Effect of nitrogen flow ratios on the structure and mechanical properties of (TiVCrZrY)N coatings prepared by reactive magnetron sputtering

This study reports the influence of growth conditions on the characteristics of (TiVCrZrY)N coatings prepared by reactive magnetron sputtering at various N₂-to-total (N₂ + Ar) flow ratio, which is R_N. The crystal structures, microstructure, and mechanical properties for different R_N were characterized by electron spectroscopy for chemical analysis, X-ray diffraction, atomic force microscopy, field-emission-scanning electron microscopy, transmission electron microscopy, and nanoindentation. The results indicate that the TiVCrZrY alloy and nitride coatings have hexagonal close-packed (hcp)-type and sodium chloride (NaCl)-type solid-solution structures, respectively. The voids in the coatings are eliminated and the growth of the columnar crystal structures is inhibited along with an increasing R_N. As a consequence, highly packed equiaxed amorphous structures with smooth surfaces are formed. The coatings accordingly achieved a pronounce hardness of 17.5 GPa when R_N = 100%.     

Influence of N2 flow ratio on the properties of hafnium nitride thin films prepared by DC magnetron sputtering

Hafnium nitride (Hf-N) thin films were deposited on fused silica at different N₂ flow ratio (N₂/N₂ + Ar) using a reactive DC magnetron sputtering system. A gradual evolution in the composition of the films from Hf₃N₂, HfN, to higher nitrides was found through X-ray diffraction (XRD). Films of Hf₃N₂ and HfN show positive temperature coefficients of resistivity, while higher nitride has a negative one. Highly oriented growth of (0 0 1) Hf₃N₂ and NaCl-structure (1 0 0) HfN films were fabricated on fused silica substrate at relatively lower temperature of 300 °C. The electrical resistivity values of both as-deposited and post-deposition annealed films were measured by a four-point probe method. The obtained minimum resistivity of as-deposited film is 20 μΩ cm, and this result shows potential application of HfN films as electrode materials in electronic devices.     

脉冲磁控溅射法制备单斜相氧化铒涂层

用中频脉冲反应磁控溅射法,在溅射功率为78 W,93 W和124 W以及衬底温度分别为室温,500 ℃及677 ℃下制备了氧化铒涂层.采用原子力显微镜、纳米压痕、X射线衍射和掠入射X射线衍射法研究了涂层的形貌、力学性能及物相结构.测量了涂层的电学性能.结果显示,脉冲磁控溅射沉积氧化铒涂层具有较高的沉积速率.实验制备得到了单斜相结构的氧化铒涂层.提高溅射功率时,沉积速率从28 nm/min增大至68 nm/min,涂层的结晶质量显著下降.提高衬底温度至500 ℃和677 ℃时,单斜相衍射峰强度下降.分析认为 关键词： 氧化铒 脉冲磁控溅射 单斜晶相     

Influence of germanium incorporation on the structural and electrical properties of boron-doped ultrathin poly-Si1−x Ge x films deposited by chemical vapour deposition

A few properties of polycrystalline silicon germanium (poly-Si_1?x Ge _x ) films can be tailored by modulating the germanium incorporation. In this paper, the structural, mechanical and electrical properties of heavily doped ultrathin (~100 nm) poly-Si_1?x Ge _x films (0.84 ≤ x ≤ 0.88) fabricated by low-pressure chemical vapour deposition were investigated. For a boron concentration of ~2.2 × 10²¹ atoms/cm³, a slight increase of germanium fraction significantly enhances the deposition rate, crystallinity and Hall mobility while having negligible influence on the Young’s modulus and hardness. The grain size increases from ~6 to ~12 nm while the grain structure becomes more columnar. In addition, the resistivity decreases from 7.4 to 1.1 m Ω cm with a corresponding increase in the Hall mobility from ~0.9 to ~4.2 cm² V^?1 s^?1. However, the Young’s modulus (~101 GPa) and hardness (~8.8 GPa) are virtually unaffected within the range of germanium fraction explored. In practice, poly-SiGe layer having low resistivity, high modulus, high mobility and low surface roughness can be successfully applied for resonators, biosensors and nanoswitches among others.     

