Effect of annealing temperature on microstructure, hardness and adhesion properties of TiSixNy superhard coatings

A series of TiSi_xN_y superhard coatings with different Si contents were prepared on M42 steel substrates using two Ti and two Si targets by reactive magnetron sputtering at 500 °C. These samples were subsequently vacuum-annealed at 500, 600, 700, 800 and 900 °C, respectively. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), microindenter, Rockwell hardness tester and scratch tester were applied to investigate the microstructure, phase configuration, hardness and adhesion properties of as-deposited and annealed samples. The results indicated that there were two bonds, TiN and Si₃N₄, in all presently deposited TiSi_xN_y thin films, that structure was nanocomposite of nanocrystalline (nc-) TiN embedded into amorphous Si₃N₄ matrices. Annealing treatment below 900 °C played a little role in microstructure and hardness of the coatings although it greatly affected those of steel substrates. The film-substrate adhesion strength was slightly increased, followed by an abrupt decrease with increasing annealing temperature. Its value got to the maximum at 600 °C. Annealing had little effect on the friction coefficient with its value varying in the range of 0.39-0.40.     

Comparison study on structure of Si and Cu doping CrN films by reactive sputtering

CrN, CrSiN and CrCuN films were deposited by DC magnetron reactive sputtering with hot pressed pure Cr, CrSi, and CrCu targets, respectively. As substrate bias increased from −50 V to −200 V, the preferred orientation of CrN films changed from (1 1 1) to (2 0 0). And the Si doping did not change this condition. However, the Cu doping films kept (2 0 0) orientation all along. CrN films presented typical columnar structure, and the alloying of Si and Cu could restrain columnar growth leading to dense structure. The CrSiN film was composed of nanocrystallites distributed in amorphous Si₃N₄, while no amorphous phase existed in CrCuN films.     

Structural and mechanical properties of multi-element (TiVCrZrHf)N coatings by reactive magnetron sputtering

In this study, (TiVCrZrHf)N multi-component coatings with quinary metallic elements were deposited by reactive magnetron sputtering system. The composition, structure, and mechanical properties of the coatings deposited at different N₂ flow rates were investigated. The (TiVCrZrHf)N coatings deposited at N₂ flow rates of 0, 1, and 2 SCCM showed an amorphous structure, whereas those deposited at N₂ flow rates of 4 and 6 SCCM showed a simple face-centered cubic solid solution structure. A saturated nitride coating was obtained for N₂ flow of 4 SCCM and higher. By increasing N₂ flow to 4 SCCM, the hardness and modulus reached a maximum value of 23.8 ± 0.8 and 267.3 ± 4.0 GPa, respectively.     

Influence of silicon on the microstructure and mechanical properties of Zr-Si-N composite films

A series of Zr-Si-N composite films with different Si contents were synthesized in an Ar and N₂ mixture atmosphere by the bi-target reactive magnetron sputtering method. These films’ composition, microstructure and mechanical properties were characterized by energy dispersive spectroscopy, X-ray diffraction, scanning electron microscopy, atomic force microscopy and nanoindentation. Experimental results revealed that after the addition of silicon, Si₃N₄ interfacial phase formed on the surface of ZrN grains and prevented them from growing up. Zr-Si-N composite films were strengthened at low Si content with the hardness and elastic modulus reaching their maximum values of 29.8 and 352 GPa at 6.2 at% Si, respectively. With a further increase of Si content, the crystalline Zr-Si-N films gradually transformed into amorphous, accompanied with a remarkable fall of films’ mechanical properties. This limited enhancement of mechanical properties in the Zr-Si-N films may be due to the low wettability of Si₃N₄ on the surface of ZrN grains.     

Crystallization of amorphous Si3N4 and superhardness effect in HfC/Si3N4 nanomultilayers

HfC/Si₃N₄ nanomultilayers with various thicknesses of Si₃N₄ layer have been prepared by reactive magnetron sputtering. Microstructure and mechanical properties of the multilayers have been investigated. The results show that amorphous Si₃N₄ is forced to crystallize and grow coherently with HfC when the Si₃N₄ layer thickness is less than 0.95 nm, correspondingly the multilayers exhibit strong columnar structure and achieve a significantly enhanced hardness with the maximum of 38.2 GPa. Further increasing Si₃N₄ layer thickness leads to the formation of amorphous Si₃N₄, which blocks the coherent growth of multilayer, and thus the hardness of multilayer decreases quickly.     

