Correlation study between structural, magnetic and transport properties of annealed Co thin films

This paper presents structural, magnetization and transport properties measurements carried out on as-deposited Co (400 Å) thin film as well as samples annealed in the temperature range 100-500 °C in steps of 100 °C for 1 h. The samples used in this work were deposited on float glass substrates using ion beam sputtering technique. The magnetization measurements carried out using MOKE technique, clearly indicates that as-deposited as well as annealed samples up to 500 °C show well saturation magnetization with applied magnetic field. The as-deposited sample shows coercivity value (H_c) of 26 Oe, and it is increased to 94 Oe for 500 °C-annealed sample. A minimum coercivity value of 15 Oe is obtained for 200 °C annealed sample. The XRD measurements of as deposited films show microcrystalline nature of Co film, which becomes crystalline with increase in annealing temperature. The corresponding resistivity measurements show gradual decrease in resistivity. AFM technique was employed to study the surface morphology of as deposited film as well as annealed thin films. Observed magnetization, and resistivity behaviour is mainly attributed to the (i) change in crystal structure (ii) increase in grain size and (iii) stress relaxation due to the annealing treatment.     

Growth of ultra-fine cobalt ferrite particles by a sol–gel method and their magnetic properties

Ultra-fine CoFe₂O₄ particles are fabricated by a sol–gel method and magnetic and structural properties of powders are investigated. Cobalt ferrite powders fired at and above 450 °C have only a single-phase spinel structure and behave ferrimagnetically. Powders annealed at 350 °C have a typical spinel structure and are of the paramagnetic and ferrimagnetic nature, simultaneously. With X-ray diffraction and Mossbauer spectroscopy measurements, the formation of nano-crystallized particles is confirmed when cobalt ferrite is annealed at 200 °C. In addition, the transition from the paramagnetic to the ferrimagnetic state is observed in samples fired at 200 °C as the measuring temperature decreases from the room to liquid nitrogen temperature. The magnetic behaviour of CoFe₂O₄ powders fired at and above 350 °C shows that an increase of the annealing temperature yields a decrease in the coercivity and, in contrast, an increase in the saturation magnetization. The maximum coercivity and the saturation magnetization of cobalt ferrite powders prepared by the sol–gel method are 2020 Oe and 76.5 e.m.u. g^–1, respectively.     

Effect of growth temperature on the structural and transport properties of magnetite thin films prepared by pulse laser deposition on single crystal Si substrate

Magnetite (Fe₃O₄) thin films are prepared by pulsed laser deposition using an α-Fe₂O₃ target on silicon (111) substrate in the substrate temperature range of 350 °C to 550 °C. X-ray diffraction (XRD) measurement shows that the film deposited at 450 °C is a single phase Fe₃O₄ film oriented along [111] direction. However, the film grown at 350 °C reveals mixed oxide phases (FeO and Fe₃O₄), while the film deposited at 550 °C is a polycrystalline Fe₃O₄. X-ray photoelectron spectroscopy study confirms the XRD findings. Raman measurements reveal identical spectra for all the films deposited at different substrate temperatures. We observe abrupt increase in the resistivity behavior of all the films around Verwey transition temperature (T_V) (125 K-120 K) though the transition is broader in the film deposited at 350 °C. We observe that the optimized temperature for the growth of Fe₃O₄ film on Si is 450 °C. The electrical transport behavior follows Shklovskii and Efros variable range hopping type conduction mechanism below T_V for the film deposited at 450 °C possibly due to the granular growth of the film.     

Formation of ternary carbide Fe3Mo3C by mechanical activation and subsequent heat treatment

Ternary carbide, Fe₃Mo₃C was prepared from the powder mixture of Fe/Mo/C = 1/1/1 which was ground for 3 h in a planetary ball mill and subsequently heated at a temperature as low as 700°C, its amount increased with heating temperature. In contrast, when the 1 h-ground and unground samples were heated at 700–1000°C, Mo₂C formed. From the results obtained about the effect of mixing ratio, grinding time and heating temperature of Fe/Mo/C samples on the formation of Fe₃Mo₃C, it was found that the formation of Fe₃Mo₃C strongly depends on the mixing homogeneity and the activated state of the particles of Fe, Mo and C components induced by mechanical grinding. Fe₃Mo₃C obtained belongs to a hard magnet, having saturation magnetization of 0.4 emu g^–1, remanence of 0.13 emu g^–1 and coercivity of 200 Oe.     

