(Fe,Ti) 16N2 films with high saturation magnetization prepared by facing target sputtering

(Fe,Ti)-N films with a Ti concentration of 10 at.% were prepared on Si(100) and NaCl substrates by facing targets sputtering. The effects of the nitrogen pressure (P_N) and the substrate temperature (T_s) on the formation of various (Fe,Ti)-N phases and their microstructures were investigated in detail. X-ray diffractometer and transmission electron microscope provided complete identification of the phases present in the films and the characterization of their microstructures. Films deposited at a lower P_N = 1 3 × 10⁻² Pa or a lower T_s = RT consist of mainly -phase. Films deposited at a higher P_N = 1.3 2 × 10⁻¹ Pa or a higher T_s = 200 °C contain a great many γ' and Fe₂N phases with a higher nitrogen content. When P_N = 4 7 × 10⁻² Pa and T_s = 100 150 °C, it is advantageous to the formation of ′' phase. These films exhibit a high saturation magnetization (M_s) up to the range of 2.3 2.5 T, which is larger than that of pure iron.     

Deposition of WNxCy thin films for diffusion barrier application using the dimethylhydrazido (2) tungsten complex (CH3CN)Cl4W(NNMe2)

Tungsten nitride carbide (WN_xC_y) thin films were deposited by chemical vapor deposition using the dimethylhydrazido (2⁻) tungsten complex (CH₃CN)Cl₄W(NNMe₂) (1) in benzonitrile with H₂ as a co-reactant in the temperature range 300 to 700 °C. Films were characterized using X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy and four-point probe to determine film crystallinity, composition, atomic bonding, and electrical resistivity, respectively. The lowest temperature at which growth was observed from 1 was 300 °C. For deposition between 300 and 650 °C, AES measurements indicated the presence of W, C, N, and O in the deposited film. The films deposited below 550 °C were amorphous, while those deposited at and above 550 °C were nano-crystalline (average grain size < 70 Å). The films exhibited their lowest resistivity of 840 µΩ-cm for deposition at 300 °C. WN_xC_y films were tested for diffusion barrier quality by sputter coating the film with Cu, annealing the Cu/WN_xC_y/Si stack in vacuum, and performing AES depth profile and XRD measurement to detect evidence of copper diffusion. Films deposited at 350 and 400 °C (50 and 60 nm thickness, respectively) were able to prevent bulk Cu transport after vacuum annealing at 500 °C for 30 min.     

Compositionally graded Pb(Zr,Ti)O3 thin films with different crystallographic orientations

Compositionally graded ferroelectric PbZr_xTi_1−xO₃ (PZT) films were deposited using a sputtering method and crystallized in situ at 500 °C. The films showed purely (100) or (111) crystallographic orientation when grown on Si/SiO₂/TiO₂/Pt substrates, while they exhibited c-axis epitaxial microstructure when prepared on MgO/Pt substrates. Their crystallographic orientation was controlled owing to a thin TiO_x layer sputtered on substrates prior to PZT deposition. Analysis performed by Auger depth profile clearly confirmed the variation of composition in the films. Coercive fields from 80 kV/cm to 200 kV/cm and remnant polarization as large as 45 μC/cm² were obtained. However, no typical offset was observed on hysteresis loops, unlike previous works related to graded PZT films.     

Microstructure, mechanical and tribological properties of Ti(C, N)/a-C gradient composite films

Ti(C, N)/a-C composite films with compositional gradient from Ti-TiN-Ti(C, N) to Ti-containing a-C layers have been prepared by closed-field unbalanced magnetron sputtering. Within the composite films, the carbon contents gradually increase and achieve maximum in the a-C layer by increasing the power applied to the graphite targets, the nitrogen contents gradually decrease to zero from Ti(C, N) layer of the interface to a-C layer of the films. In order to achieve a good combination of the mechanical and tribological properties in the composite films, a designed experimental parameter basing on various substrate rotation speeds is also selected. Results show that the compositional gradient result in the microstructure change of composite films where the Ti(C, N) layers consist of fine nanocolumnar Ti(C, N) grains and the a-C layers consist of 2-7 nm TiC nanocrystallites embedded in an amorphous C matrix. The Ti(C, N) layers also exhibit clear multilayer structure where the period thickness gradually decreases as substrate rotation speed increases. Under higher rotation speed, disappearance of the multilayer structure is accompanied with simultaneous increase in the crystallinity of Ti(C, N) layer and also the Ti(C, N) grain size. In the a-C layer, the TiC nanocrystallites embedded in the a-C matrix is produced by the high rotation speeds. The Ti(C, N)/a-C gradient composite films exhibit high microhardness values (~5000 H_V) and low friction coefficient (~ 0.15), which is related to the hard Ti(C, N) layer and self-lubricate a-C layer, respectively. The combination of the Ti(C, N) layer with a-C layer increases the load and the wear resistance capacity of the composite films, which gives satisfactory friction performance in the pin-on-disk tests with a wear rate of 3.7 × 10^− 17 m³/mN.     

