Structure and magnetic properties of co-sputtered Co–C thin films

We studied the structure and magnetic properties of co-sputtered Co_1−xC_x thin films using a transmission electron microscope (TEM) and a SQUID magnetometer. These properties were found to depend critically on deposition temperature, T_S, and composition, x. Generally, phase separation into metallic Co and graphite-like carbon phases proceeds with increasing T_S and decreasing x. Plan view and cross-sectional TEM images of the films prepared showed that Co grains about 10–20 nm in diameter and 30–50 nm in height are three-dimensionally separated by graphite-like carbon layers 1–2 nm thick. Optimum magnetic properties with saturation magnetization of 380 emu/cc and coercivity of 400 Oe were obtained for a film with x=0.5 and T_S=350°C.     

Out-of-equilibrium Sm–Fe based phases

Structure and magnetic properties of nanocrystalline P6/mmm out-of-equilibrium precursors of hard magnetic R-3m Sm₂(Fe,M)₁₇C (M=Ga,Si,) and I4/mmm Sm(Fe,Co,Ti)₁₁ equilibrium phases, are presented. Their structure is explained with a model ground on the R_1???s T_5?+?2s formula (R=rare-earth, s=vacancy rate, T=transition metal) where s Sm atoms are statistically substituted by s transition metal pairs. The Rietveld analysis (RA) provides the stoichiometry of the precursors, 1:9 and 1:10, respectively precursor of 2:17 and 1:12 phases. The interpretation of the Mössbauer spectra of the 1:9 and 1:10 phases, is based on the correlation between δ and the Wigner–Seitz Cell volumes, calculated from the structural parameters. The δ behaviour of each crystallographic site versus Co content, defines the Co location while it confirms that of Si and Ga obtained by RA. Substitution occurs in 3 g site, whatever Co or M. The Sm(Fe,Co,Ti)₁₀ and Sm(Fe,M)₉C Curie temperature (T_c) are compared to those of the equilibrium phases, the effects of Fe substitution and C addition are discussed. The maximum μ ₀H_c is obtained for low M or Co content, for auto-coherent diffraction domain size ～30 nm. SmFe_8.75Ga_0.25C and SmFe_8.75Si_0.25C with T_c of 680 and 690 K, show respectively M_r and μ ₀H_c of 58 emu/g, 27 kOe and 95 emu/g, 15 kOe, values higher than those obtained for Sm₂(Fe,M)₁₇ carbides.     

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.     

Thermal conductivity of the amorphous and nanocrystalline phases of the beech wood biocarbon nanocomposite

Natural composites (biocarbons) obtained by carbonization of beech wood at different carbonization temperatures T _carb in the range of 800–2400°C have been studied using X-ray diffraction. The composites consist of an amorphous matrix and nanocrystallites of graphite and graphene. The volume fractions of the amorphous and nanocrystalline phases as functions of T _carb have been determined. Temperature dependences of the phonon thermal conductivity κ(T) of the biocarbons with different temperatures T _carb (1000 and 2400°C) have been analyzed in the range of 5–300 K. It has been shown that the behavior of κ(T) of the biocarbon with T _carb = 1000°C is controlled by the amorphous phase in the range of 5–50 K and by the nanocrystalline phase in the range of 100–300 K. The character of κ(T) of the biocarbon with T _carb = 2400°C is determined by the heat transfer (scattering) in the nanocrystalline phase over the entire temperature range of 5–300 K.     

Structure and electrical properties of Sb2Te3 and Bi0.4Sb1.6Te3 metastable phases obtained by HPHT treatment

We have obtained the metastable phase of the thermoelectric alloy Bi_0.4Sb_1.6Te₃ with electron type conductivity for the first time using the method of quenching under pressure after treatment at P=4.0 GPa and T=400–850 °C. We have consequently performed comparative studies with the similar phase of Sb₂Te₃. The polycrystalline X-ray diffraction patterns of these phases are similar to the known monoclinic structure α-As₂Te₃ (C2/m) with less monoclinic distortion, β ≈ 92°. We have measured the electrical resistivity and the Hall coefficient in the temperature range of T=77?450 K and we have evaluated the Hall mobility and density of charge carriers. The negative Hall coefficient indicates the dominant electron type of carriers at temperatures up to 380 K in the metastable phase of Sb₂Te₃ and up to 440 K in the metastable state of Bi_0.4Sb_1.6Te₃. Above these temperatures, the p-type conductivity proper to the initial phases dominates.     