Characterization of TiN thin films grown by low-frequency (60 Hz) plasma enhanced chemical vapor deposition

The characteristics of TiN thin films grown on glass substrates by very low frequency (60 Hz) PECVD were investigated along with the reactive plasma generated using a 60 Hz power source. The TiN film depositions were performed using a gaseous mixture of H₂, N₂ and TiCl₄ onto a substrate positioned between two electrodes using a floating substrate holder with a heating unit. The substrate is electrically floated to avoid sample damages due to ion bombardment. As-grown TiN films showed a NaCl-type fcc structure with a (200) crystallographic plane, low resistivity (～60 μΩ cm) and gold-like color. Crystallinity was improved, impurities such as O and Cl were reduced, and the atomic ratio of N/Ti became stoichiometric with the increase of substrate temperature. Particularly, no chlorine component was detected above 500 °C. Also, the N₂ partial pressure strongly affected the deposition rate and ratio of N/Ti. Otherwise, impurities and crystallinity barely changed with the change of N₂ pressure. The atomic ratio of N/Ti, impurities, and crystallinity of the films significantly affected the optical and electrical properties. Consequently, we produced stoichiometric Cl-free TiN films with golden color above 500 °C at 60 mTorr. The effects of temperature played an important role in controlling the film properties compared to the N₂ partial pressure.     

Mechanical, tribological, and electrochemical behavior of Cr1−xAlxN coatings deposited by r.f. reactive magnetron co-sputtering method

Chromium aluminum nitride (Cr_1−xAl_xN) coatings were deposited onto AISI H13 steel and silicon substrates by r.f. reactive magnetron co-sputtering in (Ar/N₂) gas mixture from chromium and aluminum targets. Properties of deposited Cr_1−xAl_xN coatings such as compositional, structural, morphological, electrochemical, mechanical and tribological, were investigated as functions of aluminum content. X-ray diffraction patterns of Cr_1−xAl_xN coatings with different atomic concentrations of aluminum (0.51 < x < 0.69) showed the presence and evolution of (1 1 1), (2 0 0), and (1 0 2) crystallographic orientations associated to the Cr_1−xAl_xN cubic and w-AlN phases, respectively. The rate of corrosion of the steel coated with Cr_1−xAl_xN varied with the applied power; however, always being clearly lower when compared to the uncoated substrate. The behavior of the protective effect of the Cr_1−xAl_xN coatings is based on the substitution of Cr for Al, when the power applied to the aluminum target increases. The mechanical properties were also sensitive to the power applied, leading to a maximum in hardness and a reduced elastic modulus of 30 and 303 GPa at 350 W and a monotonic decrease to 11 and 212 GPa at 450 W, respectively. Finally, the friction coefficient measured by pin-on disk revealed values between 0.45 and 0.70 in humid atmosphere.     

Phase transformations of Fe3N-Fe4N iron nitrides at pressures up to 30 GPa studied by in situ X-ray diffractometry

The parameters of the equation of state of the stable ?-Fe₃N _x (where x = 0.8) nitride in the Fe-N system have been determined at pressures up to 30 GPa and temperatures up to 1273 K. The parameters V ₀ = 81.48(2) Å^?3, K _T = 162(3) GPa, K _T = 4.0 = 1.66(2), γ₀ = 555 K, and q = 1 have been determined for ?-Fe₃N_0.8 by the approximation of the P-V-T data with the Vinet equation of state and the thermal parameters within the Mie-Grüneisen-Debye formalism. No anomalous change in the volume of the cell owing to possible magnetic transitions has been revealed. The instability of Fe₄N at high pressures and Fe₃N in the presence of a deficit of nitrogen in the system has been established. The stable phase in the temperature range of 300–673 K and the pressure range of 20–30 GPa is ?-Fe₃N rather than ?-Fe₃N_0.8.     

