Search for novel amorphous alloys with high crystallization temperature by combinatorial arc plasma deposition

This paper describes a combinatorial search for novel amorphous alloys with high crystallization temperatures (T_x) using combinatorial arc plasma deposition (CAPD). The CAPD technique can deposit 1089 (33 × 33) thin film samples with different compositions on a substrate at one time. These 1089 samples on the substrate are individually referred to as CAPD samples and collectively referred to as a thin film library. Thin film libraries of Ir-Zr-Fe, Ir-Zr-Al, Mo-Zr-Al, Mo-Zr-Si, Ru-Zr-Fe and Ru-Zr-Si were deposited by CAPD. The compositions and phases of the CAPD samples were measured by energy dispersive X-ray fluorescence spectrometry and X-ray diffractometry, respectively. The results revealed that each library included amorphous CAPD samples. Since it is impossible to measure the T_x, fracture strength, fracture strain and Young's modulus of the CAPD samples by conventional measurement methods, larger samples having the same compositions as the amorphous CAPD samples were fabricated by a sputtering system. Since all CAPD samples of Ir-Zr-Fe and Ir-Zr-Al were too brittle, their corresponding sputter-deposited samples were not prepared. Sputter-deposited Mo-Zr-Al, Mo-Zr-Si, Ru-Zr-Fe and Ru-Zr-Si samples with ∼50 at.% Mo- or Ru-content were fabricated, and T_x and mechanical properties of these sputter-deposited samples were evaluated. All the sputter-deposited samples of Mo-Zr-Al and Mo-Zr-Si showed high T_x exceeding 973 K and as well as brittle characteristics. Ru₅₀Zr₃₅Fe₁₀ samples showed high T_x exceeding 1273 K and a low fracture strength of 0.26 GPa. Samples of Ru₅₁Zr₅Si₄₄ showed a high T_x of 923 K and a high fracture strength of 1.25 GPa.     

Short-to-medium-range order in Mg65Cu25Y10 metallic glass

The atomic configurations of liquid and glassy Mg₆₅Cu₂₅Y₁₀ alloy have been simulated in the temperature range of 300 K to 2000 K via ab initio molecular dynamics. The variations of pair correlation function (PCF), structure factor (SF), coordination number (CN) and bond pairs with the temperature for this alloy are characterized. It has been shown that the atoms are near densely packed and icosahedral type of short-range order (SRO) is predominant in the glass state. Icosahedral medium range order (MRO) can be formed by vertex or intercross connection of icosahedral SROs. In this work, an icosahedral MRO which is composed of 55 atoms has been found. It has been also clarified that Mg and Cu occupy the centre or vertex, and Y atoms only occupy the vertex of the icosahedron in this glassy alloy. It is believed that these findings have implication for understanding the glass forming mechanism of magnesium based metallic glasses.     

Effect of air post contamination on mechanical properties of amorphous carbon nitride thin films

We report in this study the mechanical, structural and compositional characteristics of amorphous carbon nitride films (a-CN_x) deposited on Si(100) using RF magnetron sputtering of graphite targets in pure nitrogen and under different RF powers. The properties of the films were determined in their as deposited state using nuclear reaction analysis (NRA), elastic recoil detection (ERDA), infrared (IR) absorption and Raman spectroscopy. The mechanical properties were obtained combining nanoindentation and residual stress measurements. The presence of various types of C-N bonds, as well as the post-deposition contamination of the deposited films by oxygen and water (voids) is revealed. The measured hardness and Young modulus were 0.9-2.03 and 23-27 GPa, respectively. These results have been analysed in term of the matrix flexibility which results from the nitrogen content and the porous character of the films, which can affect deeply the estimation of the physical-mechanical properties of the films.     

Phase formation in ion bombarded metallic films

The interplay of several events, ranging from production, migration and interaction of defects, to irradiation enhanced atomic diffusion and chemical mixing, is responsible for phase formation in surface layers of ion bombarded metallic alloys. The problem is so complicated that even the interpretation and the prediction of extreme cases such as the attainment of a crystalline, or a glassy product are presently beyond the possibilities of first principle approaches, and empirical criteria have been proposed to this end. In this work we limit ourselves to the very beginning of phase formation, i.e. thenucleation stage, in the frame of an atomistic model. In a binary alloy, after formation of collision cascades, the relaxation to metastable equilibrium of the locally altered compositional profile due to preferential migration to the cascade-matrix interface of one alloy component, is schematized by charge transfer events As a result, dimers of an effective alloy are formed. Conditions specific of glass and respectively crystal formation are extracted from an analysis of surface and thermochemical properties of starting and effective alloys.     