Structural investigation of thin TiO2 films prepared by evaporation and post‐heating

Thin films of TiO₂ have been prepared by reactive evaporation of Ti₂O₃ at substrate temperatures from 150 °C to 350 °C and by post‐heating at 150 °C to 850 °C. The mass density of the films increases with increasing substrate and annealing temperature. The crystalline structure of the film prepared at 350 °C is anatase and becomes rutile upon annealing at 850 °C. All other films are amorphous as‐prepared and become anatase upon annealing above 250 °C. The crystallinity is higher for films prepared at lower temperature and does not increase with annealing temperature. Coatings with reproducible optical properties are obtained when deposited and post‐annealed at 250 °C.     

Preparation of cobalt oxide films by plasma-enhanced metalorganic chemical vapour deposition

Co oxide films were prepared on glass substrates at 150–400°C by plasma-enhanced metalorganic chemical vapour deposition using cobalt (II) acetylacetonate as a source material. NaCl-type CoO films were formed at low O₂ flow rate of 7cm³ min^–1 and at a substrate temperature of 150–400°C. The CoO films possessed (100) orientation, independent of substrate temperature. Deposition rates of the CoO films were 40–47 nm min^–1. The CoO film deposited at 400 °C was composed of closely packed columnar grains and average diameter size at film surface was 60 nm. At high O₂ flow rate of 20–50 cm³ min^–1, high crystalline spinel-type Co₃O₄ films were formed at a substrate temperature of 150–400°C. The Co₃O₄ film deposited at 400°C possessed (100) preferred orientation and the film deposited at 150°C possessed (111) preferred orientation. Deposition rates of the Co₃O₄ films were 20–41 nm min^–1. Both Co₃O₄ films with (100) and (111) orientation had columnar structure. The shape and average size of the columnar grains at the film surface were different; a square shape and 35 nm for (100)-oriented Co₃O₄ film and a hexagonal shape and 60 nm for (111)-oriented film, respectively.     

Synthesis and magnetic properties of Fe5C2 by reaction of iron oxide and carbon monoxide

The formation behaviour and magnetic properties of Fe₅C₂ were investigated. Iron oxides, as starting material, were carburetted with carbon monoxide gas by heat treatment. Fe₅C₂ was formed as a single phase in the reaction temperature range 350 to 375° C. The amount of carbon monoxide gas was controlled by mixing with nitrogen gas to prevent free carbon deposition by the disproportionation of carbon monoxide. Synthesized Fe₅C₂ particles were identified as a single phase by XRD and the weight change measurement of reactants. The saturation magnetization of Fe₅C₂ was about 100e.m.u.g^–1, regardless of the reaction temperature. The coercive force decreased from 800 to 400 Oe with increasing reaction temperature.     

Effect of deposit conditions on magnetic parameters of electroless CoFeB films

Electroless CoFeB films with soft magnetic characteristics were fabricated on poly-ester plastic substrate using sodium tetrahydroborate (NaBH₄) as reducer. The change of film composition corresponding to magnetic characteristics was dependent on deposition conditions. As the concentration of NaBH₄ and bath pH increase, the surface roughness of films reduces approximately from 160 to 137 nm. The soft magnetic film exhibited large saturation magnetization of 145 emμ/cc and low coercivity of about 7.6 Oe. Low boron content in film was found resulting in higher coercivity. At 2 GHz, the real permeability and imaginary permeability of films are respectively 275 and 141 as the concentration of reducer is 0.066 mol/L. Hysteresis loops of films show a remanence close to the saturation magnetization and along the hard axis display anisotropic field of 75 Oe.     

Synthesis of single nanocrystal phase γ′-Fe4N on NaCl substrate by DC magnetron sputtering

The single-phase γ′-Fe₄N nanocrystal magnetic films with grain size of d = 40–60 nm were synthesized on single crystal NaCl (1 0 0) substrate by DC magnetron sputtering at 150 °C. The structure, morphology of the single-phase γ′-Fe₄N films were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), and the magnetic properties of samples prepared at different substrate temperatures were investigated by superconducting quantum interference device (SQUID). It is shown that substrate temperature has a significant influence on the crystalline structure and magnetic properties for Fe–N films. As substrate temperature was increased, the saturation magnetization for the deposited films increased, but the coercivity reduced.     