Structure and mechanical properties of reactive sputtering CrSiN films

CrSiN films with various Si contents were deposited by reactive magnetron sputtering using the co-deposition of Cr and Si targets in the presence of the reactive gas mixture. Comparative studies on microstructure and mechanical properties between CrN and CrSiN films with various Si contents were carried out. The structure of the CrSiN films was found to change from crystalline to amorphous structure as the Si contents increase. Amorphous phase of Si₃N₄ compound was suggested to exist in the CrSiN film. The growth of films has been observed from continuous columnar structure, granular structure to glassy-like appearance morphology with the increase of silicon content. The film fracture changed from continuous columnar structure, granular structure to glassy-like appearance morphology with the increase of silicon content. Two hardness peaks of the films as function of Si contents have been discussed.     

SiOxNy thin films with variable refraction index: Microstructural, chemical and mechanical properties

In this work amorphous silicon oxynitride films with similar composition (ca. Si_0.40N_0.45O_0.10) were deposited by reactive magnetron sputtering from a pure Si target under different N₂-Ar mixtures. Rutherford backscattering (RBS) studies revealed that the coatings presented similar composition but different density. The mechanical properties evaluated by nanoindentation show also a dependence on the deposition conditions that does not correlate with a change in composition. An increase in nitrogen content in the gas phase results in a decrease of hardness and Young's modulus.The microstructural study by high resolution scanning electron microscopy (SEM-FEG) on non-metalized samples allowed the detection of a close porosity in the form of nano-voids (3-15 nm in size), particularly in the coatings prepared under pure N₂ gas. It has been shown how the presence of the close porosity allows tuning the refraction index of the films in a wide range of values without modifying significantly the chemical, thermal and mechanical stability of the film.     

Synthesis and characterization of superhard Ti-Si-N films obtained in an inductively coupled plasma enhanced chemical vapor deposition (ICP-CVD) with magnetic confinement

Using a novel inductively coupled plasma enhanced chemical vapor deposition (ICP-CVD) with magnetic confinement system, Ti-Si-N films were prepared on single-crystal silicon wafer substrates by sputtering Ti and Si (5 at.%:1 at.%) alloyed target in argon/nitrogen plasma. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), atomic force microscopy (AFM) and Nano Indenter XP tester were employed to characterize nanostructure and performances of the films. These films were essentially composed of TiN nanocrystallites embedded in an amorphous Si₃N₄ matrix with maximum hardness value of 44 GPa. Experimental results showed that the film hardness was mainly dependent on the TiN crystallite size and preferred orientation, which could be tailored by the adjustment of the N₂/Ar ratio. When the N₂/Ar ratio was 3, the film possessed the minimum TiN size of 10.5 nm and the maximum hardness of 44 GPa.     

The effects of Si3N4 interlayer on the thermal stability and hardness of Ti/TiNx (x = 0.5-1) nanolayered coatings

The polycrystalline Ti/TiN_x multilayer films were deposited by magnetron sputtering, and the as-deposited multilayer coatings were annealed at 500-800 °C for 2-4 h in vacuum. We investigated the effects of annealing temperature and annealing time on the microstructural, interfacial, and mechanical properties of the polycrystalline Ti/TiN_x multilayer films. It was found that the hardness increased with annealing temperature. This hardness enhancement was probably caused by the preferred crystalline orientation TiN(1 1 1). The X-ray reflectivity measurements showed that the layer structure of the coatings could be maintained after annealing at 500 °C and the addition of the Si₃N₄ interlayer to Ti/TiN_x multilayer could improve the thermal stability to 800 °C.     

