Structural and optical properties of zinc nitride films prepared by rf magnetron sputtering

Zinc nitride films were prepared on quartz substrates by rf magnetron sputtering using pure zinc target in N₂-Ar plasma. X-ray diffraction (XRD) analysis indicates that the films just after deposition are polycrystalline with a cubic structure and a preferred orientation of (4 0 0). X-ray photoelectron spectroscopy (XPS) analysis also confirms the formation of N-Zn bonds and the substitution incorporation of oxygen for nitrogen on the surface of the films. The optical band gap is calculated from the transmittance spectra of films just after deposition, and a direct band gap of 1.01 ± 0.02 eV is obtained. Room temperature PL measurement is also performed to investigate the effect of defect on the band gap and quality of the zinc nitride films.     

Optical band gap of zinc nitride films prepared on quartz substrates from a zinc nitride target by reactive rf magnetron sputtering

Polycrystalline zinc nitride films have been synthesized onto quartz substrates from the zinc nitride target and the nitrogen working gas by reactive rf magnetron sputtering at room temperature. X-ray diffraction study indicates that polycrystalline zinc nitride films are of cubic structure with the lattice constant a = 0.979(1) nm and have preferred orientations with (3 2 1) and (4 4 2). Its absorption coefficients as well as the film thickness are calculated from the transmission spectra, which are measured with a double beam spectrophotometer. The optical band gap has been determined from the photon energy dependence of absorption coefficient, an indirect transition optical band gap of 2.12(3) eV has been obtained.     

Characterization and field emission characteristics of carbon nanotubes modified by titanium carbide

Carbon nanotubes (CNTs) were modified by depositing a thin layer of titanium film on the surface using magnetron sputtering method, followed by vacuum annealing at 900 °C for 2 h. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirmed that the as-deposited thin titanium film reacted with carbon atoms to form titanium carbide after annealing. The experiment results show that the thickness of sputter-deposited titanium film has significant effect on the field emission J-E characteristic of modified CNTs film. The titanium carbide-modified CNTs film obtained by controlling the titanium sputtering time to 2 min showed an improved field emission characteristics with a significant reduction in the turn-on electric field and an obvious increase in the emission current density as well as an improvement in emission stability. The improvement of field emission characteristics achieved is attributed to the low work function and good resistance to ion bombardment of titanium carbide.     

Optical and hydrophobic properties of co-sputtered chromium and titanium oxynitride films

The chromium and titanium oxynitride films on glass substrate were deposited by using reactive RF magnetron sputtering in the present work. The structural and optical properties of the chromium and titanium oxynitride films as a function of power variations are investigated. The chromium oxynitride films are crystalline even at low power of Cr target (≥60 W) but the titanium oxynitride films are amorphous at low target power of Ti target (≤90 W) as observed from glancing incidence X-ray diffraction (GIXRD) patterns. The residual stress and strain of the chromium oxynitride films are calculated by sin² ψ method, as the average crystallite size decreases with the increase in sputtering power of the Cr target, higher stress and strain values are observed. The chromium oxynitride films changes from hydrophilic to hydrophobic with the increase of contact angle value from 86.4° to 94.1°, but the deposited titanium oxynitride films are hydrophilic as observed from contact angle measurements. The changes in surface energy were calculated using contact angle measurements to substantiate the hydrophobic properties of the films. UV-vis and NIR spectrophotometer were used to obtain the transmission and absorption spectra, and the later was used for determining band gap values of the films, respectively. The refractive index of chromium and titanium oxynitride films increases with film packing density due to formation of crystalline chromium and titanium oxynitride films with the gradual rise in deposition rate as a result of increase in target powers.     

Preparation of boron carbon nitride thin films by radio frequency magnetron sputtering

Boron carbon nitride films were deposited by radio frequency magnetron sputtering using a composite target consisting of h-BN and graphite in an Ar-N₂ gas mixture. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results suggest that the films are atomic-level hybrids composed of B, C and N atoms. The boron carbon nitride films prepared in the present experiment have a disordered structure. The sputtering power varied from 80 W to 130 W. This sputtering power was shown to have regular effect on the composition of boron carbon nitride films. The samples deposited at 80 W and 130 W are close to the stoichiometry of BC₃N. The sample deposited at 110 W is close to the stoichiometry of BCN. The samples deposited at 100 W and 120 W approach to BC₂N. It is very significant for us to synthesize boron carbon nitride compound with controllable composition by changing the sputtering power.     

