Effects of substrate temperature on properties of NbNx films grown on Nb by pulsed laser deposition

NbN_x films were deposited on Nb substrate using pulsed laser deposition. The effects of substrate deposition temperature, from room temperature to 950 °C, on the preferred orientation, phase, and surface properties of NbN_x films were studied by X-ray diffraction, atomic force microscopy, and electron probe micro analyzer. We find that the substrate temperature is a critical factor in determining the phase of the NbN_x films. For a substrate temperature up to 450 °C the film showed poor crystalline quality. With temperature increase the film became textured and for a substrate temperature of 650−850 °C, mix of cubic δ-NbN and hexagonal phases (β-Nb₂N + δ′-NbN) were formed. Films with a mainly β-Nb₂N hexagonal phase were obtained at deposition temperature above 850 °C. The c/a ratio of β-Nb₂N hexagonal shows an increase with increased nitrogen content. The surface roughness of the NbN_x films increased as the temperature was raised from 450 to 850 °C.     

Preparation and characterization of ZnSn-substituted barium ferrite thin films

The preparation of ZnSn-substituted barium ferrite films by sputtering deposition was studied. The as-sputtered films were amorphous, and annealing at a minimum of 750 °C was required to crystallize the films, based on the X-ray diffraction analysis and the magnetic measurements. Scanning electron microscopy combined with energy-dispersive X-ray spectroscopic microanalysis confirmed that the films were single phase with the composition BaZn_xSn_xFe_12−2xO₁₉, x=0.2−0.3, and their thicknesses were 0.4-1.0 μm when annealed at 750-900 °C. Atomic and magnetic force microscopy studies showed no significant grain growth upon annealing and that the films consisted of single-domain grains forming interaction-cluster-type domains. The natural ferromagnetic resonance frequency was determined at around 4 GHz, together with substantial magnetic losses that make these films promising candidates for microwave absorbers.     

Dielectric behavior of spin-deposited nanocrystalline nickel-zinc ferrite thin films processed by citrate-route

Nanocrystalline nickel-zinc ferrite thin films with the general formula Ni_1−xZn_xFe₂O₄, where x=0.0, 0.2, 0.4 and 0.6 were fabricated via a chemical route known as the citrate precursor route. These films were spin-deposited on indium-tin oxide coated glass, fused quartz and amorphous Si-wafer substrates, and annealed at various temperatures up to 650 °C. The films annealed below 400 °C were found to be X-ray amorphous, while the films annealed at and above 400 °C were polycrystalline exhibiting a single-phase spinel structure. The average grain size of the films evaluated by transmission electron microscopy, is found to be in the range 4-8.5 nm. The room temperature DC resistivity of the films is in the range 10³-10⁷ Ω m. Dielectric constant and dielectric loss were measured in the frequency range 100 Hz-1 MHz. Dielectric constant of the films is found to lie between 25 and 44, while the loss factor is if the order of 10⁻². The higher values of the dielectric constant for films having higher zinc concentration are attributable to the enhanced hopping between Fe²⁺ and Fe³⁺ ions in these samples. The M-H hysteresis measurement of the nickel ferrite thin films annealed at 650 °C showed narrow hysteresis loop—a characteristic of soft ferromagnetic material.     

Vanadium-Al2O3 nanostructured thin films prepared by pulsed laser deposition: Optical switching

The formation and optical response of VO_x nanoparticles embedded in amorphous aluminium oxide (Al₂O₃) thin films by pulsed laser deposition is studied. The thin films have been grown by alternate laser ablation of V and Al₂O₃ targets, which has resulted in a multilayer structure with embedded nanoparticles. The V content has been varied by changing the number of pulses on the V target. It is found that VO_x nanoparticles with dimensions around 5 nm have been formed. The structural analysis shows that the vanadium nanoparticles are oxidized, although probably there is not a unique oxide phase for each sample. The films show a different optical response depending on their vanadium content. Optical switching as a function of temperature has been observed for the two films with the highest vanadium content, at transition temperatures of about −20 °C and 315 °C thus suggesting the presence of nanoparticles with compositions V₄O₇ and V₂O₅, respectively.     