(Ti,Al,Si,C)N nanocomposite coatings synthesized by plasma-enhanced magnetron sputtering

Materials’ surface service property could be enhanced by transition metal nitride hard coatings due to their high hardness, wear and high temperature oxidation resistance, but the higher friction coefficient (0.4-0.9) of which aroused terrible abrasion. In this work, quinternary (Ti,Al,Si,C)N hard coating 3-4 μm was synthesized at 300 °C using plasma enhanced magnetron sputtering system. It was found that the coating's columnar crystals structure was restrained obviously with the increase of C content and a non-columnar crystals growth mode was indicated at the C content of 33.5 at.%. Both the XRD and TEM showed that the (Ti,Al,Si,C)N hard coatings had unique nanocomposite structures composed of nanocrystalline and amorphous nc-(Ti,Al)(C,N)/nc-AlN/a-Si₃N₄/a-Si/a-C. However, the coatings were still super hard with the highest hardness of 41 GPa in spite of the carbon incorporation. That a-C could facilitate the graphitization process during the friction process which could improve the coating's tribological performance. Therefore, that nanocomposite (Ti,Al,Si,C)N coatings with higher hardness (>36 GPa) and a lower friction coefficient (<0.2) could be synthesized and enhance the tribological performance and surface properties profoundly.     

Ultra-thin a-SiNx protective overcoats for hard disks and read/write heads

This paper reports that amorphous silicon nitride (a-SiNx) overcoats were deposited at room temperature by microwave ECR plasma enhanced unbalanced magnetron sputtering. The 2 nm a-SiNx overcoat has better anti-corrosion properties than that of reference a-CNx overcoats (2-4.5 nm). The superior anti-corrosion performance is attributed to its stoichiometric bond structure, where 94.8% Si atoms form Si-N asymmetric stretching vibration bonds. The N/Si ratio is 1.33 as in the stoichiometry of Si3N4 and corresponds to the highest hardness of 25.0 GPa. The surface is atomically smooth with RMS < 0.2 nm. The ultra-thin a-SiNx overcoats are promising for hard disks and read/write heads protective coatings.     

Ellipsometric study of a-Be3N2 thin films prepared by radio frequency magnetron sputtering

The ellipsometric characterizations of amorphous beryllium nitride (a-Be₃N₂) thin films deposited on Si (1 0 0) and quartz at temperature <50 °C using reactive RF sputtering deposition were examined in the wavelength range 280-1600 nm. X-ray diffraction of the films showed no structure, suggesting the Be₃N₂ films grown on the substrates are amorphous. The composition and chemical structures of the amorphous thin films were determined by using electron spectroscopy for chemical analysis. The surface morphology of a-Be₃N₂ was characterized by atomic force microscopy. The thicknesses and optical constants of the films were derived from spectroscopic ellipsometry measurements. The variation of the optical constants with thickness of the deposited films has been investigated. From the angle dependence of the polarized reflectivity we deduced a Brewster angle of 64°. At any angle of incidence, the a-Be₃N₂ shown high transmissivity (80-99%) and low reflectivity (<18%) in the visible and near infrared regions. Hence, the a-Be₃N₂ could be a good candidate for antireflection optical coatings under conditions of optimized the type of polarization and the angle of incidence.     

Sputtering pressure effects on the structural and mechanical properties of TiVCr alloy coatings

In this study, TiVCr alloy coatings were deposited on Si substrates by magnetron sputtering system at different working pressures (0.33-1 Pa). The TiVCr coatings have a composite structure with amorphous and body-centered cubic (bcc) crystal phases comprised of bundles of fine fibrous structures and V-shaped columnar structures, respectively. Compared with the amorphous zone, the crystalline zone has a denser and more compact structure. The coating microstructure became more porous as working pressure increased. Consequently, the crystal zones of the deposited coatings at 0.33 Pa obtained higher hardness (11.6 GPa) while the deposited coatings at 1 Pa achieved lower hardness (4.5 GPa).     

Intrinsic mechanical properties of ultra-thin amorphous carbon layers

In this work, we extracted the film's hardness (H_F) of ultra-thin diamond-like carbon layers by simultaneously taking into account the tip blunting and the substrate effect. As compared to previous approaches, which did not consider tip blunting, this resulted in marked differences (30-100%) for the H_F value of the thinner carbon coatings. We find that the nature of the substrate influences this intrinsic film parameter and hence the growth mechanisms. Moreover, the H_F values generally increase with film thickness. The 10 nm and 50 nm thick hydrogenated amorphous carbon (a-C:H) films deposited onto Si have H_F values of, respectively, ∼26 GPa and ∼31 GPa whereas the 10 nm and 50 nm thick tetrahedral amorphous carbon (t-aC) films deposited onto Si have H_F values of, respectively, ∼29 GPa and ∼38 GPa. Both the a-C:H and t-aC materials also show higher density and refractive index values for the thicker coatings, as measured, respectively by X-ray reflectometry and optical profilometry analysis. However, the Raman analysis of the a-C:H samples show bonding characteristics which are independent of the film thickness. This indicates that in these ultra-thin hydrogenated carbon films, the arrangement of sp² clusters does not relate directly to the hardness of the film.     