The interface structure and band alignment at alumina/Cu(Al) alloy interfaces—Influence of the crystallinity of alumina films

Both epitaxial and amorphous ultra-thin alumina films were grown on a Cu-9 at.%Al(1 1 1) substrate by selective oxidation of Al in the alloy in ultra high vacuum. The crystallinity of the alumina films was controlled by oxidation temperature. The photoelectron spectra of Al 2p, O 1s and valence band were measured in-situ during oxidation. The influence of the crystallinity on the interface structure between the alumina films and the substrate was discussed by analyzing the Al 2p spectra composed of multiple peaks. The energy difference between the Fermi level of the substrate and the valence band maximum of the alumina films (band offset) was derived from the valence band spectra. The energy band alignment at the interface between each of the two alumina films and the substrate was revealed by combining the binding energy values of the core levels with the band offset values. The influence of the alumina crystallinity on the band alignment was discussed.     

Carbon nitride films by RF plasma assisted PLD: Spectroscopic and electronic analysis

Carbon nitride (CNx) thin films have been grown on Si 〈1 0 0〉 by 193 nm ArF ns pulsed laser ablation of a pure graphite target in a low pressure atmosphere of a RF generated N₂ plasma and compared with samples grown by PLD in pure nitrogen atmosphere. Composition, structure and bonding of the deposited materials have been evaluated by X-ray photoelectron spectroscopy (XPS), and Raman scattering. Significant chemical and micro-structural changes have been registered, associated to different nitrogen incorporation in the two types of films analyzed. The intensity of the reactive activated species is, indeed, increased by the presence of the bias confined RF plasma, as compared to the bare nitrogen atmosphere, thus resulting in a different nitrogen uptake in the growing films. The process has been also investigated by some preliminary optical emission studies of the carbon plume expanding in the nitrogen atmosphere. Optical emission spectroscopy reveals the presence of many excited species like C⁺ ions, C atoms, C₂, N₂; and CN radicals, and N₂⁺ molecular ions, whose relative intensity appears to be increased in the presence of the RF plasma. The films were also characterised for electrical properties by the “four-probe-test method” determining sheet resistivity and correlating surface conductivity with chemical composition.     

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.     

An XPS study on ion beam induced oxidation of titanium silicide

Titanium silicides (TiSi₂) films grown on Si(1 0 0) substrate were investigated by ex situ XPS depth profiling after athermal ion beam induced oxidation (IBO) at 12 keV O₂⁺ incident energy and normal incidence. The composition and stoichiometry of these films were quantitatively determined as chemical state relative concentrations versus sputter time. “In depth” silicon and titanium oxidation states have been obtained after spectra deconvolution, showing a mixture of silicon dioxide, titanium dioxide, titanium suboxides, elemental titanium and residual traces of titanium nitride. Thermochemical data based on the corresponding enthalpies of formation of the oxides cannot explain our experimental results as in the case of low energy IBO, an oxygen defective altered layer is formed, presenting features of a reduced TiO_x phase.     

Photomodulated reflectance study on optical property of InN thin films grown by reactive gas-timing rf magnetron sputtering

The photoreflectance (PR) spectroscopy has been applied to investigate the band-gap energy (E_g) of indium nitride (InN) thin films grown by rf magnetron sputtering. A novel reactive gas-timing technique applied for the sputtering process has been successfully employed to grow InN thin films without neither substrate heating nor post annealing. The X-ray diffraction (XRD) patterns exhibit strong peaks in the orientation along (0 0 2) and (1 0 1) planes, corresponding to the polycrystalline hexagonal-InN structure. The band-gap transition energy of InN was determined by fitting the PR spectra to a theoretical line shape. The PR results show the band-gap energy at 1.18 eV for hexagonal-InN thin films deposited at the rf powers of 100 and 200 W. The high rf sputtering powers in combination with the gas-timing technique should lead to a high concentration of highly excited nitrogen ions in the plasma, which enables the formation of InN without substrate heating. Auger electron spectroscopy (AES) measurements further reveal traces of oxygen in these InN films. This should explain the elevated band-gap energy, in reference to the band-gap value of 0.7 eV for pristine InN films.     