SiCN thin film prepared at room temperature by r.f. reactive sputtering

Silicon–carbon nitride (SiCN) thin films were deposited on Si substrate at room temperature by r.f. reactive sputtering. Fourier transform infrared spectroscopy (FTIR), optical absorption spectra (α(λ)) and electrical conductivity (σ) were studied for the thin films. The effect of the annealing on IR and σ was investigated at different temperatures. IR analysis indicates that Si–H, C–N, Si–C, Si–N, C–N and CN bonds are present in a-SiCN:H films. A shift of the stretching mode for Si–H bond to the high-wavenumber side is observed with increasing the nitrogen flow ratio γ_N2(=N₂/(Ar+H₂+N₂+CH₄)). The shift is from 2000 to 2190 cm⁻¹ when γ_N2=13.7%. The study shows that the film structure and optical and electrical properties are obviously modified readily by controlling the process parameters of deposition. The improvement in the film properties, e.g., good thermal stability, is explained mainly in terms of the cross-linked structure between the Si, C and N atoms.     

High-rate reactive magnetron sputtering of zirconia films for laser optics applications

ZrO₂ exhibits low optical absorption in the near-UV range and is one of the highest laser-induced damage threshold (LIDT) materials; it is, therefore, very attractive for laser optics applications. This paper reports explorations of reactive sputtering technology for deposition of ZrO₂ films with low extinction coefficient k values in the UV spectrum region at low substrate temperature. A high deposition rate (64 % of the pure metal rate) process is obtained by employing active feedback reactive gas control which creates a stable and repeatable deposition processes in the transition region. Substrate heating at 200 °C was found to have no significant effect on the optical ZrO₂ film properties. The addition of nitrogen to a closed-loop controlled process was found to have mostly negative effects in terms of deposition rate and optical properties. Open-loop O₂ gas-regulated ZrO₂ film deposition is slow and requires elevated (200 °C) substrate temperature or post-deposition annealing to reduce absorption losses. Refractive indices of the films were distributed in the range n = 2.05–2.20 at 1,000 nm and extinction coefficients were in the range k = 0.6 × 10^?4 and 4.8 × 10^?3 at 350 nm. X-ray diffraction analysis showed crystalline ZrO₂ films consisted of monoclinic + tetragonal phases when produced in Ar/O₂ atmosphere and monoclinic + rhombohedral or a single rhombohedral phase when produced in Ar/O₂ + N₂. Optical and physical properties of the ZrO₂ layers produced in this study are suitable for high-power laser applications in the near-UV range.     

Giant temperature coefficient of resistance in Co-doped ZnO thin films

A novel high-performance thermistor material based on Co-doped ZnO thin films is presented. The films were deposited by the pulsed laser deposition technique on Si (111) single-crystal substrates. The structural and electronic transport properties were correlated as a function of parameters such as substrate temperature and Co-doped content for Zn_1?x Co _x O (x=0.005,0.05,0.10 and 0.15) to prepare these films. The Zn_1?x Co _x O films were deposited at various substrate temperatures between 20 and 280 °C. A value of 20 %/K for the negative temperature coefficient of resistance (TCR) with a wide range near room temperature was obtained. It was found that both TCR vs. temperature behavior and TCR value were strongly affected by cobalt doping level and substrate temperature. In addition, a maximal TCR value of over 20 %?K^?1 having a resistivity value of 3.6 Ω?cm was observed in a Zn_0.9Co_0.1O film near 260 °C, which was deposited at 120 °C and shown to be amorphous by X-ray diffraction. The result proved that the optimal Co concentration could help us to achieve giant TCR in Co-doped ZnO films. Meanwhile, the resistivities of the films ranged from 0.4 to 270 Ω?cm. A Co-doped ZnO/Si film is a strong candidate of thermometric materials for non-cooling and high-performance bolometric applications.     