Microhardness properties of Cu–W amorphous thin films

Pure copper, pure tungsten and amorphous Cu₅₀W₅₀ and Cu₆₆W₃₄ alloy films were deposited by the direct current magnetron sputtering technique on cooled glass substrates. The film microhardness has been investigated as a function of alloy composition and substrate potential bias during deposition. The microhardness exhibited a maximum at Cu concentrations close to 50 at%, similar to the case of completely miscible binary alloys. The ion bombardment caused by the negative substrate polarization increased the film microhardness. The annealing of the amorphous Cu–W films up to 250 °C in vacuum increased the film microhardness by 10–20% apparently owing to the formation of the W(Cu) crystalline phase dispersed within a predominantly amorphous film matrix.     

Optical and structural properties of (Ba, Sr)TiO3 thin films grown by radio-frequency magnetron sputtering

We studied the structural and optical properties of (Ba, Sr)TiO₃ (BST) films deposited on the transparent substrates at various temperatures of 350–650°C and annealed at 450–650°C. Improved crystallization can be observed on 650°C annealed film whose substrate temperature is 350°C. The refractive index increased from 2.17 to 2.59 at =410 nm for the BST films deposited at 350–650°C and it varied from 2.17 to 2.25 after annealing up to 650°C. In addition, the refractive-index dispersion data related to the short-range-order structure of BST films obeyed the single-oscillation energy model. The indirect energy gap of the films deposited on Al₂O₃ and quartz substrates was found to be about 3.5 eV. According to the analysis of reflectance data, the optical inhomogeneity of films can be reduced by depositing the films at intermediate temperatures 450–550°C.     

Titanium oxy-nitride films deposited on stainless steel by an ion beam assisted deposition technique

Surfaces of stainless steel SUS304 were coated with titanium oxy-nitride (TiON) films at temperatures of 400–770°C using an ion-beam assisted deposition technique constructed from an electron beam evaporator for Ti evaporation and a microwave ion source for ionizing nitrogen gas. The N ions were accelerated at energies of 0.5–2.0 keV. Most of the deposited TiON films consisted of (60–80)% TiN and (40–20)% TiO₂, and the fraction of TiO₂ increased with increasing substrate temperature. Hardness of the TiNO films varied in the range from 160 GPa to 260 GPa with increasing substrate temperature. The titanium oxy-nitride film could be deposited on stainless steel without a significant deterioration surface layer at 600°C. However, when TiNO films were deposited at temperatures higher than 700°C, the thickness of the TiNO films were significantly thinner and a thick layer containing nitride such as Cr₂N, CrFe, Fe₂N and Fe₄N was formed in a near surface region of stainless steel because more nitrogen diffused into stainless steel.     

Synthesis of carbon nanotube films by thermal CVD in the presence of supported catalyst particles. Part I: The silicon substrate/nanotube film interface

The interface between the silicon substrate and a carbon nanotube film grown by thermal CVD with acetylene (C₂H₂) and hydrogen at 750 or 900 °C has been characterized by high resolution and analytical transmission electron microscopy, including electron spectroscopic imaging. Silicon (0 0 2) substrates coated with a thin (2.8 nm) iron film were heat treated in the CVD furnace at the deposition temperature in a mixture of flowing argon and hydrogen whereby nanosized particles of (Fe,Si)₃O₄ formed. These particles were reduced to catalytic iron silicides with the –(Fe, Si), ₂–Fe₂Si and ₁–Fe₂Si structures during CVD at 900 °C, and multi-wall carbon nanotubes grew from supported particles via a base-growth mechanism. A limited number of intermediate iron carbides, hexagonal and orthorhombic Fe₇C₃, were also present on the substrate surface after CVD at 900 °C. The reduction of the preformed (Fe, Si)₃O₄ particles during thermal CVD at 750 °C was accompanied by disintegration leading to the formation of a number of smaller (<5 and up to 10 nm) iron and silicon containing particles. It is believed that the formation of these small particles is a prerequisite for the growth of aligned multi-wall carbon nanotube films.     

