Tribological behavior of hafnium diboride thin films

Transition metal diborides and their coatings offer an excellent combination of high hardness, high chemical stability and high thermal conductivity, thus they are excellent candidates for a wide range of tribological applications. In this work, stoichiometric hafnium diboride films were grown by chemical vapor deposition from a single-source, heteroatom-free precursor Hf(BH₄)₄ under conditions that afford highly conformal and smooth films. HfB₂ films of thickness ∼ 0.6 μm deposited on steel substrates were subjected to pin-on-disk wear testing against a counter face disc of AISI 440C martensitic stainless steel. Based on wear measurements, both as-deposited (X-ray amorphous) and annealed (nanocrystalline) samples showed very high wear resistance compared to uncoated samples. For the annealed samples, SEM analysis indicated the formation of a wear resistant composite body in the wear scar, even at depths far exceeding the film thickness, which appears to dramatically improve wear resistance. No mild-to-severe wear transition was observed which indicates that mild wear occurred throughout the wear test. This ensemble of results, when considered in the light of high contact pressures (∼ 700 MPa) used in the study, makes the HfB₂ material potentially attractive for wear-resistant applications.     

Effect of annealing on pulsed laser deposited zirconium oxide thin films

Zirconium oxide thin films were deposited using pulsed laser ablation from a ceramic ZrO₂ target on unheated substrates. Subsequently, the films were annealed in air in the temperature range 400-800 °C. The films were characterized by X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and optical spectroscopy to investigate the variation of the structural, chemical, and optical properties upon annealing. As-deposited films were amorphous and had a large surface density of ablated particles. Annealing resulted in the growth of monoclinic nano-crystalline, uniform, and transparent films that were slightly sub-stoichiometric. The annealed films were compact and had high values of the refractive index. Extinction coefficients were small, and may be related to the presence of defects. The films exhibited the presence of an indirect band gap, related to defects, and a direct band gap, related to fundamental absorption.     

Influence of O2/Ar flow ratio on the structure and optical properties of sputtered hafnium dioxide thin films

Hafnium dioxide (HfO₂) thin films were deposited on a quartz substrate by RF reactive magnetron sputtering. The influence of O₂/Ar flow ratio on the deposition rate, structure and optical properties of HfO₂ thin films were systematically studied using X-ray diffraction (XRD), scan electron microscopy (SEM) and UV-visible spectroscopy. The results show that the deposition rate decreases obviously when the O₂/Ar flow ratio increases from 0 to 0.25 and then, decreases little as the O₂/Ar flow ratio further increases to 0.50. The HfO₂ thin films prepared are all polycrystalline with a monoclinic phase. The thin film deposited with pure argon shows a preferential growth and has considerably improved crystallinity and much larger crystallite size. Meanwhile, after oxygen is introduced into the deposition, the thin films prepared have random orientation, weakened crystallinity and smaller crystallite size. The refractive index is higher for the thin film deposited without oxygen and increases as the O₂/Ar flow ratio increases from 0.25 to 0.50. The band gap energy of the thin film increases with an increasing O₂/Ar flow ratio.     

Amorphous and nanocrystalline sputtered Mg–Cu thin films

Binary Mg–Cu amorphous alloys were first fabricated in 1980s via liquid quenching. In this study, the Mg_1−xCu_x (x varying from 38 at.% to 82 at.%) partially amorphous thin films are prepared via co-sputtering. Upon thermal annealing, the Mg₂Cu or MgCu₂ nanocrystalline phases are induced in the Mg-rich or Cu-rich thin films, respectively. Due to the presence of fine nanocrystalline Mg₂Cu or MgCu₂ particles in the Mg–Cu amorphous matrix, the as-sputtered thin films show satisfactory Young's modulus 100 GPa and hardness 4 GPa.     