Low temperature plasma production of hydrogenated nanocrystalline silicon thin films

The hydrogenated nanocrystalline silicon (nc-Si:H) thin films were produced by capacitively-coupled plasma enhanced chemical vapor deposition (PECVD) technique at low substrate temperatures (T_s ≈ 40–200 °C). Firstly, for particular growth parameters, the lowest stable T_s was determined to avoid temperature fluctuations during the film deposition. The influence of the T_s on the structural and optical properties of the films was investigated by the Fourier transform infrared (FTIR), UV–visible transmittance/reflectance and X-ray diffraction (XRD) spectroscopies. Also, the films deposited at the center of the PECVD electrode and those around the edge of the PECVD electrode were compared within each deposition cycle. The XRD and UV–visible reflectance analyses reveal the nanocrystalline phase for the films grown at the edge at all T_s and for the center films only at 200 °C. The crystallinity fraction and lateral dark conductivity decrease with lowered T_s. FTIR analyses were used to track the hydrogen content, void fraction and amorphous matrix volume fraction within the films. The optical constants obtained from the UV–visible transmittance spectroscopy were correlated well with the FTIR results. Finally, the optimal T_s was concluded for the application of the produced nc-Si:H in silicon-based thin film devices on plastic substrates.     

Solid-phase synthesis of Co7Sm2(110) epitaxial nanofilms: Structural and magnetic properties

The solid-phase synthesis of the Co₇Sm₂ and Co₁₇Sm₂ magnetically hard phases in Co/Sm/Co(110) epitaxial film systems has been experimentally investigated. The Co₇Sm₂ phase is first formed at the Sm/Co interface at a relatively low (～300°C) temperature. As the annealing temperature increases to ～450°C, the Co₁₇Sm₂(110) phase grows epitaxially on the Co₇Sm₂(110) phase. The saturation magnetization and biaxial anisotropy constant in the samples vary with the formation of the Co₇Sm₂ and Co₁₇Sm₂ phases. Investigations of the solid-phase synthesis in the nanofilms reveal the existence of a new structure phase transition at 300°C in the Co-Sm system with a high cobalt content.     

Metastable (GaSb)(1−x)(Sn2)x alloys: Crystal growth and phase stability of single crystal and polycrystalline layers

Single-phase metastable (GaSb)_(1−x)(Sn₂)_x alloys with x ⩽ 0.23 far exceeding the equilibrium solid solubility limit of x ⪅ 0.02 for Sn in GaSb, have been grown by rf sputter deposition. The key feature allowing the growth of single phase alloys was the use of low energy ion-bombardment-induced collisional mixing during deposition. Films grown at elevated temperatures T_s on GaAs(100) substrates were found to be single crystals while polycrystalline films with very strong (220) perferred orientation and grain sizes of 20–40 nm were obtained on amorphous glass substrates. The maximum film growth temperatures T_m at which single phase films could be obtained was a function of the negative substrate potential V_s during deposition and the composition x. For V_s = 75 V, T_m ranged from 375 °C at x = 0.06 to 125 °C at x = 0.23. Crystal growth and post-annealing studies both indicated that the transformation from the single-phase metastable state to the equilibrium (GaSb + βSn) state occurs through a continuous set of metastable GaSb-rich phases and that Sn precipitates out first in the α-diamond structure and then transforms to the β-tetragonal structure. In single crystal films, the GaSb-rich phase precipitates out coherently with the alloy matrix. The activation energy for phase separation ranged from ∼ 1.4 eV for alloys with x = 0.06 to 0.9 eV at x = 0.23. A phase map for crystal growth, plotted as a function of T_s and x, and an annealing transformation diagram for (GaSb)_0.86(Sn₂)_0.14 was determined.     