Characteristics of high sensitivity ethanol gas sensors based on nanostructured spinel Zn1−xCoxAl2O4

Nanocrystalline powders of Zn_1−xCo_xAl₂O₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) mixed oxides, with cubic spinel structure were successfully prepared by the ethylene glycol mediated citrate sol-gel method. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). X-ray diffraction results showed that the samples were in single phase with the space group Fd-3m. TEM analysis showed that the powders with spherical shape were uniform in particle size of about 17-24 nm with mesoporous in nature. Further investigations were carried out by FT-IR. Thick films of as-prepared Zn_1−xCo_xAl₂O₄ powders were fabricated using screen-printing technique. The response of Zn_1−xCo_xAl₂O₄ based thick films towards different reducing gases (liquefied petroleum gas, hydrogen, hydrogen sulfide, ethanol gas and ammonia) was investigated. The sensor response largely depends on the composition, temperature and the test gas species. The Co (cobalt) content has a considerable influence on the gas-sensing properties of Zn_1−xCo_xAl₂O₄. Especially, Zn_0.4Co_0.6Al₂O₄ composition exhibited high response with better selectivity to 100 ppm C₂H₅OH gas at 150 °C. The instant response (∼7 s) and fast recovery (∼16 s) are the main features of this sensor.     

Effects of different sintering temperature and Nb2O5 content on structural and magnetic properties of Z-type hexaferrites

Nb-doped Z-type hexaferrites (Ba₃(Co_0.4Zn_0.6)₂Fe₂₄O₄₁) with composition of Ba₃(Co_0.4Zn_0.6)₂Fe₂₄O₄₁+x Nb₂O₅ (where x=0.0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.2, 1.6 and 2.0 wt%) were prepared by a solid-state reaction method. The effects of different sintering temperature (T_s) and Nb₂O₅ content on the sintering behaviors, phase composing, microstructure, and magnetic properties of the samples were investigated. The results from X-ray diffraction and scanning electron microscopy show that as the amount of Nb₂O₅ additive increases, the major phase changes to Z-phase, Simultaneously, M-phase and a small amount of niobate phase appear. The Nb₂O₅ additive promotes the grain growth as reaction center at lower sintering temperature (1220 °C), but at higher temperature (1260 °C), niobate phase separated out in grain boundaries as secondary phase will restrain abnormal grain growth, so closed pores in grains are not formed. The Nb₂O₅ additive can enhance densification, improve initial permeability of hexaferrites by increasing the grain growth of hexaferrite and the displacement of ions in the sintering process due to the aberration and activation of crystal lattice, which is accompanied by the solubility of Nb⁵⁺ in the hexaferrites. A relative density of 96%, maximum initial permeability (32–33), minimum coercivity (454–455 A/m) and resonance frequency above 400 MHz were obtained for the sample with 0.8 wt% Nb₂O₅ sintered at 1260 °C for 6 h.     

Tribological properties of the Ti-Al-N thin films with different components fabricated by double-targeted co-sputtering

Ti-Al-N films with different chemical compositions were deposited on stainless steel by changing the relative substrate position to targets using double-targeted reactive magnetron sputtering technique in the same process. The tribological behavior of the Ti-Al-N films was investigated in the temperature ranging from room temperature to elevated temperature in air without any lubricant on UMT-3 multifunctional friction and wear tribometer. The structure of the as-deposited films and the worn surface after tribometer testing were identified using XRD, EDS and SEM. It was found that the chemical composition of the as-deposited films altered with substrate position from Ti_0.82Al_0.18N to Ti_0.12Al_0.88N. XRD results revealed that the sputtered films before heat treatment were amorphous, but different phases such as TiN, AlN and TiAlN were formed after heat treatment of 700 °C × 1 h. Friction and wear tests indicated the films with x = 0.57, 0.65 exhibited the best tribological performance during the Ti_1−xAl_xN films system because of its hard phase and the formation of transfer films.     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Room-temperature ferromagnetism in Sn1−xMnxO2 nanocrystalline thin films prepared by ultrasonic spray pyrolysis