Taguchi design for fabrication of high-performance as-deposited Fe-Sm-O thin films

The Taguchi experimental design was used in this study to obtain optimal conditions for which as-deposited Fe-Sm-O thin films with both good soft magnetic properties and high electrical resistivity could be fabricated by r.f. magnetron sputtering method. The factors considered were the number of Sm₂O₃ chips, sputtering power and time, base vacuum, Ar work pressure, and O₂ partial pressure. The results showed that the optimal conditions were as follows: four Sm₂O₃ chips sputtering power of 350 W, sputtering time of 10 min, base vacuum of 2.6×10^-4Pa, work pressure of 0.2 Pa and O₂ content in Ar of 5%. The thin film fabricated at those conditions had the composition of Fe_75.3Sm_4.3O_20.4. The properties of as-deposited Fe_75.3Sm_4.3O_20.4 thin film were: saturation magnetization of 16.3 kG, coercivity of 0.9 Oe, effective permeability of 2200 in the range of 0.5–100 MHz, and electrical resistivity of 190 cm. The percentage contribution of each factor to electrical resistivity, soft magnetic properties such as magnetic permeability, coercivity and saturation magnetization were also calculated.     

Preparation of nickel and Ni-Zn ferrite films by thermal decomposition of metal acetylacetonates

Nickel and Ni-Zn ferrite (Ni_1–x Zn _x Fe₂O₄) films were prepared on various substrates (quartz glass, MgO single crystal, etc.) by thermal decomposition of metal acetylacetonates (Ni (acac)₂ · 2H₂O, Zn (acac)₂ · 2H₂O and Fe (acac)₃). Typical decomposition and heat treatment conditions for obtaining a single phase of NiFe₂O₄ film were as follows: evaporation temperature of Ni-Fe complexes: 230°C, the mole concentration of Fe (acac)₃,R (%) = Fe (acac)₃/(Fe (acac)₃ + Ni (acac)₂ · 2H₂O) = 33, substrate temperature: 330 to 550° C, and heat treatment of the as-grown film: 800 to 1000° C, 1 h. Ni_1–x Zn _x Fe₂O₄ films were obtained by controlling the compositionR in Ni-Fe complexes and the evaporation temperature of Zn (acac)₂ · 2H₂O. The Ni-Zn ferrite film at the compositionx = 0.37 (Ni_0.63Zn_0.37Fe₂O₄) gave the maximum saturation magnetization _s = 60 emu g^–1 and the coercive forceHc 25 Oe. These films showed a magnetic anisotropy which makes the magnetization easy parallel to film surface.     

Magnetic properties and microstructures of single-layered Fe100 − xPtx films deposited onto heated substrates

The single-layered Fe_100 − xPt_x films of 30 nm thick with Pt contents (x) of 35-57 at.% are deposited on heated Si (100) substrate at a temperature (Ts) of 620 °C by magnetron co-sputtering. When the Pt content in the Fe-Pt alloy film is 35 at.%, the value of in-plane coercivity (Hc_//) is close to perpendicular coercivity (Hc_⊥) and both values are about 800 kA/m. The FePt films exhibit perpendicular magnetic anisotropy when the Pt content increases to the values of between 45 and 51 at.%. The perpendicular coercivity, saturation magnetization (Ms) and perpendicular squareness (S_⊥) for Fe₅₄Pt₄₆ film are as high as 1113 kA/m, 0.594 Wb/m² and 0.96, respectively. These magnetic properties reveal its significant potential as perpendicular magnetic recording media. Upon further increasing the Pt content to 57 at.%, the coercivity of the Fe-Pt film decreases drastically to below 230 kA/m and tends to be closer to in-plane magnetic anisotropy.     

Preparation of spinel-type ferrite thin films by the dip-coating process and their magnetic properties

Films of spinel-type ferrite, MFe₂O₄ (M=Ni, Co, Mg, Li_0.5Fe_0.5) have been prepared by a dip-coating method from the sol-gel process. Ferric nitrate, nickel nitrate, cobalt nitrate and lithium nitrate were used as raw materials, and glycerol and formamide were used as solvents. A film was prepared by dipping a silica glass plate. The spinel-type ferrite was obtained by heat-treatment at 700–900°C for 2 h in air. The film thickness was about 0.8 m. The saturation magnetization, _r, of the film and powder with composition 50NiO·50Fe₂O₃ was 196 emu cm^–3 and 29.1 emu g^–1, respectively, and the coercive force,H _c, was 140 and 95 Oe, respectively, after heat-treatment at 800°C for 2 h. In particular, the films were shown to have a much largerH _c than the powder. The grain growth of spinel ferrite may be subject to restriction because it is in progress above an amorphous base-plate. The crystals are therefore aligned with the base-plate and have uniaxial anisotropy.     