Structural and thermochemical properties, and energetics of C8(NO2)8 and C20(NO2)4n (n = 0–4)

Density-functional-theory calculations, at the B3LYP level with the 6–31 G basis set, have been performed to investigate the structural and electronic properties of octanitrocubane, C₈(NO₂)₈, and polynitrofullerenes of type C₂₀(NO₂)_4n, with n = 0–4, in their ground states. Having determined their energetically optimized geometric structures, energetics, and vibrational frequencies, we have calculated the enthalpies of combustion and decomposition of these molecules. Extrapolating from the so-obtained data, we have also estimated, as a by-product, the enthalpy values of C₂₀(NO₂)₂₀.     

Growth of CNx/BN:C multilayer films by magnetron sputtering

Symmetric CN_x/BN:C multilayer thin films, with nominal compositional modulation periods of Λ=2.5, 5, and 9 nm were deposited by unbalanced dual cathode magnetron sputtering from C (graphite) and B₄C targets in an Ar/N₂ (60/40) discharge. The multilayers and single-layer of the constituent CN_x and BN:C compounds were grown to a total thickness of 0.5 μm onto Si(001) substrates held at 225°C and a negative floating potential of 30 V (E_i≈24 eV). Layer characterizations were performed by TEM, X-ray reflectivity, RBS, and nanoindentation measurements. Results show that CN_0.33 and BN:C (35, 50, and 15 at.% of B, N, and C, respectively) layers were prepared at the above conditions. It is suggested that all films exhibit a three-dimensional interlocked structure with a cylindrical texture in the film growth direction. The structure was continuous over relatively well defined and smooth CN_x/BN:C interfaces. All coatings exhibit extreme elasticity with elastic recoveries as high as 85–90% (10 mN maximum load) attributed to the observed structure. However, the multilayers were stiffer and more elastic compared to that of the single-layers and thus shows promise for improved protective properties.     

Growth structure investigation of MgF2 and NdF3 films grown by molecular beam deposition on CaF2(111) substrates

The growth structure of MgF₂ and NdF₃ films grown on polished CaF₂(111) substrates deposited by molecular beam deposition has been investigated using transmission electron microscopy (TEM) of microfractographical and surface replications as well as cross-sectional TEM, atomic force microscopy, packing density, and absorption measurements. It has been shown that by taking advantage of ultrahigh vacuum environments and a special stratification property of MgF₂ and NdF₃ films, the preparation of nanocrystalline films of high packing density and low optical absorption is possible at a substrate temperature of 425 K.     

Preparation and characterization of C60S16 and C70S48 thin films

In this study, we have investigated different methods for preparation of thin films of C₆₀ and C₇₀-sulfur compounds. Films of good quality were obtained by reaction of amorphous C₆₀ and C₇₀ films with a saturated sulfur solution in toluene at 40°C or with saturated sulfur vapour at a temperature of 140°C for several hours. The quality of the fullerene-sulfur films were strongly dependent on the microstructure of the initially deposited fullerene film and the synthesis temperature. X-ray diffraction analyses showed that both methods lead to the formation of films consisting of C₆₀S₁₆ and C₇₀S₄₈ (space groups C 2/c and Amm2, respectively). C₆₀S₁₆ films synthesised on Al₂O₃(012) and Si(100) substrates were texture-free while C₇₀S₄₈ films typically exhibited a preferential (100) orientation. The films were also characterised by Raman and IR- spectroscopy, which confirmed that the interactions between the fullerene molecules and the S₈ rings are weak. The fullerene-sulfur compounds were found to be unstable at high vacuum conditions. Both materials C₆₀S₁₆ and C₇₀S₄₈ are non-conductive at room temperature with conductivities less then 10⁻⁵ (Ω/cm).     