过滤阴极真空电弧制备非晶金刚石红外保护膜

采用过滤阴极真空电弧技术,通过施加不同衬底偏压制备了非晶金刚石薄膜.利用纳米压痕仪和光谱椭偏仪测试薄膜的力学性能和光学性能,利用KLA-Tencor台阶仪测试硅衬底在薄膜沉积前后的曲率半径,并根据Stoney方程计算薄膜应力,利用可见光拉曼光谱和电子能量损耗谱研究了薄膜的微结构.实验表明:当衬底负偏压为80 V时,薄膜的硬度、弹性模量、光学带隙和折射率均达到最大值,随着偏压的升高或降低,各参量分别降低;此时,薄膜的sp3杂化含量最高,斜坡系数却最小;在宽红外波段范围内,薄膜的消光系数趋近于零,即红外透明;另外,薄膜具有接近金刚石的高硬度和高模量,并且其微结构以及光学和力学性能可调,因此是一种优异的红外光学窗口增透保护薄膜材料.     

Microstructure and optical absorption properties of Au-dispersed CoO thin films

Au nanoparticles dispersed cobalt monoxide (CoO) composite films were fabricated via a chemical solution approach combined with a spin-coating processing. Au particles were spherical approximately and uniformly dispersed in the amorphous CoO matrix. The mean diameters of Au particles in the Au/CoO thin films with 40 mol% Au are about 30 nm. The optical absorption peaks due to the surface plasmon resonance (SPR) of Au particles were observed in the UV-vis absorption spectra in the wavelength range of 550-650 nm. The SPR peaks exhibit a red shift and intensify with increasing Au content from 10 to 40 mol%, but show a blue shift and weaken from 40 to 60 mol%. The band gap E_g decreases with increasing Au contents from 10 to 40 mol% but increases by further increasing Au content.     

Intrinsic low energy bombardment of titanium chromium oxide thin films prepared by reactive sputtering

Titanium chromium oxide thin films were deposited by a DC reactive magnetron sputtering from separate Ti and Cr metallic targets in a reactive atmosphere. A constant current density J_Ti =150 A m⁻² was used to sputter the titanium target, whereas the current density on the chromium target was systematically changed from J_Cr=0–200 A m⁻². X-Ray diffraction, electron probe microanalysis and atomic force microscopy were used to investigate the effect of an increasing current density of the chromium target on the structural, compositional and morphological parameters of the coatings. A continuous evolution of the Ti_xCr_1−xO_y composition was observed (x=1–0.34 and y=2–1.7), whereas an amorphisation of the material and a maximum of the surface roughness was obtained for J_Cr=50–100 A m⁻². In the same way, energy distribution of the neutral and ionic species impinging on the surface of the growing film were determined by energy-resolved mass spectrometry. Mean energies and the relative fluxes of positive and negative ions were determined from their energy distributions. The behaviour of these species was also affected by the chromium current density especially between J_Cr=50 and 100 A m⁻². Similarities in the changes of the thin films properties and the characteristics of ionic species are discussed, so as to establish some relationships between the plasma parameters and the deposited films.     

Low temperature processed highly conducting, transparent, and wide bandgap Gd doped CdO thin films for transparent electronics

Gadolinium (Gd) doped cadmium oxide (CdO) thin films are grown at low temperature (100 °C) using pulsed laser deposition technique. The effect of oxygen partial pressures on structural, optical, and electrical properties is studied. X-ray diffraction studies reveal that these films are polycrystalline in nature with preferred orientation along (1 1 1) direction. Atomic force microscopy studies show that these films are very smooth with maximum root mean square roughness of 0.77 nm. These films are highly transparent and transparency of the films increases with increase in oxygen partial pressure. We observe an increase in optical bandgap of CdO films by Gd doping. The maximum optical band gap of 3.4 eV is observed for films grown at 1 × 10⁻⁵ mbar. The electrical resistivity of the films first decreases and then increases with increase in oxygen partial pressure. The lowest electrical resistivity of 2.71 × 10⁻⁵ Ω cm and highest mobility of 258 cm²/Vs is observed. These low temperature processed highly conducting, transparent, and wide bandgap semiconducting films could be used for flexible optoelectronic applications.     