Sn_1−xMn_xO₂ (x=0.01-0.05) thin films were synthesized on quartz substrate using an inexpensive ultrasonic spray pyrolysis technique. The influence of doping concentration and substrate temperature on structural and magnetic properties of Sn_1−xMn_xO₂ thin films was systematically investigated. X-ray diffraction (XRD) studies of these films reflect that the Mn³⁺ ions have substituted Sn⁴⁺ ions without changing the tetragonal rutile structure of pure SnO₂. A linear increase in c-axis lattice constant has been observed with corresponding increase in Mn concentration. No impurity phase was detected in XRD patterns even after doping 5 at% of Mn. A systematic change in magnetic behavior from ferromagnetic to paramagnetic was observed with increase in substrate temperature from 500 to 700 °C for Sn_1−xMn_xO₂ (x=0.01) films. Magnetic studies reveal room-temperature ferromagnetism (RTFM) with 3.61×10⁻⁴ emu saturation magnetization and 92 Oe coercivity in case of Sn_1−xMn_xO₂ (x=0.01) films deposited at 500 °C. However, paramagnetic behavior was observed for the films deposited at a higher substrate temperature of 700 °C. The presence of room-temperature ferromagnetism in these films was observed to have an intrinsic origin and could be obtained by controlling the substrate temperature and Mn doping concentration.     

Effect of aluminium doping and annealing on structural and optical properties of cerium oxide nanocrystals

Nanocrystalline fluorite-like structures of Ce_1−xAl_xO_2−δ compounds were prepared by the chemical precipitation method using cerium chloride and aluminium chloride as precursors. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and diffuse reflectance spectroscopy (DRS). The effects of aluminium doping concentration and annealing on particle size, lattice parameter and band gap energies were investigated. The particle size of Al-doped CeO₂ samples were found to decrease with Al concentration and it increases from 6 to 20 nm as annealing temperature increases to 900 °C.     

Formation of silicon nanodots from dysprosium-doped amorphous SiCxOy films grown by hot-filament assisted chemical vapor deposition of CH3SiH3 and Dy(DPM)3 gas jets

We report on Si nanodot formation by chemical vapor deposition (CVD) of ultrathin films and following oxidation. The film growth was carried out by hot-filament assisted CVD of CH₃SiH₃ and Dy(DPM)₃ gas jets at the substrate temperature of 600 °C. The transmission electron microscopy observation and X-ray photoelectron spectroscopy analysis indicated that ∼35 nm Dy-doped amorphous silicon oxycarbide (SiC_xO_y) films were grown on Si(1 0 0). The Dy concentration was 10-20% throughout the film. By further oxidation at 860 °C, the smooth amorphous film was changed to a rough structure composed of crystalline Si nanodots surrounded by heavily Dy-doped SiO₂.     

Hydrothermal synthesis and magnetic properties of gadolinium-doped CoFe2O4 nanoparticles

CoFe_2−xGd_xO₄ (x=0-0.25) nanoparticles were synthesized via a simple hydrothermal process at 200 °C for 16 h without the assistance of surfactant. The as-synthesized powders were characterized by X-ray diffraction, transmission electron microscopy, and a vibrating sample magnetometer. The X-ray diffraction results showed that the as-synthesized powders were in the pure phase with a doping amount of ≤0.25, and the peaks could be readily indexed to the cubic spinel cobalt ferrite. Transmission electron microscopy and high resolution transmission electron microscopy observations revealed that the gadolinium-doped cobalt ferrite nanoparticles were single crystal, roughly spherical, uniformly distributed, and not highly agglomerated. The room temperature magnetic field versus magnetization measurements confirmed a strong influence of gadolinium doping on the saturation magnetization and coercivity due to large lattice distortion and grain growth of small particles.     