Influence of reactive gas and temperature on structural properties of magnetron sputtered CrSiN coatings

CrSiN coatings were deposited on stainless steel (Grade: SA304) and silicon Si(1 0 0) substrates, with varying argon-nitrogen gas proportions and deposition temperature, using reactive magnetron sputtering technique in the present work. The influence of sputtering (Ar) and reactive gas proportions (N₂) and temperature on the structural properties of the CrSiN coating was investigated. A small amount of silicon content (3.67 at.% Si) plays a crucial role in addition to the nitrogen content for the formation of different phases in the CrSiN coatings as observed in the present work. For example, the coating with comparatively low nitrogen content, 40% N₂, during deposition, formed a crystalline structure consisting of nano-crystalline CrN which is separated by an amorphous SiN phase, as evident from X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The formation of CrN(1 1 1) and Cr₂N(1 1 1) phases has occurred at 30% N₂ with 3.67% Si content, which transformed in to CrN(1 1 1) and CrN(2 0 0) with increase in N₂ content but with same Si content. The surface topography and morphology of the coatings were analyzed by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM), respectively. A less columnar growth is observed in CrSiN coatings deposited at low argon content, Ar:N₂ (20:80), and with 3.67 at.% Si in the coatings. However, it becomes dense with increase in nitrogen content and temperature. The XRD analysis showed that the intensity of a dominating peak (1 1 1) is decreasing from (80:20) to (60:40) argon:nitrogen environment. With a further increase of nitrogen content, from (60:40), in the sputtering gas mixture, to (40:60) argon-nitrogen, there is a sudden increase in (1 1 1) peak and above (40:60), the peak reduction rate is very slow than the previous one. The (1 1 1) and (2 0 0) peak intensity variations are very limited due to high nitrogen content, above 50%, and considerable amount of Si atoms, 3.67 at.%, present in the CrN coatings.     

Evaluation of Si3N4/Si interface by UV Raman spectroscopy

The stresses at Si₃N₄/Si (1 0 0), (1 1 1) and (1 1 0) interfaces were measured by UV Raman spectroscopy with a 364 nm excitation laser whose penetration depth into the Si substrate was estimated to be 5 nm. The Si₃N₄ films were formed on Si (1 0 0), (1 1 1) and (1 1 0) using nitrogen-hydrogen (NH) radicals produced in microwave-excited high-density Xe/NH₃ mixture plasma. The localized stress detected from Raman peak shift was compressive at the (1 0 0) interface, and tensile at the (1 1 1) and (1 1 0) interfaces. The results showed that stress had strong correlation with the total density of subnitrides at the Si₃N₄/Si interface, and also with the full-width at half-maximum (FWHM) of Si the 2p_3/2 photoemission spectrum arising from the substrate. We believe that the localized stress affected subnitride formation because the amount of subnitride and the FWHM of Si 2p_3/2 decreased while the interface stress shifted in the tensile direction.     

Structure and mechanical properties of Ni-P electrodeposited coatings

The coatings with different phosphorus contents were obtained by varying the concentration of H₃PO₃ in the electroplating bath. With the increase of phosphorus content, the structure of the Ni-P electrodeposited coatings transformed from microcrystalline to a mixture of nanocrystalline and amorphous phases, then to amorphous phase. A high hardness value of 710 HV_0.1 of as-deposited Ni-P coating was obtained at 8.3 at.% phosphorus content, and high wear resistance was accordingly achieved. The refined nanocrystalline grains with average size of about 7 nm were found to be responsible for the high hardness and improved wear resistance of the as-deposited Ni-P electrodeposited coating.     

