Vacuum-plasma sprayed nanostructured titanium oxide films

Nanostructured titanium oxide films were fabricated by vacuum-plasma spraying. The microstructure of the films was characterized with SEM, TEM, and XRD. The chemical state of the titanium oxide of the films was analyzed using XPS. The results indicated that the vacuum-plasma sprayed nanostructured titanium oxide films possessed a corallike structure with small pores and agglomerated grains, which was composed of nanosized particles. The main phases of the films were anatase and rutile, and their relative content was determined by the plasma parameters. Low-valence titanium cations were also found in the films.     

Photoluminescence in laser ablated nanostructured indium oxide thin films

Nanocrystalline indium oxide films have been deposited using pulsed laser ablation technique at different substrate temperatures and the films are post-annealed at different temperatures. The structural, optical and electrical properties of the films are investigated by XRD, SEM, AFM, UV–vis spectra, photoluminescence spectra and electrical conductivity measurements. X-ray diffractograms of the as-deposited and post-annealed films A–C show that films are amorphous at lower substrate temperatures and transform to mixture of amorphous and crystalline phases. The grain size determination based on Debye Scherrer's formula shows that the average grain size of the crystallites in the films ranges from 6 to 32 nm. Dislocation density, biaxial strain, lattice strain and lattice stress of the films are also calculated. SEM micrographs show that all the films are densely packed with the crystallites in the nanodimensions. SEM images show porous nanocrystalline nature for the films of samples B and C which make them suitable for gas sensing. The as-deposited samples show decrease in resistivity with increase in substrate temperature and the lowest resistivity obtained is 6.6 × 10^?5 Ω m for the as-deposited films at substrate temperature 773 K. Efficient photoluminescence emission is observed in all the films and this can be attributed to higher values of rms surface roughness exhibited by these films. In₂O₃ films exhibit a PL emission property in the UV region at room temperature which suggests possible applications in nanoscale optoelectronic devices in the future.     

Synthesis and characterization of sol-gel derived gallium-doped zinc oxide thin films

Gallium-doped ZnO (GZO) semiconductor thin films were prepared by a sol-gel spin coating process. The effects of Ga dopant concentrations on the microstructure, electrical resistivity, optical properties, and photoluminescence (PL) were studied. XRD results showed that all the as-prepared GZO films had a wurtzite phase and a preferred orientation along the [0 0 2] direction. ZnO thin films doped with Ga had lower electrical resistivity, lower RMS roughness, and improved optical transmittance in the visible region. The lowest average electrical resistivity value, 2.8 × 10² Ω cm, was achieved in the ZnO thin films doped with 2% Ga, which exhibited an average transmittance of 91.5%. This study also found that the optical band gap of Ga-doped films was 3.25 eV, slightly higher than that of undoped samples (3.23 eV), and the PL spectra of GZO films showed strong violet-light emission centers at about 2.86 eV (the corresponding wavelength of which is about 434 nm).     

Structural studies of zinc oxide films grown by RF magnetron sputtering

The main purpose of this study consists of researching the piezoelectric characteristics of ZnO films grown by RF magnetron sputtering in reactive plasma. In this way the influence of deposition parameters, such as RF power and plasma oxygen content, on the structural and morphological properties of the films are analyzed.ZnO films are grown on SiO₂/Si(1 0 0) substrate using a zinc oxide target. Different RF powers (from 50 to 200 W) and reactive plasmas (from 5 to 15% of oxygen content) have been tested and optimized to produce good quality films suitable for fabricating surface acoustic wave (SAW) devices.Crystalline structures and morphological characteristics of the films are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively.SAW devices are fabricated with “IDT(Al)/ZnO/SiO₂Si” configuration. The frequency response of these devices is measured for their characterization.     