X-ray photoelectron spectroscopic study on surface reaction on titanium by laser irradiation in nitrogen atmosphere

The surface reaction on titanium due to pulsed Nd:YAG laser irradiation in a nitrogen atmosphere was investigated using X-ray photoelectron spectroscopy (XPS). The laser, with a wavelength of 532 nm (SHG mode), was irradiated on a titanium substrate in an atmosphere-controlled chamber, and then the substrate was transported to an XPS analysis chamber without exposure to air. This in situ XPS technique makes it possible to clearly observe the intrinsic surface reaction. The characteristics of the surface layer strongly depend on the nitrogen gas pressure. When the pressure is 133 kPa, an oxynitride and a stoichiometric titanium nitride form the topmost and lower surface layers on the titanium substrate, respectively. However, only a nonstoichiometric titanium oxide layer containing a small amount of nitrogen is formed when the pressure is lower than 13.3 kPa. Repetition of laser shots promotes the formation of the oxide layer, but the formation is completed within a few laser shots. After the initial structure is formed, the chemical state of the surface layer is less influenced by the repetition of laser shots.     

Photoemission investigations on nanostructured TiO2 grown by cluster assembling

Nanostructured titanium dioxide (ns-TiO₂) films were grown by supersonic cluster beam deposition method. Transmission electron microscopy demonstrated that films are mainly composed by TiO₂ nanocrystals embedded in an amorphous TiO₂ phase while their electronic structure was studied by photoemission spectroscopy. The cluster assembled ns-TiO₂ films are expected to exhibit several structural and chemical defects owing to the large surface to volume ratio of the deposited clusters. Ultraviolet photoemission spectra (hv = 50 eV) from the valence band unveil the presence of a restrained amount of surface Ti 3d defect states in the band gap, whereas Ti 2p core level X-ray photoelectron (hv = 630 eV) spectra do not manifestly disclose these defects.     

PIIID复合强化处理轴承钢表面TiN膜层的XPS表征

用等离子体浸没离子注入与沉积(PIIID)复合强化新技术在AISI52100轴承钢基体表面成功合成了硬而耐磨的氮化钛薄膜。膜层表面的化学组成和相结构分别用X射线衍射(XRD)和X射线光电子能谱(XPS)表征;膜层表面的原子力显微镜(AFM)形貌显示出TiN膜结晶完整,结构致密均匀。XRD测试结果表明,TiN在(200)晶面衍射峰最强,具有择优取向。Ti(2p)的XPS谱峰泰勒拟合分析揭示出,Ti(2p_1/2)峰和Ti_2p3/2峰均有双峰出现,表明氮化物中的Ti至少存在不同的化学状态;N(1s)的XPS谱峰在396.51, 397.22和399.01 eV附近出现了三个分峰,分别对应于TiNO_y,TiN和N—N键中的氮原子。结合O(1s)的XPS结果,证实膜层中除生成有稳定的TiN相外,还有少量钛的氧化物和未参与反应的单质氮。整个膜层是由TiN,TiO₂,Ti—O—N化合物和少量单质氮组成的复合体系。     

Effect of deposition and annealing temperature on mechanical properties of TaN film

Tantalum nitride films (TaN) were synthesized by microwave ECR-DC sputtering. The effects of deposition and annealing temperature on mechanical properties of TaN films were investigated. Cross-section pattern, microstructure and binding energy of the films were investigated by scanning electron microscope (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. Mechanical properties were evaluated using nano-indentation and scratch tester. The results showed that the maximal hardness value of approximately 40 GPa was deposited in the TaN sample at 573 K. While the preparation temperature decreased, the hardness, modulus and adhesion of TaN film also decreased. Hardness and modulus also decreased with the increase in annealing temperature. Meanwhile the adhesion strength was also sensitive to the annealing temperature, with a maximum adhesion strength of 40 N measured in the TaN film annealed at 448 K. The results demonstrated that a desirable mechanical property of TaN films deposited by DC reactive magnetron sputtering can be obtained by controlling the deposition and annealing temperature.     

Angle resolved photoemission study of the Ce/Pd(1 1 1) interface

X-ray and UV excitation angle resolved photoemission spectroscopy of ultra-thin films of cerium deposited on a Pd(1 1 1) single-crystal surface has been carried out. Both core level and valence band spectra show a formation of a surface alloy exhibiting d- and f-electron orbital hybridization. An azimuth and polar angle mapping of X-ray excited photoemission intensities results in a surface-geometrical structure information. Mapping of ultra-violet photoelectron intensities as a function of emission angles is used for a band mapping and an electronic structure determination. The d-, f-hybridization occurs even for 0.7 ML of Ce deposited at room temperature. The surface annealing at 260 °C enhances this behavior. A shift of Pd 4d-derived states to higher binding energy in the Ce-Pd systems is observed.     

