drastic decreasing of hardness and modulus of the films.     

氮流量比对磁控溅射(CoCrFeNi)Nx高熵合金薄膜的组织和性能的影响

采用直流磁控溅射法制备(CoCrFeNi)N_x高熵薄膜,研究了氮流量比对薄膜的力学性能和电磁性能的影响。结果表明,在不同氮流量比条件下制备的(CoCrFeNi)N_x薄膜,都具有致密的组织、简单的FCC结构并呈现(200)择优取向。随着氮流量比从10%提高到30%,薄膜的硬度和弹性模量随之增大,其最大值达到14 GPa和212 GPa;电阻率基本上呈增大的趋势,最大值达到138 μΩ?cm;饱和磁化强度和磁导率随之减小,薄膜饱和磁化强度最高为427.43 emu/cm³。薄膜的矫顽力约为0。     

Investigation of structural,optical and micro-mechanical properties of (NdyTi1 − y)Ox thin films deposited by magnetron sputtering

TiO₂ and (Nd_yTi_1 − y)O_x thin films were deposited by reactive magnetron sputtering process from mosaic Ti–Nd targets and characterised by X-ray diffraction (XRD), Raman optical spectroscopy and nanoindentation technique. XRD measurements revealed that as-prepared titanium dioxide and TiO₂ thin films with 4 and 7 at.% of Nd had nanocrystalline rutile structure, while coatings with larger amount of Nd were amorphous. Raman spectroscopy investigations showed that the increase of the neodymium concentration caused amorphisation of the coatings and hindered their crystal growth. All as-prepared coatings were transparent in the visible wavelength range with a transmittance of approximately 80%. The refractive index and extinction coefficient of the thin films gradually decreased with the increase of the neodymium concentration. Micro-mechanical properties, i.e. hardness and elastic modulus, were determined using traditional load-controlled nanoindentation testing and continuous stiffness measurements. The highest hardness and elastic modulus values were obtained for thin films with 7 at.% of Nd and were approximately 14.8 GPa and 166.3 GPa, respectively.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Preparation of Cr(N,O) thin films by RF reactive unbalanced magnetron sputtering

Chromium oxynitride thin films were deposited by radio-frequency (RF) reactive unbalanced magnetron sputtering at various O₂ flow rates onto Si(100) and glassy carbon substrates. The compositions of the thin films were analyzed by Rutherford backscattering spectroscopy. The thin films were found to contain up to 44 at.% oxygen. In Fourier-transform infrared spectra, a peak attributed to the Cr-N bond of CrN was observed, but no peak attributable to the Cr-O bond of Cr₂O₃ was found. The textures of the thin films were observed by transmission electron microscopy, which revealed that samples had a columnar structure. The hardness of the thin films was measured by nanoindentation. The hardness increased from 20 GPa to a maximum value of 31 GPa with increasing oxygen content.