Annealing temperature dependence of the optical and structural properties of selenium-rich CdSe thin films

Structural and optical properties of selenium-rich CdSe (SR-CdSe) thin films prepared by thermal evaporation are studied as a function of annealing temperature. X-ray diffraction (XRD) patterns show that the as-prepared films were amorphous, whereas the annealed films are polycrystalline. Analyzing XRD patterns of the annealed films reveal the coexistence of both (hexagonal) Se and (hexagonal) CdSe crystalline phases. Surface roughness of SR-CdSe films is measured using atomic force microscope (AFM). Analyses of the absorption spectra in the wavelength range (200-2500 nm) of SR-CdSe thin films indicates the existence of direct and indirect optical transition mechanisms. The optical band gap (E_g) of as-prepared film is 1.92 and 2.14 eV for the indirect allowed and direct allowed transitions respectively. After annealing, the absorption coefficient and optical band gap were found to decrease, while the values of refractive index (n) and the extinction coefficient (k_ex) increase. The dispersion of the refractive index is described using the Wimple-Di Domenico (WDD) single oscillator model and the dispersion parameters are calculated as a function of annealing temperature. Besides, the high frequency dielectric constant (?_∞) and the ratios of the free carrier concentration to its effective mass (N/m*) are studied as a function of annealing temperature. The results are discussed and correlated in terms of amorphous-crystalline transformations.     

New process for synthesis of nickel oxide thin films and their characterization

Sol-gel spin coating method has been successfully employed for the deposition of nanocrystalline nickel oxide (NiO) thin films. The films were annealed at 400-700 °C for 1 h in an air and changes in the structural, morphological, electrical and optical properties were studied. The structural properties of nickel oxide films were studied by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis shows that all the films are crystallized in the cubic phase and present a random orientation. Surface morphology of the nickel oxide film consists of nanocrystalline grains with uniform coverage of the substrate surface with randomly oriented morphology. The electrical conductivity showed the semiconducting nature with room temperature electrical conductivity increased from 10⁻⁴ to 10⁻² (Ω cm)⁻¹ after annealing. The decrease in the band gap energy from 3.86 to 3.47 eV was observed after annealing NiO films from 400 to 700 °C. These mean that the optical quality of NiO films is improved by annealing.     

Structural and optical analysis of ZnBeMgO powder and thin films

We here report the structural and optical studies of Zn_1−x−yBe_xMg_yO (0 ≤ x ≤ 0.15; 0 ≤ y ≤ 0.20) powders and thin films. From the Rietveld refinement of the powder X-ray diffraction (XRD) patterns it was revealed that the value of ‘a’ lattice parameter remains almost unchanged whereas ‘c’ parameter reduces with Be and Mg co-doping in ZnO. The Zn-O bond length also decreases in co-doped samples. Raman studies of the pure ZnO powder showed all the characteristic peaks of the wurtzite hexagonal structure and with (Be, Mg) co-doping new modes appeared which can be attributed to arise as a result of substitution. The XRD of the films prepared from the powders using pulsed laser deposition (PLD) technique exhibited the preferential orientation and with increase in co-doping the (0 0 0 2) peak also shifts to higher 2θ values suggesting the incorporation of Be/Mg at the Zn-site. From the UV-visible optical transmittance measurement it was noticed that the band gap of the pristine ZnO film is 3.3 eV which enhanced up to 4.51 eV for Zn_0.7Be_0.1Mg_0.2O film which lies in the solar blind region and is very useful in the realization of deep UV detectors.     

Amorphous forming ability of Co-X （X=Cr, Mo, W） magnetic thin films

Co-X(X=Cr, Mo, W) magnetic thin films were prepared by using DC magnetron sputtering, and their structures were examined by using X-ray diffraction (XRD). The amorphous forming ability (AFA) of the three alloy systems was discussed based on thermodynamic calculation and experiments. The results show that the Co-Mo thin films exhibit the largest AFA among them, and the Co-W thin films are condition-dependent amorphous while the Co-Cr thin films are hard to be amorphous, which is consistent with the thermodynamic calculation. The difference in AFA for the alloys of these three systems is finally ascribed to three main factors: differences in electronegativity, electron density and atomic size between Co and X elements.     