Defects in thin film silicon at the transition from amorphous to microcrystalline structure

Defects in thin film silicon with different structure all the way from amorphous to microcrystalline were investigated by electron spin resonance with emphasis on amorphous material prepared close to the transition to crystalline growth. Electron beam irradiation and stepwise annealing is used for reversible variation of the defect density over three orders of magnitude. The electron irradiation enhances mainly the native paramagnetic defects. Additional resonances are found as satellites to the central line, which anneal rapidly at temperatures below 100 °C. These features are most pronounced for the amorphous material prepared close to the transition to crystalline growth. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

FeSiBP bulk metallic glasses with high magnetization and excellent magnetic softness

Fe-based amorphous alloy ribbons are one of the major soft magnetic materials, because of their superior magnetic properties such as the relatively high saturation magnetization (J_s) of 1.5–1.6 T and good magnetic softness. However, the preparation of the ordinary amorphous magnetic alloys requires cooling rates higher than 10⁴ K/s due to the low glass-forming ability (GFA) and thus restricts the material outer shape. Recently, Fe-metalloid-based bulk metallic glasses (BMGs) containing glass-forming elements such as Al, Ga, Nb, Mo, Y and so forth have been developed. These alloys have high GFA, leading to the formation of BMG rod with diameters of mm-order. However, the glass-forming metal elements in BMGs result in a remarkable decrease in magnetization. Basically, J_s depends on Fe content; hence, high J_s requires high Fe content in the Fe-based amorphous alloys or BMGs. On the other hand, high GFA requires a large amount of glass-forming elements in the alloys, which results in lower Fe content. Therefore, in substances, the coexistence of high J_s and high GFA is difficult. Since this matter should be immensely important from academia to industry in the material field, a great deal of effort has been devoted; however, it has remained unsolved for many years. In this paper, we present a novel Fe-rich FeSiBP BMG with high J_s of 1.51 T comparable to the ordinary Fe–Si–B amorphous alloy now in practical use as well as with high GFA leading to a rod-shaped specimen of 2.5 mm in diameter, obtained by Cu-mold casting in air.     

Equilibrium and kinetic surface segregation in binary alloy thin films

A general theoretical analysis of the effect of film thickness on equilibrium and kinetic surface segregation in binary alloy thin films is presented. In this analysis, a constrained condition that represents the finite size of thin film system has been introduced to the modified Darken model, which has been used to describe both equilibrium and kinetic surface segregation in bulk materials. Simulation of surface segregation for alloy thin films can be carried out for all composition ranges and all film thicknesses if only knowing the surface segregation parameters for bulk materials. Simulations of equilibrium and kinetic surface segregation in Cu(1 1 1)Ag binary alloy thin film are presented.     

Formation of amorphous layers by solid-state reaction. from thin Ir films on Si(100)

Received: 18 November 1997 / Accepted: 16 October 1998 / Published online: 24 February 1999     

Surface modification of γ-TiAl alloys by acetylene plasma deposition

Surfaces of two γ-TiAl alloys, Ti-47 at% Al-2at% Nb-2 at% Cr (MJ12) and Ti-47 at% Al-2 at% Nb-2 at% Mn + 0.8 at% TiB₂ (MJ47), have been modified by acetylene plasma deposition at bias voltages of −4, −5 and −6 kV for 3.6 × 10³ s (1 h) and 1.44 × 10⁴ s (4 h). Knoop hardness (HK) of the alloys is increased with the increase of bias voltage and prolonged time for the deposition. HK of MJ12 and MJ47 deposited at −6 kV for 1.44 × 10⁴ s is, respectively, 3.36 and 3.32 times as hard as the untreated alloys. SEM and AFM analyses show that the deposited alloys compose of a number of nano-dots which reflect their surface properties. The phases analyzed by XRD are in accord with the elements analyzed by EDX.     

Multifractal analysis of ITO thin films prepared by electron beam deposition method

In this work, we developed the multifractality and its formalism to investigate the surface topographies of ITO thin films prepared by electron beam deposition method for various annealing temperatures from their atomic force microscopy (AFM) images. Multifractal analysis shows that the spectrum width, Δα (Δα = α_max − α_min), of the multifractal spectra, f(α), can be used to characterize the surface roughness of the ITO films quantitatively. Also, it is found that the f(α) shapes of the as-deposited and annealed films remained left hooked (that is Δf = f(α_min) − f(α_max) > 0), and falls within the range 0.149-0.677 depending upon the annealing temperatures.     