X-ray photoelectron spectroscopic study of catalyst based zinc oxide thin films

X-ray photoelectron spectroscopy (XPS) is a powerful tool for surface and interface analysis, providing an elemental composition of surfaces and the local chemical environment of adsorbed species. The surface composition and chemical states of the F/ZnO and In/ZnO catalysts deposited using spray technique have been studied by high resolution and high sensitivity X-ray photoelectron spectroscopy. A hybrid multiline method is proposed for quantitative XPS analysis that combines the first principles approach with the experimental determination of overall response function. The chemical shifts of XPS core lines for Zn (2P_3/2, F 1s and In 3d) and Auger parameter for zinc (β_Zn = 2012.6, 2011.48 eV for F/ZnO and In/ZnO, respectively) have been calculated. The results have been used to determine the bond iconicity (0.55).     

纯Ar气氛中退火对Al掺杂ZnO薄膜性能的影响

用射频磁控溅射技术制备了高度择优取向的Al掺杂ZnO(ZAO)薄膜,并对薄膜在纯氩气中进行了400～600℃的退火处理.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、光谱仪和四探针测试仪等对退火前后薄膜进行了表征和光学、电学性能研究.研究表明,纯氩气中退火处理对ZAO薄膜的晶体、光学和电学性能有影响.原位沉积的薄膜电阻率2.59Ωcm,可见光区透过率约70%.500℃纯Ar气氛中退火1h后,ZAO薄膜的平均晶粒有所长大,薄膜内应力达到最小,接近于松弛状态;薄膜可见光区平均透过率从70%提高到80%左右;而薄膜的电阻率变化不明显,从2.59Ωcm降低到1.13Ωcm.     

Ta-doped multifunctional bioactive nanostructured films

Ta-doped multifunctional bioactive nanostructured films (MuBiNaFs) were deposited by DC magnetron sputtering or ion implantation assisted magnetron sputtering of composite (Ti,Ta)C + Ca₃(PO₄)₂ and (Ti,Ta)C + CaO targets produced by self-propagating high-temperature synthesis method. The films were characterized in terms of their structure, elemental and phase composition using X-ray diffraction, transmission electron microscopy, X-ray photoelectron, Raman, and IR spectroscopy. The films deposited in an Ar atmosphere consisted of (Ti,Ta)C, Ti_xO_y, and CaO phases in an amorphous matrix with P-O, C-O, and O-H bonding. In the films deposited in a gaseous mixture of Ar + 14%N₂, apart from the (Ti,Ta)(C,N), Ti_xO_y, and CaO phases, the indication of diamond-like carbon, bcc Ta and traces of P-O bonding were observed. The MuBiNaFs demonstrated high hardness in the range of 38-44  GPa, Young's modulus 310-350  GPa, high percentage of elastic recovery 70-75%, low friction coefficient down to 0.17-0.25 (both in air and under physiological solution) and two orders of magnitude lower wear rate compared with Ti substrate. Ti ion implantation of growing films was shown to be an effective instrument to decrease their high internal stress. Static water contact angle measurements indicated hydrophilic nature of film surfaces. The electrochemical tests demonstrated that the Ta-doped films had positive values of corrosion potential with low current density. In vitro studies showed that cultured IAR-2 epitheliocytes and MC3T3-E1 osteoblastic cells were well spread on the surface of films and their actin cytoskeleton was well organized. Osteoblastic cells had a high rate of proliferation on all examined films and expressed alkaline phosphatase activity, an early-stage differentiation marker. The MuBiNaF revealed a high level of biocompatibility and biostability at experiments in vivo.     