激光清洗阳极氧化膜对铝合金焊缝性能的影响分析

针对铝合金焊接边阳极氧化膜,采用非接触、高效激光清洗新技术进行清理,并分析激光清理阳极氧化膜层对焊缝组织性能的影响。实验结果表明:采用激光功率100 W、扫描速度10 mm/s,可以实现5μm厚度阳极氧化膜层的完全清理。焊缝成形均匀,焊缝表面泛有金属光泽,焊缝无聚集状气孔、杂质等内部缺陷。经激光清理的铝合金接头抗拉强度为298~303 MPa,拉伸断裂延伸率6.2%~6.5%,激光清理焊缝与机械刮削焊缝的性能范围一致。     

Surface engineering with light alloys—Hard coatings, thin films, and plasma nitriding

Light alloys have been attracting increasing attention over the past decade, since they can be used to reduce weight and save energy. For many years, light metals such as titanium and aluminum have also been used to synthesize hard compound coatings such as physically vapor deposited (PVD) TiN, (Ti,Al)N, and chemically vapor deposited (CVD) Al₂O₃. The coatings field is developing rapidly. Combining plasma-aided coating and diffusion processes has led to the development of so-called “duplex treatment,” consisting of plasma nitriding and subsequent hard coating. Another interesting development is TiN coating of aluminum vacuum parts, such as pumps, to reduce degassing and make the cleaning of the surfaces easier. Despite the many advantageous properties of light alloys, their surface properties sometimes cause problems. For example, galling may be a severe problem with titanium parts, and plasma nitriding has been applied successfully to combat it. However, due to adherent oxide scale, plasma nitriding of aluminum has proven to be more difficult. In this paper, we discuss some recent trends in the application of plasma-aided coating, thin film deposition, and diffusion processes, and give practical examples of industrial applications.     

Structural characteristics and optical properties of plasma assisted reactive magnetron sputtered dielectric thin films for planar waveguiding applications

Thin films of aluminum oxide (Al₂O₃), tantalum pentoxide (Ta₂O₅), titanium oxide (TiO₂), yttrium oxide (Y₂O₃) and zirconium oxide (ZrO₂) were deposited by plasma assisted reactive dual magnetron sputtering to determine their suitability as a host for a rare earth doped planar waveguide upconversion laser. The effect of deposition parameters such as cathode, plasma power and oxygen gas flows were studied and the operational working points were determined. Both power and lambda control were used to optimize the optical quality of each material. By using lambda control feedback system, the magnetron power fluctuates to sustain a fixed oxygen flow in the target area reducing the compound layer growth on the material and maintaining a healthy deposition rate. The optical properties, structure and crystalline phase of each film were found to be dependent on the process parameters. X-ray diffraction (XRD) analysis revealed that the thin films varied from amorphous to highly crystalline depending on the deposition conditions. X-ray photoelectron spectroscopy (XPS) was utilized for surface compositional analysis revealing that films had varying stoichiometric ratios which are controlled for each material by the deposition parameters chosen. The waveguide loss for the thin film layers was investigated and Ta₂O₅ was shown to have a slab waveguide loss of ~ 1 dB/cm at both visible and infra-red wavelengths making it ideal for planar waveguide and laser applications. TiO₂, Y₂O₃ and ZrO₂ were found to deposit in a highly crystalline phase. Waveguiding in the TiO₂ layers was not possible at 633 nm or in the infrared region. The Y₂O₃ samples gave low loss (2–4 dB/cm) at the 1.3 and 1.5 μm wavelengths but no waveguiding at 633 nm or 833 nm was possible. Atomic force microscopy showed rough surface topography for TiO₂, Y₂O₃ and ZrO₂ akin to their crystalline growth with the SEM images confirming the regular crystalline columnar structure for the case of Y₂O₃ and ZrO₂.     