Growth of ZnO thin films on c-plane Al2O3 by molecular beam epitaxy using ozone as an oxygen source

The growth of c-axis oriented ZnO thin films on c-plane Al₂O₃ via molecular beam epitaxy (MBE) using dilute ozone (O₃) as an oxygen source was investigated. Four-circle X-ray diffraction (XRD) indicates that films grown at 350 °C are epitaxial with respect to the substrate, but with a broad in-plane and out-of-plane mosaic. The films were highly conductive and n-type. Epitaxial film growth required relatively high Zn flux and O₃/O₂ pressure. The growth rate decreased rapidly as growth temperature was increased above 350 °C. The drop in growth rate with temperature reflects the low sticking coefficient of Zn at moderately high temperatures and limited ozone flux for the oxidation of the Zn metal. Characterization of the films included atomic force microscopy (AFM), X-ray diffraction, photoluminescence, and Hall measurements. These results show that molecular beam epitaxy of ZnO using ozone is rate limited by the ozone flux for growth temperatures above 350 °C.     

Epitaxial growth of YSZ buffer layer for YBa2Cu3O7−δ coated conductor by reel-to-reel pulsed laser deposition

Yttria-stabilized zirconia (YSZ) buffer layers were deposited on CeO₂ buffered biaxially textured Ni-W substrate by reel-to-reel pulsed laser deposition (PLD) for the application of YBa₂Cu₃O_7−δ (YBCO) coated conductor and the influence of substrate temperature and laser energy on their crystallinity and microstructure were studied. YSZ thin films were prepared with substrate temperature ranging from 600 to 800 °C and laser energy ranging from 120 to 350 mJ. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to investigate how thin film structure and surface morphology depend on these parameters. It was found that the YSZ films grown at substrate temperature below 600 °C or laser energy above 300 mJ showed amorphous phase, the (0 0 1) preferred orientation and the crystallinity of the YSZ films were improved with increasing the temperature, but the surface roughness increased simultaneously, the SEM images of YSZ films on CeO₂/NiW tapes showed surface morphologies without micro-cracks. Based on these results, we developed the epitaxial PLD-YSZ buffer layer process at the tape transfer speed of 3-4 m/h by the reel-to-reel system for 100 m class long YBCO tapes.     

Effects of post-thermal annealing temperature on the optical and structural properties of gold particles on silicon suboxide films

In this work, silicon suboxide (SiO_x) thin films were deposited using a RF magnetron sputtering system. A thin layer of gold (Au) with a thickness of about 10 nm was sputtered onto the surface of the deposited SiO_x films prior to the thermal annealing process at 400 °C, 600 °C, 800 °C and 1000 °C. The optical and structural properties of the samples were studied using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and optical transmission and reflection spectroscopy. SEM analyses demonstrated that the samples annealed at different temperatures produced different Au particle sizes and shapes. SiO_x nanowires were found in the sample annealed at 1000 °C. Au particles induce the crystallinity of SiO_x thin films in the post-thermal annealing process at different temperatures. These annealed samples produced silicon nanocrystallites with sizes of less than 4 nm, and the Au nanocrystallite sizes were in the range of 7-23 nm. With increased annealing temperature, the bond angle of the Si-O bond increased and the optical energy gap of the thin films decreased. The appearance of broad surface plasmon resonance absorption peaks in the region of 590-740 nm was observed due to the inclusion of Au particles in the samples. The results show that the position and intensity of the surface plasmon resonance peaks can be greatly influenced by the size, shape and distribution of Au particles.     

Conductivity and sintering property of LaNi1 − xFexO3 ceramics prepared by Pechini method

Preparation of LaNi_1 − xFe_xO₃, which is one of the candidate materials of solid oxide fuel cell cathode, current collecting layer and interconnect coating was examined with Pechini method and solid state reaction method. Single phase LaNi_1 − xFe_xO₃ with large Ni content has successfully been prepared by low temperature sintering as 750 °C with Pechini method, whereas large amount of raw materials has remained with solid state reaction method by sintering at the same temperature. It can be ascribed to more homogenous cation distribution in raw powder material prior to sintering with Pechini method. It has also been revealed that LaNi_1 − xFe_xO₃ with x lower than 0.3 is thermodynamically unstable in air above 1000 °C. LaNi_0.6Fe_0.4O₃ showed superior property as cathode material with high electrical conductivity, thermodynamic stability and appropriate sintering property.     