Si-doped multifunctional bioactive nanostructured films

Si-doped multifunctional bioactive nanostructured films (MuBiNaFs) were deposited by DC magnetron sputtering of composite TiC_0.5 + CaO + Si (A) and TiC_0.5 + CaO + Si₃N₄ (B) targets produced by self-propagating high-temperature synthesis method. The films were characterized in terms of their structure, elemental and phase composition using X-ray diffraction, scanning and transmission electron microscopy, electron energy loss spectroscopy, glow discharge optical emission spectroscopy, Raman, and IR spectroscopy. The Ti-Si-Ca-P-C-O-(N) films consisted of TiC(N) as a main phase with a minor amount of TiO_x, SiN_x, SiO_x, SiC, and CaO phases probably mainly in amorphous state at the grain boundaries and COO- groups on the film surface. The excess of carbon atoms in the Ti-Si-Ca-P-C-O-N film (target A) precipitated in a DLC form. The films showed hardness in the range of 26-31 GPa, reduced Young's modulus of 200-270 GPa, and high percentage of elastic recovery of 60-71%. The best Ti-Si-Ca-C-O-N films exhibited low friction coefficient both in physiological solution and Dulbecko modified Eagle medium with fetal calf serum, hydrophilic properties, improved electrochemical characteristics, and excellent impact resistance. Nevertheless, the wear resistance of the Ti-Si-Ca-C-O-N films against Al₂O₃ ball was lower compared with the best Si-free MuBiNaFs. In vitro studies showed that the Si-doped Ti-Ca-C-O-N films possess improved osteoconductive characteristics during early stage of cell/material interaction. The film surface was highly adhesive for IAR-2 epithelial and MC3T3-E1 osteoblastic cells. The films revealed a high level of biocompatibility and biostability in experiments in vivo. The Ti-Si-Ca-C-O-N film (target A) did not show any bactericidal activity during cultivation of bacterial strains both on solid and in liquid Luria Bertani mediums. The film did not reveal any bactericidal and toxic activity against macrophages and therefore did not change bacterial status and defence system of macro-organisms.     

Substrate effect on mechanical characterizations of aluminum-doped zinc oxide transparent conducting films

The measurements of thin-film mechanical properties are generally influenced by the elastic and plastic responses of substrates and consequently may be inaccurate. Thus in this study, the effects of three different substrates, including sapphire, glass and polyimide, on the mechanical characterizations of aluminum-doped zinc oxide transparent conducting films are evaluated. From nanoindentation tests, it was found that a high film/substrate hardness ratio contributed an early-initiated substrate effect. For a hard film/soft substrate system (zinc oxide on polyimide), the measured hardness and elastic modulus markedly dropped at very small indentation depths due to the insufficient strength of the soft substrate to sustain the applied stress. A modification of the Bhattacharya model and the calibration of the King model were also made in this study; some important factors were established. Moreover, the interface adhesion energy between the film and soft substrate, measured by nanoscratch, was high because the compliant deformation of the soft substrate released accumulated stresses and then retarded interface delamination.     

Characteristics of atomic layer deposited transparent aluminum-doped zinc oxide thin films at low temperature

Various aluminum-doped zinc oxide(AZO) films were prepared on Si substrate by atomic layer deposition(ALD) at 100℃. The effect of the composition of AZO films on their electrical, optical characteristics,structural property and surface topography was investigated. The appearance of electrical resistivity shows their semiconducting properties. In most of the visible light band, all the AZO films present transparency of more than 80%. Al doping suppresses the AZO film crystallization.When the Al doping concentration increases up to 3.95 at%, the AZO film has some small multicrystal grains with random orientation. Al doping improves the roughness of i-ZnO film. The root mean square(RMS) roughness of samples prepared by ALD is much smaller than that prepared by radio-frequency magnetron sputtering reported.     

Magnetic interactions in nanostructured films and arrays

This paper presents recent results on magnetic interactions in CoPt:C nanocrystalline films and Co:C magnetic nanodot arrays. The local magnetic properties were studied by magnetic force microscopy. We discuss the limit of the using ΔM for characterization of magnetic interactions in these CoPt:C nanocrystalline films. The magnetic force microscopy images of patterned Co:C nanodot arrays show the presence of “macro”-domains (domains formed by several separate dots). This behavior is attributed to the exchange coupling between the dots.     

Multicomponent nanostructured films for various tribological applications

Many engineering materials working under severe cutting, stamping, or bearing conditions including humid and corrosive environments, as well as temperature fluctuation require a combination of chemical, mechanical, and tribological properties. For load-bearing metallic implants, the combination of excellent mechanical and tribological properties with biocompatibility and bioactivity is also of great importance. Desired properties can be achieved in hard films based on carbides, borides and nitrides of transition metals by alloying with metallic (Al, Cr, Zr) or nonmetallic (O, P, Si, Ca) elements. The present work demonstrates the potential of self-propagating high-temperature synthesis (SHS), magnetron sputtering (MS), and ion implantation assisted MS of SHS-composite targets to produce multicomponent nanostructured films with enhanced combination of properties. Three groups of recently developed films for mechanical engineering and medicine are considered: hard tribological Ti–(Al, Cr)–(Si, B, C, N) films with enhanced thermal stability, corrosion and oxidation resistance; nanocomposite and multilayered TiCrBN/WSe_x films with improved lubrication; and multifunctional bioactive nanostructured (Ti, Ta)–(Ca, Zr)–(C, N, O, Si, P) films (MuBiNaFs).     