HVOF coatings for steam oxidation protection

In the context of the European project ‘Coatings for Supercritical Steam Cycles’ (SUPERCOAT), the use of steam oxidation resistant coatings on currently available ferritic materials with high creep strength but poor oxidation resistance was investigated in order to allow increase in the operating temperature of steam power plants from 550 to 650 °C. Among the explored coating techniques for this application, chosen on the basis of being potentially appropriate for coating steam turbine components, High Velocity Oxy Fuel (HVOF) thermal spray has resulted in one of the most successful techniques. Different alloyed materials such as FeCrAl, NiCrSiFeB, FeAl, NiCr and FeCr have been deposited, optimized and tested under flowing steam at 650 °C. Characterization of as deposited and tested samples by metallography, SEM‐EDS and XRD was carried out. Some of these coatings form protective pure chromium or aluminium oxides exhibiting excellent behaviour for at least 15 000 h of exposure, whereas others form less stable complex mixed oxides which nevertheless grow at considerably slower rates than the oxides formed on uncoated P92 (9 wt% Cr ferritic steel).     

混合电容器多孔氧化钌阴极涂层的制备与表征

采用电沉积方法制备了混合电容器钽基多孔氧化钌阴极涂层材料,探讨了电沉积过程中电沉积液的pH值随电沉积时间的变化关系,研究了电沉积时间对氧化钌沉积质量的影响.用X射线衍射和扫描电镜分别表征了热处理前后的涂层结构及涂层的多孔形貌,用循环伏安法测量了涂层的电容,并研究了热处理温度对电容量大小及其稳定性的影响.结果表明:电沉积的氧化钌为非晶态,涂层为纳米多孔结构;热处理有利于涂层孔隙结构及大小的均匀性,不同温度的热处理使涂层具有不同的电容,经热处理后涂层的电容稳定;经100℃热处理1 h后的多孔氧化钌涂层具有最大的比电容.     

The growth and structure of thin oxide films on ceria-sol-coated nickel

The influence of 14-nm thick ceria ceramic coatings deposited by the sol-gel technique on the early-stage oxidation of polycrystalline nickel at 973 K was studied by analytical electron microscopy, Auger electron spectroscopy, Rutherford backscattering spectrometry and X-ray diffraction. The size of the ceria particles in the coating was modified prior to oxidation by vacuum annealing. It was found that ceria particle size is a crucial factor affecting the oxidation kinetics, oxide microstructure, and distribution of cerium within the oxide film. Coarse ceria particles applied to the nickel surface were ineffective in the inhibition of oxidation and were spread throughout the whole oxide. Coatings with small ceria particles markedly improved the oxidation resistance. After oxidation such particles were present in the surface region of nickel oxide, acting as the sources of cerium ions segregated at the nickeloxide grain boundaries. The stereological analysis of oxide microstructure as well as microchemical examination supported the predominant role of grain-boundary segregation of cerium ions decreasing the oxidation rate. The results are discussed in terms of reactive-element effect on the development of microstructure of nickel oxide film during initial stages of oxidation.     

Influence of europium oxide doping on the structural and optical properties of pulsed laser ablated barium tungstate thin films

Nanostructured Eu₂O₃ doped Barium tungstate (BaWO₄) crystallites are successfully synthesized using pulsed laser deposition (PLD) technique. The influence of different Eu₂O₃ doping concentrations (1,2,3 & 5 wt.%) on the structural, surface morphological and optical properties are systematically studied using XRD, micro-Raman, SEM, AFM, UV-vis and photoluminescence spectroscopy. All the films are polycrystalline with tetragonal scheelite structure. The vibrational analysis of the atoms in BaWO₄ is studied by micro-Raman spectra using factor group analysis. The surface morphological analysis by SEM and AFM reveals the presence of fine nanoparticles with distinct grain boundaries in all the films. The band gap energy variation in the Eu₂O₃ doped BaWO₄ films is in accordance with the variation of the sizes of nano particles in the films. The films with higher Eu³⁺ doping concentrations (≥2 wt.%) show a PL emission peak centered around 614 nm when excited at 394 nm which can be attributed to the ⁵D₀ → ⁷F₂ (0-2) transition of Eu³⁺ ion.