The nano-structural properties of hydrogenated a-Si and Si-C thin films alloys by GISAXS and vibrational spectroscopy

Amorphous hydrogenated silicon (a-Si:H) with high hydrogen content (10-40 at.%), and non-stehiometric silicon-carbon (Si_1−xC_x) thin films with a variation of the carbon to silicon ratio up to 0.3, were deposited by using a magnetron sputtering source. The Si_1−xC_x thin films were partially crystallised after deposition by thermal annealing up to 1050 °C.The GISAXS (Grazing Incidence Small Angle X-ray Scattering) spectra of all of the prepared specimens indicate the presence of “particles” in the “bulk” of the films. For the a-Si:H samples, “particles” are most probably voids agglomerates with a variation in size between 3 and 6 nm. The mean value of the size distribution of the “particles” increases while its width slightly decreases with the hydrogen content in the film. This indicates a better structural ordering which is consistent with the results of Raman spectroscopy that show a decrease of the ratio between intensities of transversal acoustic (TA) and transversal optic (TO) phonon peaks, I_TA/I_TO, and a narrowing of the TO peak with increasing hydrogen content. These results are discussed as a consequence of the beneficial influence of hydrogen bombardment during the film growth.For Si_1−xC_x thin films, the “particles” are assumed to be SiC nano-crystals with a size between 2 and 14 nm and they are larger in films with a higher carbon concentration. Inside each of the films, the crystals are larger closer to surface and they grow faster in the direction parallel to the surface than in that which is perpendicular to it.     

Electron impinging on metallic thin film targets

Based on the Vicanek and Urbassek theory [M. Vicanek, H.M. Urbassek, Phys. Rev. B 44 (1991) 7234] combined to a home-made Monte Carlo simulation, the present work deals with backscattering coefficients, mean penetration depths and stopping profiles for 1-4 keV electrons normally incident impinging on Al and Cu thin film targets. The cross-sections used to describe the electron transport are calculated via the appropriate analytical expression given by Jablonski [A. Jablonski, Phys. Rev. B 58 (1998) 16470] whose new improved version has been recently given [Z. Rouabah, N. Bouarissa, C. Champion, N. Bouaouadja, Appl. Surf. Sci. 255 (2009) 6217]. The behavior of the backscattering coefficient, mean penetration depth and stopping profiles versus the metallic film thickness at the nanometric scale and beyond is here analyzed and discussed.     

Au doped Sb3Te phase-change material for C-RAM device

Au doped Sb₃Te phase-change films have been investigated by means of in situ temperature-dependent resistance measurement. Crystallization temperature of 2 at.% Au doped Sb₃Te has been enhanced to 161 °C, which leads to a better data retention. The physical stability of the film has been improved evidently after adding Au as well. Resistance contrast has been improved to 1.1 × 10⁴, one order of magnitude higher than that of pure Sb₃Te. X-ray diffraction patterns indicate the polycrystalline Au-SbTe series have hexagonal structure, similar with pure Sb₃Te alloy, when Au doping dose is less than 9 at.%.     

Photoelectron-spectroscopic and reactivity investigation of thin Pd-Sn films prepared by magnetron sputtering

We have studied Pd-Sn layers with different composition prepared by magnetron sputtering. Layers were sputtered onto Al₂O₃ and SiO₂ substrates and studied by X-ray photoelectron spectroscopy (XPS). Spectra confirmed that after vacuum annealing residual oxygen and carbon have been removed and bimetallic bonds have been created. The shift of Pd 3d_5/2 core level to higher binding energy followed by the peak narrowing in dependence on the composition was observed, accompanied by the shift of the Pd 4d in the valence band region, induced by hybridization of Pd-d and Sn-s,p states. Experiments carried out on a gas-flow reactor indicate increasing temperature of the CO oxidation with tin ratio in the alloy.     