Si3N4的晶体化和ZrN/Si3N4纳米多层膜的超硬效应

研究了Si₃N₄层在ZrN/Si₃N₄纳米多层膜中的晶化现象及其对多层膜微结构与力学性能的影响. 一系列不同Si₃N₄层厚度的ZrN/Si₃N₄纳米多层膜通过反应磁控溅射法制备. 利用X射线衍射仪、高分辨透射电子显微镜和微力学探针表征了多层膜的微结构和力学性能. 结果表明，由于受到ZrN调制层晶体结构的模板作用，溅射条件下以非晶态存在的Si₃N₄层在其厚度小于0.9 nm时被强制晶化为NaCl结构的赝晶体，ZrN/Si₃N₄纳米多层膜形成共格外延生长的柱状晶，并相应地产生硬度升高的超硬效应. Si₃N₄随层厚的进一步增加又转变为非晶态，多层膜的共格生长结构因而受到破坏，其硬度也随之降低.     

Formation of Cr-modified silicide coatings on a Ti-Nb-Si based ultrahigh-temperature alloy by pack cementation process

Cr-modified silicide coatings were prepared on a Ti-Nb-Si based ultrahigh temperature alloy by Si-Cr co-deposition at 1250 °C, 1350 °C and 1400 °C for 5-20 h respectively. It was found that both coating structure and phase constituents changed significantly with increase in the co-deposition temperature and holding time. The outer layers in all coatings prepared at 1250 °C for 5-20 h consisted of (Ti,X)₅Si₃ (X represents Nb, Cr and Hf elements). (Ti,X)₅Si₄ was found as the only phase constituent in the intermediate layers in both coatings prepared at 1250 °C for 5 and 10 h, but the intermediate layers in the coatings prepared at 1250 °C for 15 and 20 h were mainly composed of (Ti,X)₅Si₃ phase that was derived from the decomposition of (Ti,X)₅Si₄ phase. In the coating prepared at 1350 °C for 5 h, single (Ti,X)₅Si₃ phase was found in its outmost layer, the same as that in the outer layers in the coatings prepared at 1250 °C; but in the coatings prepared at 1350 °C for 10-20 h, (Nb_1.95Cr_1.05)Cr₂Si₃ ternary phase was found in the outmost layers besides (Ti,X)₅Si₃ phase. In the coatings prepared at 1400 °C for 5-20 h, (Nb_1.95Cr_1.05)Cr₂Si₃ ternary phase was the single phase constituent in their outmost layers. The phase transformation (Ti,X)₅Si₄ → (Ti,X)₅Si₃ + Si occurred in the intermediate layers of the coatings prepared at 1350 and 1400 °C with prolonging co-deposition time, similar to the situation in the coatings prepared at 1250 °C for 15 and 20 h, but this transformation has been speeded up by increase in the co-deposition temperature. The transitional layers were mainly composed of (Ti,X)₅Si₃ phase in all coatings. The influence of co-deposition temperature on the diffusion ability of Cr atoms was greater than that of Si atoms in the Si-Cr co-deposition processes investigated. The growth of coatings obeyed inverse logarithmic laws at all three co-deposition temperatures. The Si-Cr co-deposition coating prepared at 1350 °C for 10 h showed a good oxidation resistance due to the formation of SiO₂ and Nb, Cr-doped TiO₂ scale after oxidation at 1250 °C for 10 h.     

The impact of ultra thin silicon nitride buffer layer on GaN growth on Si (1 1 1) by RF-MBE

Ultra thin films of pure silicon nitride were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma with a high content of nitrogen atoms. The effect of annealing of silicon nitride surface was investigated with core-level photoelectron spectroscopy. The Si 2p photoelectron spectra reveals a characteristic series of components for the Si species, not only in stoichiometric Si₃N₄ (Si⁴⁺) but also in the intermediate nitridation states with one (Si¹⁺) or three (Si³⁺) nitrogen nearest neighbors. The Si 2p core-level shifts for the Si¹⁺, Si³⁺, and Si⁴⁺ components are determined to be 0.64, 2.20, and 3.05 eV, respectively. In annealed sample it has been observed that the Si⁴⁺ component in the Si 2p spectra is significantly improved, which clearly indicates the crystalline nature of silicon nitride. The high resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM) and photoluminescence (PL) studies showed a significant improvement of the crystalline qualities and enhancement of the optical properties of GaN grown on the stoichiometric Si₃N₄ by molecular beam epitaxy (MBE).