Effect of annealing process on TiN/TiC bilayers grown by pulsed arc discharge

In this work, a study of annealing process effect on TiN/TiC bilayer is presented. The annealing temperature was varied between room temperature and 500 °C. Materials were produced by the plasma-assisted pulsed vacuum arc discharge technique. In order to grow the films, a target of Ti with 99.9999% purity and stainless-steel 304 substrate were used. For the production of TiN layer, the reaction chamber was filled up with nitrogen gas until reaching 25 Pa and the discharge was performed at 310 V. The TiC layer was grown in a methane atmosphere at 30 Pa and 270 V. X-ray diffraction and X photoelectron spectroscopy were employed for studying the structure and chemical composition evolution during the annealing process. At 400 °C, TiO₂ phase begun to appear and it was well observed at 500 °C. Crystallite size and microstrain was obtained as a function of the annealing temperature. XPS technique was employed for analyzing the bilayers before and after the annealing process. Narrow spectra of Ti2p, N1s and O1s were obtained, presenting TiO phases.     

Structure evolution from nanocolumns to nanoporous of nitrogen doped amorphous carbon films deposited by magnetron sputtering

Different nitrogen doped amorphous carbon (CNx) films were obtained by magnetron sputtering of carbon target in argon and nitrogen atmosphere at the increasing negative bias voltages from 0 to 150 V. The films structures have experienced great change, from the novel column to nanoporous structure at the bias voltage of 0 V to the porous structure at 150 V. The proposed growth process was that the CNx nuclei grew at 0 V acted as the “seeds” for the growth of the nanocolumns, and ion etching effects at 150 V induced the formation of nanoporous structures. Furthermore, a comparison study showed that the field emission properties of the CNx films were related with the introduction of the nitrogen atoms, the size and concentration of sp² C clusters and the surface roughness. The films with rougher surface have lower threshold field.     

Effect of ECR-assisted microwave plasma nitriding treatment on the microstructure characteristics of FCVA deposited ultra-thin ta-C films for high-density magnetic storage applications

There are higher technical requirements for protecting layer of magnetic heads and disks used in future high-density storage fields. In this paper, ultra-thin (2 nm thickness) tetrahedral amorphous carbon (ta-C) films were firstly prepared by filtered cathodic vacuum arc (FCVA) method, then a series of nitriding treatments were performed with nitrogen plasma generated using electron cyclotron resonance (ECR) microwave source. Here it highlighted the influence of nitrogen flow and applied substrate bias voltage on the structural characteristics of ta-C films during the plasma nitriding process. The chemical compositions, element depth distribution profiles, physical structures and bonding configurations of plasma-nitrided ta-C films were investigated by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and UV-vis Raman spectroscopy. The experimental results show that the carbon nitride compounds (CN_x) are formed in nitrogenated ta-C films in which the N content and its depth distribution depends on bias voltage to large extent rather than N₂ flow. The N content of nitrogenated ta-C films can reach 16 at.% for a substrate bias of −300 V and a N₂ flow of 90 sccm. With increasing nitrogen content, there is less G peak dispersion and more ordering of structure. Furthermore, appropriate nitriding treatment (substrate bias: −100 V, N₂ flow: 150 sccm) can greatly increase the fraction of sp³ and sp³C-N bonds, but the values begin to fall when the N content is above 9.8 at.%. All these indicate that suitable ECR-assisted microwave plasma nitriding is a potential modification method to obtain ultra-thin ta-C films with higher sp³ and sp³C-N fractions for high-density magnetic storage applications.     

Deposition of titanium nitride and hydroxyapatite-based biocompatible composite by reactive plasma spraying

Titanium nitride is a bioceramic material successfully used for covering medical implants due to the high hardness meaning good wear resistance. Hydroxyapatite is a bioactive ceramic that contributes to the restoration of bone tissue, which together with titanium nitride may contribute to obtaining a superior composite in terms of mechanical and bone tissue interaction matters.The paper presents the experimental results in obtaining composite layers of titanium nitride and hydroxyapatite by reactive plasma spraying in ambient atmosphere. X-ray diffraction analysis shows that in both cases of powders mixtures used (10% HA + 90% Ti; 25% HA + 75% Ti), hydroxyapatite decomposition occurred; in variant 1 the decomposition is higher compared with the second variant. Microstructure of the deposited layers was investigated using scanning electron microscope, the surfaces presenting a lamellar morphology without defects such as cracks or microcracks. Surface roughness values obtained vary as function of the spraying distance, presenting higher values at lower thermal spraying distances.