Structure and photoluminescence properties of epitaxial SnO2 films grown on α-Al2O3 (0 1 2) by MOCVD

SnO₂ thin films have been successfully deposited on α-Al₂O₃ (0 1 2) substrates by metalorganic chemical vapor deposition (MOCVD) in the temperature range 500-700 °C. The films were epitaxially grown in the tetragonal SnO₂ phase and were (1 0 1) oriented. In-plane orientation relationship [0 1 0]SnO₂||[1 0 0]Al₂O₃ and [1 0 1?]SnO₂||[1? 2? 1]Al₂O₃ was determined between the film and substrate. Photoluminescence (PL) spectra measured at room temperature revealed that the film grown at 700 °C showed an intense ultra-violet (UV) PL peak at 333 nm, which was a band-edge emission peak in SnO₂ films. At a temperature of 13 K, a new broad PL band centered at about 480 nm was observed. The corresponding PL mechanisms are discussed in detail.     

Structural and optical properties of SrCu2O2 films deposited on sapphire substrates by pulsed laser deposition

We deposited SrCu₂O₂ (SCO) films on sapphire (Al₂O₃) (0 0 0 1) substrates by pulsed laser deposition. The crystallographic orientation of the SCO thin film showed clear dependence on the growth temperature. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis showed that the film deposited at 400 °C was mainly oriented in the SCO [2 0 0] direction, whereas when the growth temperature was increased to 600 °C, the SCO film showed a dominant orientation of SCO [1 1 2]. The SCO film deposited at 500 °C was obvious polycrystalline, showing multi peaks from (2 0 0), (1 1 2), and (2 1 1) diffraction in the XRD spectrum. The SCO film deposited at 600 °C showed a band gap energy of 3.3 eV and transparency up to 80% around 500 nm. The photoluminescence (PL) spectra of the SCO films grown at 500 °C and 600 °C mainly showed blue-green emission, which was attributed to the intra-band transition of the isolated Cu⁺ and Cu⁺–Cu⁺ pairs according to the temperature dependent-PL analysis.     

Effect of Al content on the properties of Cr1−xAlxC films prepared by RF reactive magnetron sputtering

Cr_1−xAl_xC films were deposited on high-speed steel by RF reactive magnetron sputtering. In this study, we aimed to identify the effect of the Al content on the properties of Cr_1−xAl_xC films. We found that Cr_1−xAl_xC films exhibited a fine columnar grain microstructure with some special characteristics, such as high hardness of Hv 1426, a low friction coefficient of 0.29, and a large contact angle of 90° for x = 0.18. Furthermore, an increase in Al content resulted in a decrease in film hardness and an increase in contact angle. Moreover, on annealing at 923 K, the mechanical properties of the films improved and a dense protective film of complex Cr₂O₃ and Al₂O₃ oxides was formed on the surface for better wear resistance, which will ultimately increase the lifetime of the high-speed steel substrate.     

Difference in high-temperature oxidation resistance of amorphous Zr-Si-N and W-Si-N films with a high Si content

The high-temperature oxidation resistance of amorphous Zr-Si-N and W-Si-N films with a high Si content (≥20 at.%) deposited by reactive dc magnetron sputtering at different partial pressures of nitrogen was systematically investigated by means of a symmetrical high-resolution thermogravimetry in a flowing air up to an annealing temperature of 1300 °C (a temperature limit for Si(1 0 0) substrate). Additional analyses including X-ray diffraction (XRD), light optical microscopy (LOM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and microhardness measurement were carried out as well. The obtained results showed (i) an excellent high-temperature oxidation resistance of the Zr-Si-N films up to 1300 °C, (ii) a considerably lower oxidation resistance of the W-Si-N films. The W-Si-N films are completely oxidized at 800 °C with a subsequent volatilization of unstable WO_x oxides. On the other hand, the Zr-Si-N films are oxidized only very slightly on the surface, where a stable oxide barrier layer preventing further inward oxygen diffusion is formed. The thickness of the oxide layer is only about of 3% of the total film thickness. The phase composition, thermal stability of individual phases and amorphous structure were found to be key factors to achieve a high oxidation resistance.