Micro/nanomechanical properties of aluminum-doped zinc oxide films prepared by radio frequency magnetron sputtering

Aluminum-doped zinc oxide (ZnO) was grown on glass substrates by using RF magnetron sputtering. In order to investigate the effect of growth temperature on the mechanical properties of Al-doped ZnO films, the temperature of the substrates during deposition was controlled at room temperature (R.T.), 150 °C, and 300 °C. The crystal structure and topography of the deposited films were investigated by X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The mechanical properties of films were measured by using nanoindentation and micro-reciprocating pin-on-plate tester to characterize the hardness, modulus, and tribological behavior. The tribological behavior of silicon (100) wafer was also obtained to compare with that of the Al-doped ZnO. It was found that Al-doped ZnO films with (002) oriented plane was favored at high growth temperature. The mechanical properties of the films were significantly affected by growth temperature. The film grown at room temperature showed a relatively low friction coefficient of 0.25 and high wear resistance.     

由氧化锌烟灰氨法制取高纯锌

开发了用NH3-NH4Cl水溶液浸出炼铅炉渣烟化炉氧化锌烟灰制取高纯锌的新工艺.Zn的浸出率＞96%,浸出液加H2O2后净化除Sb和As,然后采用加锌粉两段逆流除Cu,Cd,Pb,电积过程中电能消耗2 500～2 700 kW@h/t.电锌含Zn＞99.999%,杂质元素Cu,Cd,Co,Ni,Fe,As,Sb均小于0.0001%,Pb＜0.000 3%.     

Optoelectronic studies of sol-gel derived nanostructured CdO-ZnO composite films

Compositional dependence of the optoelectronic properties of sol-gel derived CdO-ZnO composite films with volume ratio of Cd:Zn ranging from 1:0 to 0:1 (with a step of 1/4) has been studied. After heat treatments in air the prepared thin films were investigated by studying their structural, morphological, d.c. electrical and optical properties. X-ray diffraction (XRD) results suggest that the samples are polycrystalline and the crystallinity of them increased with Cd ratio. The average grain size is in the range of 20-34 nm. As composition and structure changed due to the Cd volume ratio, the order of the carrier concentration was varied from 10¹⁶ to 10²⁰ cm⁻³ with Cd ratio and the mobility increased from less than 2 to 45 cm² V⁻¹ s⁻¹. It was found that the transmittance and the band gap decreased as Cd ratio increased. The optical constants of the film were studied and the dispersion of the refractive index was discussed in terms of the Wemple-DiDomenico single oscillator model. The real and imaginary parts of the dielectric constant of the films were also determined. The volume energy loss (VELF) increases more than the surface energy loss (SELF) at their particular peaks. The third-order nonlinear polarizability parameter is higher for CdO-ZnO thin films with higher concentration of cadmium oxide.     

纳米结构Ni-TiN复合薄膜的电沉积及腐蚀行为

采用电沉积方法在黄铜基底上制备纳米结构的Ni-TiN复合薄膜。用扫描电镜（SEM）及透射电镜（TEM）对其微观结构进行表征,利用X射线衍射（XRD）分析其平均晶粒尺寸,采用极化曲线及电化学阻抗谱（EIS）研究其腐蚀行为。结果表明,电沉积的电流密度、TiN纳米粒子的浓度、搅拌速度、溶液温度及pH值对电沉积薄膜形貌的影响较大。制备的Ni-TiNi电沉积薄膜的平均晶粒尺寸约为50nm。纳米结构的Ni-TiNi电沉积薄膜的耐腐蚀性能远优于纯Ni沉积薄膜的。