Release of nitrous oxide and dinitrogen from a transition bog under drained and rewetted conditions due to denitrification: results from a [15N]nitrate–bromide double-tracer study

Denitrification is well known being the most important nitrate-consuming process in water-logged peat soils, whereby the intermediate compound nitrous oxide (N₂O) and the end product dinitrogen (N₂) are ultimately released. The present study was aimed at evaluating the release of these gases (due to denitrification) from a nutrient-poor transition bog ecosystem under drained and three differently rewetted conditions at the field scale using a ¹⁵N-tracer approach ([¹⁵N]nitrate application, 30?kg N ha^?1) and a common closed-chamber technique. The drained site is characterized by a constant water table (WT) of –30?cm (here referred to as D30), while rewetted sites represent a constant WT of –15?cm, a constant WT of 0?cm (i.e. waterlogged), and an initial WT of 0?cm (which decreased slightly during the experiment), respectively, (here referred to as R15, R0, and R0_d, respectively). The highest N₂O emissions were observed at D30 (291?µg N₂O–N m^?2 h^?1) as well as at R0_d (665?µg N₂O–N m^?2 h^?1). At the rewetted peat sites with a constant WT (i.e. R15 and R0), considerably lower N₂O emissions were observed (maximal 37?µg N₂O–N m^?2 h^?1). Concerning N₂ only at the initially water-logged peat site R0_d considerable release rates (up to 3110?µg N₂–N m^?2 h^?1) were observed, while under drained conditions (D30) no N₂ emission and under rewetted conditions with a constant WT (R15 and R0) significantly lower N₂ release rates (maximal 668?µg N₂–N m^–2 h^?1) could be detected. In addition, it has been found that natural WT fluctuations at rewetted peat sites, in particular a rapid drop down of the WT, can induce high emission rates for both N₂O and N₂.     

Electron temperature and ion density measurements in a glow discharge of an Ar–N2 mixture

A DC glow discharge produced in N₂ gas can generate several species that are important in different applications, such as the modification of surface properties of materials. A low-pressure glow discharge apparatus was used for the the analysis of the Ar–N₂ mixture at a total pressure of 2.0 Torr, a power of 20 W and 40 l/min flow rate of gases. The emission bands were measured in the wavelength range of 200–1100 nm. The principal elements are N₂, N ₂⁺ and Ar I. The electron temperature was found in the range of 1.72–2.08 eV, and the ion density was in the order of 10¹⁰ cm^?3.     

The influence of gas flow rate on the structural,mechanical, optical and wettability of diamond-like carbon thin films

In this research, diamond-like carbon (DLC) thin films were deposited on silicon substrates by radio-frequency plasma enhanced chemical vapor deposition method using gas mixture of CH₄ and Ar. The effect of different CH₄/Ar gas ratio on the structure, refractive index, transmission and hardness of the DLC thin films were investigated by means of Raman spectroscopy, ellipsometry, Fourier transform Infrared Spectroscopy and nano-indentation methods, respectively. Nuclear resonant reaction analysis was used to measure the amount of hydrogen and carbon in the thin films. Furthermore, wettability of the thin films was achieved by measuring of water contact angle (WCA). The results indicated that the structural properties of the diamond-like carbon thin films are strongly dependent on the composition of gas mixture. Based on ellipsometry results, refractive index of the thin films varied in the range of 1.89–2.06 at 550 nm. FTIR results determined that deposition of DLC thin films on silicon substrate led to an increase of the light transmission in IR region and these films have the potential to be used in silicon optics as the antireflective coatings in this region. Nano-indentation analysis showed that the thin films hardness changed in the range of 7.5–11 GPa. On the other hand hydrogen content and fraction of C?H bonds in the samples increased by an increase in the gas ratio of CH₄/Ar. Also, WCA measurements indicated that WCA for thin films with gas ratio of 3/7 is the most and equal to 79°.     