Low temperature dependence of elastic moduli and internal friction for the glassy alloy Zr55Cu30Al10Ni5

Longitudinal and transverse wave velocities, eight kinds of elastic parameters, and dilational and shear internal frictions of Zr₅₅Cu₃₀Al₁₀Ni₅ glassy alloy were simultaneously measured as a function of temperature in the range from 77 to 373 K, using an ultrasonic pulse method. The inflections at around 150 K for wave velocities, anisotropy factor and Poisson's ratio, and the 150 K peak of shear friction seem to correspond to one topological change (pseudo‐transition) associated with an interatomic readjustment or vacancy rearrangements. The behaviors from 77 to 125 K and 125 to 373 K are due to thermal relaxation of squeezed free volumes and entropy elasticity associated with vibrational motions of clusters, respectively, accompanied by an increase in atomic distance. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stretched exponential relaxation in the Coulomb glass

The relaxation of the specific heat and the entropy to their equilibrium values is investigated numerically for the three-dimensional Coulomb glass at very low temperatures. The long time relaxation follows a stretched exponential function, f (t) = f ₀exp - (t/τ)^β , with the exponent β increasing with the temperature. The relaxation time diverges as an Arrhenius law when T→ 0. Received 24 May 2001 and Received in final form 12 September 2001     

Optical and structural parameters of the ZnO thin film grown by pulsed filtered cathodic vacuum arc deposition

Transparent conductive ZnO film was deposited on glass substrate by pulsed filtered cathodic vacuum arc deposition (PFCVAD). Optical parameters such as absorption coefficient α, the refractive index n, energy band gap E_g and dielectric constants have been determined using different methods. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. The spectra of the dielectric coefficient were used to calculate the energy band gap and the value was 3.24 eV. The experimental energy band gap was found to be 3.22 eV for 357 nm thick ZnO thin film. The envelope method was also used to calculate the refractive index and the data were consistent with K-K relation results. The structure of the film was analyzed with an x-ray diffractometer and the film was polycrystalline in nature with preferred (002) orientation.     

Optimization of plasma parameters for high rate deposition of titanium nitride films as protective coating on bell-metal by reactive sputtering in cylindrical magnetron device

Nano-structured titanium nitride (TiN) thin film coating is deposited by reactive sputtering in cylindrical magnetron device in argon and nitrogen gas mixtures at low temperature. This method of deposition using DC cylindrical magnetron configuration provides high uniform yield of film coating over large substrate area of different shapes desirous for various technological applications. The influence of nitrogen gas on the properties of TiN thin film as suitable surface protective coating on bell-metal has been studied. Structural morphological study of the deposited thin film carried out by employing X-ray diffraction exhibits a strong (2 0 0) lattice texture corresponding to TiN in single phase. The surface morphology of the film coating is studied using scanning electron microscope and atomic force microscope techniques. The optimized condition for the deposition of good quality TiN film coating is found to be at Ar:N₂ gas partial pressure ratio of 1:1. This coating of TiN serves a dual purpose of providing an anti-corrosive and hard protective layer over the bell-metal surface which is used for various commercial applications. The TiN film's radiant golden colour at proper deposition condition makes it a very suitable candidate for decorative applications.     

碳氮薄膜的制备及其拉曼光谱研究

使用自行设计的真空系统 ,采用弧光放电等离子体的方法 ,成功制备了表面光滑致密的碳氮薄膜 .牛顿环干涉图样进一步验证了薄膜厚度的均匀性 .拉曼光谱显示了 3个主要的散射峰和几个相对较弱的峰 ,拉曼光谱分析表明 ,膜的结构是一种无定形非晶碳氮膜 ,碳原子与氮原子在薄膜中以各种不同的键态存在 .通过比较样品不同区域的拉曼光谱图发现 ,谱图几乎没有变化 ,说明制备的碳氮薄膜结构是均匀的     

Nano-structured Fe thin film deposition using plasma focus device

This paper reports the deposition of nano-structured Fe thin films using 3.3 kJ Mather-type plasma focus. The conventional hollow copper anode was replaced by anode fitted with solid Fe top and the deposition was done using different numbers of deposition shots at two different angular positions. Scanning Electron Microscopy shows that the size of nano-phase agglomerate is smaller when the sample is deposited using either lesser number of deposition shots or at higher angular position with respect to anode axis. X-ray Diffraction shows that crystal structure characteristics change with increase in number of deposition shots. Measurements of magnetic properties using Vibrating Sample Magnetometer identify intermediate magnetization and coercivity in Fe thin films deposited at smaller angular position with respect to anode axis. It is concluded that the morphological, structural and magnetic characteristics of Fe thin films deposited using plasma focus device depend not only on the number of focus deposition shots but also on the angular position of the sample.