Structural properties of epitaxial SrCuO2 thin films on SrTiO3 (001) substrates

Thin films of SrCuO₂ with tetragonal structure have been epitaxially grown on SrTiO₃ (001) substrates by high-oxygen pressure sputtering technique. The interface structure between SrCuO₂ and SrTiO₃ and configuration of defects in SrCuO₂ thin films have been characterized by means of high-resolution transmission electron microscopy. Two types of film-substrate interface structure coexist and are determined as bulk-SrO-TiO₂-Sr(O) -CuO₂-Sr-bulk and bulk-SrO-TiO₂-SrO-Sr(O) -CuO₂-Sr-bulk. The planar faults with double SrO atomic layers in {100} planes in SrCuO₂ thin films are observed, which mainly arise from the coalescence of these two types of film-substrate interface structure. Meanwhile, planar faults in {110} planes are observed in thin films and structural models are proposed.     

Growth and structure of epitaxial CeO2 films on yttria-stabilized ZrO2

Thirty to a hundred-nm thick epitaxial CeO₂ layers are grown on YSZ (100), (110) and (111) surfaces of yttria-stabilized ZrO₂ (YSZ) by electron beam evaporation of Ce in oxygen at reduced pressure. Their growth, structure and thermal stability are studied with several bulk and surface sensitive techniques including Rutherford backscattering spectrometry, cross-sectional high resolution electron microscopy, low energy electron diffraction and low energy reflection electron microscopy. Excellent epitaxy is obtained on all YSZ surfaces at a growth temperature of 750 K. The surfaces of films grown on (111)-oriented substrates are flat, whereas those on the other substrates are faceted into small (111) planes. The grain sizes in the films are in the 10 nm range and smaller.     

Segregation of Cu in Cu (Ti) alloys during nitridation in NH3

Cu(Ti 27 at.%) alloys on SiO₂ were reacted in NH₃ for 30 min over the temperature range 400–700 °C. Rutherford backscattering spectrometry in conjunction with high resolution transmission electron microscopy were utilized to investigate reaction products. At 400–450 °C, Ti is observed to segregate to the free surface to react with NH₃, forming an Ti oxynitride layer. Above 500 °C, Ti segregates to both the free surface and to the alloy/SiO₂ interface, leaving relatively-pure Cu layer. Reaction between Ti and SiO₂ results in a TiO/Ti₅Si₃ bilayer structure. By use of high spatial resolution energy dispersive X-ray spcctroscopy, the presence of a Cu-containing layer at the TiO/Ti₅Si₃ interface is observed. This layer may also contain Ti, Si and/or O. We propose a mechanism for Cu segregation to this interface which requires Cu diffusion across TiO and subsequent dissociation of Ti₅Si₃. Thermodynamic calculations support this mechanism.     

(Ti,W,Cr)B2 coatings produced by dc magnetron sputtering

Transition metal diboride coatings of composition (Ti_0.44W_0.29Cr_0.27)B_1.90 were deposited on silicon substrates by dc magnetron sputtering of compound targets. The chemical composition of the targets is transferred to the sputtered films. The as-deposited films are amorphous as indicated by grazing incidence X-ray diffraction. Investigations with electron microscopy revealed that the films show a columnar nano-structure. Annealing at temperatures between 1000 °C and 1300 °C leads to the formation of nano-crystalline precipitations, which can be attributed to (Ti,W,Cr)B₂, β-(W, Ti, Cr)B and W₂B₄ phases. Annealing can be used to tailor the average grain size of the precipitates, making these films a good candidate for hard coatings re-enforced by nano-structuring.     

(3 0 1) and (1 0 1) RuO2 twins on nanostructural rutile TiO2 template

The paper deals with a statistical study on the thermal degradation of some old paper supports. The experimental data permit establishment of some regression models, which describe the dependence between the half time and the temperature at which the paper support is kept and, respectively, between the exposure time of the paper supports to a certain temperature and the absorbency value of a characteristic peak, representative for the paper support.     

Characterization of inhomogeneity in TiO2 thin films prepared by pulsed dc reactive magnetron sputtering

This article discusses an analytical method for characterizations of TiO₂ thin films and determinations of the degree of their inhomogeneity. The TiO₂ films were prepared by a pulsed dc magnetron sputtering with an operating pressure as a main experimental parameter. The obtained films were primarily characterized for film crystallinity, microstructures and optical properties by spectroscopic ellipsometry. The measured ellipsometric data were analyzed by the single-, the double, and the triple-layer models in order to match with the inhomogeneous film structure proposed in the Thornton structure zone model. The results were then compared with those obtained from grazing-incidence X-ray diffraction, field-emission scanning electron microscopy and high-resolution transmission electron microscopy. The study revealed that the pulsed dc sputtered TiO₂ films could be best described by the inhomogeneous triple-layer physical model. Although the films deposited at lower operating pressure had a dense structure with a mirror-like surface topography, the films deposited at higher operating pressure had the porous structure with the rough surface and the void.     