Characterization of (Pb,La) TiO3 thin films prepared by the sol-gel method

Pb_(1–1.5x)La_xTiO₃ thin films were synthesized by the sol-gel spin-coating technique. The films became crystallized when the spin-coated films were annealed at 600 °C and at higher temperature, and became amorphous when annealed at 550 °C. The breakdown voltage, V _B, was recorded at around 30 V for 600–650 °C annealed films and varied only slightly with the composition. The V _B value of the amorphous films was observed to be higher than that of the crystalline films. The ferroelectric properties of both the amorphous and crystalline films were found to be similar. The dielectric constant, charge storage density and optical index of refraction of the films were _r =5–20, Q _c=0.12–0.54 C cm^–2 and n=1.6–2.3, respectively. They all increased moderately with La³⁺ content in the films. One possible reason why the ferroelectric properties are not modified as the amorphous films crystallize, may be that the octahedra are equilateral, whether the films are amorphous or crystalline. Additionally, a possible cause which lowers the breakdown voltage in crystalline film, is the formation of lead vacancies due to lead loss. The electrical properties of films coated on bare silicon become significantly lowered due to interdiffusion between films and substrate. The diffusion of Si⁴⁺ ions into-the films can be prevented by coating SrTiO₃ on the silicon substrate as a buffer layer. The charge storage capacity consequently becomes substantially enhanced.     

Structural and compositional studies of magnetron-sputtered Nd–Fe–B thin films on Si(100)

The structure and composition of the Nd–Fe–B thin films deposited on Si(100) have been investigated. Films have been prepared by direct-current magnetron sputtering in pure argon and xenon sputter media separately. Deposition has been carried out keeping the substrates at room temperature and 360°C. These films were subjected to the post-deposition annealing to a temperature of 60O°C in a vacuum of 5×10–7 Torr. The stoichiometry and structure of these films were analysed and correlated to the deposition and annealing conditions. Films deposited in xenon sputter medium showed better crystalline properties than those sputtered in pure argon. This difference was attributed to the presence of reflected high-energy neutral gas particles in the argon medium. Films deposited in xenon were found to be relatively rich in boron compared with argon-sputtered films. Post-deposition annealing resulted in the interdiffusion at the interface between the film and substrate. The use of a SiO2 film as a barrier layer between the silicon substrate and the Nd–Fe–B film has been explored. Thermally grown SiO2 was found to be an effective diffusion barrier. © 1998 Chapman & Hall     

Tungsten-oxide thin films as novel materials with high sensitivity and selectivity to NO2, O3, and H2S. Part II: Application as gas sensors

The electrical response of tungsten-oxide thin films as-deposited by electron-beam deposition and annealed (at 350–800 °C for 1–3 h in O₂) to NO₂, O₃ and H₂S was studied both experimentally and theoretically. In order to interpret the kinetic characteristics of tungsten-oxide thin films on exposure to different gases, a model based on surface adsorption/desorption processes coupled with bulk diffusion was used. A link between the geometrical and chemical heterogeneities of the tungsten-oxide film surfaces and their performance characteristics as gas sensors was established. It was shown that the nature and amount of surface-adsorption sites in the different nonstoichiometric phases (W _n O_3n–2 or W _n O_3n–1) and WO₃ as well as their conduction mechanisms are defined from the phase composition of the film, the crystallographic and electronic structures of the phases, the orientation of the crystallites within the film and the geometrical shape and dimensions of the crystallites. All tungsten-oxide thin films investigated in this work are suitable for detection of very low concentrations of NO₂ (0.05–0.5 ppm in N₂ and synthetic air), ozone (25–90 ppb) and H₂S (3–15 ppm in N₂ and synthetic air) at very low working temperatures (80–160 °C). The films annealed at 400 °C for 1–2 h are very selective to ozone at 120–160 °C; the films annealed at 400 °C for 1–3 h and at 800 °C for 1 h are very sensitive to NO₂ (in N₂).