Triethylbutylammonium bis(trifluoromethanesulphonyl)imide ionic liquid as an effective electrolyte additive for Li-ion batteries

Ionic liquids are promising additives for Li-ion batteries owing to its desirable physicochemical properties. Triethylbutylammonium bis(trifluoromethanesulphonyl)imide ([N₂₂₂₄][Tf₂N]) ionic liquid was synthesized and their physical and electrochemical properties were investigated. Among several quaternary ammonium ionic liquids, [N₂₂₂₄][Tf₂N] exhibited higher conductivity (1.31 mS?cm^?1), better thermal and electrochemical stabilities, and wide electrochemical window, i.e., more than 5.9 V. Standard solution was prepared by dissolving lithium bis(trifluoromethanesulphonyl)imide (LiTf₂N) in ethylene carbonates/dimethyl carbonate (1:1, by weight). The conductivity for the electrolyte containing [N₂₂₂₄][Tf₂N] and the mixed electrolyte without additives at 25 °C are 10.24 and 8.79 mS?cm^?1, respectively. LiFePO₄ half-cell containing 0.6 mol?L^?1 LiTf₂N-based organic electrolyte with [N₂₂₂₄][Tf₂N] showed relatively high initial discharge capacity and coulombic efficiency at first cycle. It is found that the mix [N₂₂₂₄][Tf₂N] electrolyte exhibits relatively high-rate capacity. The capacity retention of half-cell containing [N₂₂₂₄][Tf₂N] is 2 % more than without additive at 0.2 C. However, the rate capacity retention of the half-cell with mix [N₂₂₂₄][Tf₂N] electrolyte is above 10 % more than without additive at 0.5 C. The results showed that [N₂₂₂₄][Tf₂N] was an effective electrolyte additive in LiFePO₄ half-cell.     

Structural and tribological properties of nitrogen doped amorphous carbon thin films synthesized by CFUBM sputtering method for protective coatings

Nitrogen doped amorphous carbon (a-C:N) films are a material that may successfully compete with DLC coatings, which have high hardness, high wear resistance, and a low friction coefficient. The a-C:N films were prepared on silicon substrate by a closed-field unbalanced magnetron sputtering method with a graphite target and using the Ar/N₂ mixture gases. And, we investigated the effects of various DC bias voltages from 0 to −300 V on the structural and tribological properties of the a-C:N films. This study was focused on improving physical properties of the a-C:N film by controlling process parameters like negative substrate DC bias voltage. The maximum hardness of the a-C:N film was 23 GPa, the friction coefficient was 0.08, and the critical load was 25 N on a Si wafer. Consequently, the structural and tribological properties of the a-C:N film showed a clear dependence on the energy of ions bombardment and the density of the sputtering and the reaction gases during film growth.     

Mittlere Energien und Driftgeschwindigkeiten von Elektronen in Stickstoff,Argon und Xenon,ermittelt aus Bildverstärkeraufnahmen von Elektronenlawinen

Local and temporal development of electron avalanches in a pulsed discharge gap (d=3,00 cm) are investigated in N₂, Ar, Xe and mixtures of N₂ and CH₄ by simultaneously applying high gain image intensifier- and photomultiplier techniques. Electron drift velocities are obtained from time-of-flight and way-of-flight measurements in these gases. The mean energy of agitation of the electrons is derived both from electron mobility and avalanche image trace profile (diffusion broadening). The results obtained (for 20°C), being in fair agreement with one another, read N₂: (4·6...5·0) eV forE/p=50...200 V/cm Torr; Ar: (9·0...9·5) eV forE/p=24... 45 V/cm Torr; Xe: (4·8...5·0) eV forE/p= 40... 90 V/cm Torr; CH₄(10% N₂): 6·3 eV forE/p= 89 V/cm Torr. The mean energy of agitation does not change very much withE/p in the ranges investigated. Some results concerning the radiation properties of these gases are included such as lifetime of the excited states, quenching pressure etc.     