Study on W/SiC interface of SiC fiber fabricated by chemical vapor deposition on tungsten filament

SiC fiber was fabricated by chemical vapor deposition on tungsten filament heated by direct current in a CH₃SiCl₃-H₂ gas system. Microstructure of W/SiC interfacial reaction zone in the fiber was identified by means of scanning electron microscope and transmission electron microscope. Results showed that the thickness of the interfacial reaction zone is between 350 and 390 nm, and two reaction products of W₅Si₃ and WC were formed during fabricating SiC fiber. Electron diffraction analysis and composition detection indicated that W₅Si₃ is adjacent to tungsten core and WC is adjacent to SiC sheath, and the W/SiC interface can be described as W/W₅Si₃/WC/SiC. Furthermore, the formation mechanism of the interfacial reaction zone is discussed.     

Native oxide consumption during the atomic layer deposition of TiO2 films on GaAs (100) surfaces

The consumption of the surface native oxides is studied during the atomic layer deposition of TiO₂ films on GaAs (100) surfaces. Films are deposited at 200 °C from tetrakis dimethyl amido titanium and H₂O. Transmission electron microscopy data show that the starting surface consists of ~2.6 nm of native oxide and X-ray photoelectron spectroscopy indicates a gradual reduction in the thickness of the oxide layer as the thickness of the TiO₂ film increases. Approximately 0.1-0.2 nm of arsenic and gallium suboxide is detected at the interface after 250 process cycles. For depositions on etched GaAs surfaces no interfacial oxidation is observed.     

Pulsed laser deposition of (WO3)1 − x(Nb2O5)x thin films: Characterization and gasochromic studies

A series of (WO₃)_{1 − x}(Nb₂O₅)_x (x = 0, 0.05, 0.1 and 0.15) mixed oxide films were fabricated by pulsed laser deposition (PLD) at 27 Pa oxygen partial pressure on ITO glass substrates. The thickness of the (WO₃)_{1 − x}(Nb₂O₅)_x thin films is about 350 ± 30 nm and their surface has a uniform morphology. A layer of platinum (Pt) was then sputtered onto the surface of the film. The hydrogen gas sensing performance of Pt catalyst activated (WO₃)_{1 − x}(Nb₂O₅)_x thin films were investigated. The cycling of the coloration was obtained from UV–vis spectra. Gasochromic coloration of (WO₃)_{1 − x}(Nb₂O₅)_x thin films were investigated at room temperature in H₂–N₂ mixtures containing 1–100 mol% of H₂. The results show that the shortest response time of (WO₃)_{1 − x}(Nb₂O₅)_x/Pt hydrogen sensor is within 30 s and the highest transmittance change (ΔT) varies from 20% to 30%.     

Densification of In2O3:Sn multilayered films elaborated by the dip-coating sol-gel route

Indium Tin Oxide (ITO) thin films have been deposited by the Sol-Gel Dip-Coating technique, the starting solutions being prepared from chlorides. These multilayered films were crystallized by means of a classical heat treatment at temperatures ranging from 500 to 600 °C. Five stacked layers are necessary to obtain a global electrical resistivity value of 2.9×10⁻³ Ω cm, for 500 °C annealed film. The paper focuses on the study of the structure of such multilayered deposits, and on the densification process, using transmission electron microscopy, Rutherford Back-scattering Spectrometry and electrical resistivity measurements. This analysis reveals structural inhomogeneities and different crystallite growth processes as a function of annealing temperature and number of deposited layers.     

Formation of CoNx ultra-thin films during direct-current nitrogen ion sputtering in ultrahigh vacuum

This study reports the formation of ultra-thin cobalt nitride (CoN_x) films on a Co/ZnO(002) crystal by low-energy ion sputtering of nitrogen in an ultrahigh vacuum system. The CoN_x film formed during ion bombardment in which the nitrogen plasma (N⁺) results in both sputtering and implantation in the formation process of CoN_x, especially for the Co adsorbed layers. Auger electron spectroscopy analysis shows that the composition ratio x as a function of sputtering time was highly related to the N⁺ ion energy that was varied from 0.5 to 2 keV. The composition ratio x of CoN_x films is inversely proportional to the ion energy. Low-energy ion sputtering is possible to fabricate ultra-thin CoN_x films and to adjust their chemical compositions.