First-principles calculations of the structural, electronic and magnetic properties of BnN20−n (n = 6−18) clusters

The structures of B _n N_20 ? n    (n = 6?18), the clusters of boron nitride, are investigated by the density functional theory calculations. The structures of the obtained low-lying isomers can be described by the following six prototypes: single ring, double ring, three-ring, graphitic-like sheet, fullerene and others. B₁₀N₁₀ is demonstrated to be the most stable cluster against the nonstoichiometric ones. Nonzero magnetic moments, 1.999, 1.998, 2.000, 3.999 and 1.999μ _B respectively, are found in five B _n N_20?n (n = 6, 7, 11, 12, 13) clusters. Further analysis indicates that the magnetic moment of the B₆N₁₄ cluster is mainly originated from the N atoms, while those of others are from the B atoms. The magnetic moment are finally attributed to the interesting issues of the 2p electrons due to the breaking of local symmetries, the change of coordination number, charge distribution and orbital hybridization.     

Structural and mechanical properties of compositionally gradient CrNx coatings prepared by arc ion plating

Compositionally gradient CrN_x coatings were fabricated using arc ion plating by gradually increasing N₂ flow rate during the deposition process. The effect of substrate bias, ranging from 0 to −250 V, on film microstructure and mechanical properties were systematically investigated with XRD, SEM, HRTEM, nanoindentation, adhesion and wear tests. The results show that substrate bias has an important influence on film microstructure and mechanical properties of gradient CrN_x coatings. The coatings mainly crystallized in the mixture of hexagonal Cr₂N, bcc Cr and fcc rock-salt CrN phases. N₂ flow rate change during deposition results in phase changes in order of Cr, Cr + Cr₂N, Cr₂N, Cr₂N + CrN, and CrN, respectively, along thickness direction. Phase fraction and preferred orientation in CrN_x coatings vary with substrate bias, exerting an effective influence on film hardness. With the increasing of bias, film microstructure evolves from an apparent columnar structure to a highly dense one. The maximum hardness of 39.1 GPa was obtained for the coatings deposited at a bias of −50 V with a friction coefficient of 0.55. It was also found that adhesion property and wear resistance of gradient CrN_x coatings were better than that of homogeneous CrN coatings.     

High pressure studies on the electrical resistivity of As–Te–bond Si glasses and the effect of network topological thresholds

The variation of resistivity in an amorphous As₃₀Te_70?x Si _x system of glasses with high pressure has been studied for pressures up to 8 GPa. It is found that the electrical resistivity and the conduction activation energy decrease continuously with increase in pressure, and samples become metallic in the pressure range 1.0–2.0 GPa. Temperature variation studies carried out at a pressure of 0.92 GPa show that the activation energies lie in the range 0.16–0.18 eV. Studies on the composition/average co-ordination number ? r? dependence of normalized electrical resistivity at different pressures indicate that rigidity percolation is extended, the onset of the intermediate phase is around ? r?=2.44, and completion at ? r?=2.56, respectively, while the chemical threshold is at ? r?=2.67. These results compare favorably with those obtained from electrical switching and differential scanning calorimetric studies.     

Practical effects of pressure-transmitting media on neutron diffraction experiments using Paris–Edinburgh presses

ABSTRACT

To understand the practical effects of pressure-transmitting media (PTM) on neutron diffraction using Paris–Edinburgh presses, diffraction patterns of MgO were collected to approximately 20?GPa using PTMs of Pb, AgCl, 4:1 methanol–ethanol (ME) mixture with and without heating, N₂, and Ar. Hydrostaticity in the sample chamber estimated from the MgO 220 peak width improves in the order of Pb, AgCl, Ar, ME mixture, N₂, and the heated ME mixture. Unlike previous results using diamond anvil cells, the unheated ME mixture is superior to Ar even after freezing, probably due to the cup on the anvil face. Considering these results and the sizable coherent scattering of Ne, which would show good hydrostaticity, we conclude that the ME mixture (preferably the heated one) is the best PTM in neutron experiments up to 20?GPa, while Ar can be substituted when a sample is reactive to alcohols.