Study of thin Ge films with amorphous and nanocrystalline phases via the techniques of EXAFS spectroscopy and AFM

The local atomic structure and surface morphology of thin semiconductor films of Ge have been studied via extended X-ray absorption fine structure spectroscopy and atomic force microscopy. The films have been obtained by thermal evaporation of a material in an ultrahigh vacuum at different substrate temperatures. The films contain both amorphous and nanocrystalline phases. The percentage of the phases depends on the condensation temperature. The classical linear dependence of grain sizes on condensation temperature T is violated at T=100°C.     

A correlation between structural and optical properties of cobalt oxide nanoparticles for various annealing conditions

Two stable phases of cobalt oxide nanoparticles of controlled sizes have been synthesized using environmentally friendly inorganic precursor. Structural characterization using X-ray diffraction (XRD) shows a single-phase spinal Co₃O₄ structure up to annealing temperature of 800 °C and a mixed phase of Co₃O₄ and CoO particles for T>900 °C. Single-phase CoO nanoparticles are also obtained by annealing the particles at a temperature >900 °C and cooling in inert atmosphere. Average macro- and micro-strain were estimated using XRD data. Macrostrain was found to be the minimum for particles annealed at 600 °C, whereas microstrain was found to decrease with increasing annealing temperature up to 900 °C. A correlation between the density of localized states (DOS) in the band gap and strain is expected because the origin of both strain and DOS are defects and bond length distortions. Sub-gap absorption measurement and model calculations have been used for the determination of DOS. For cobalt oxide nanoparticle samples we find a correlation between estimated strain and density of states in the band gap.     

New phases and chemical short range order in co-deposited CoFe thin films with bcc structure: an NMR study

A ⁵⁹Co NMR study has been carried out on several series of co-evaporated Co₁-_xFe_x thin-film alloys prepared on MgO (001), GaAs (100), and GaAs (110) substrates at deposition temperatures between 175°C and 500°C. The sample thicknesses varied between 100 Å and 1000 Å and the alloy concentrations were in the range 0:1 < x < 0:3. X-ray diffraction and NMR show that the stability limits of the bcc phase in CoFe alloys is shifted from the x = 0:25 observed in the bulk alloys down to about x = 0:11 in thin films. For x = 0:27 and at the deposition temperature of 500°C, a new ordered phase has been stabilised where Co has two Fe atoms only in its first coordination shell. Other samples, grown at lower temperatures, also exhibit an exotic chemical short range order (CSRO) where Co coordinations with zero and two Fe neighbours dominate. A mixture of bcc Co (and not fcc Co as in the bulk alloys) and unknown ordered bcc intermetallics can account for the observed CSRO. Theoretical ground-state phases for the bcc lattice are considered in order to explain the observations.     

Room temperature ferromagnetism in Zn1−xCoxS thin films with wurtzite structure

The magnetic properties of Zn_1−xCo_xS (x=0.025 and 0.05) thin films grown on α-quartz substrates at different temperatures (T_S) of 200, 400 and 600 °C by means of pulsed laser deposition are presented. The films are crystallized with wurtzite structure. Optical absorption and transmission electron microscopy measurements indicate that Co ions are substituted to Zn on tetrahedral sites. Their magnetic response is composed of ferromagnetic and paramagnetic components of which respective strengths depend on T_S and Co concentration. This behavior is interpreted as due to fluctuations in the magnetic ordering, depending on grain size and site location in grain boundaries or in crystal cores.     

Silicide formation in bilayer ultrathin iron and cobalt films on silicon

The processes that occur in ultrathin (up to 1 nm) Fe and Co layers during deposition onto the Si(100)2 × 1 surface in various sequences and during annealing of the formed structures to a temperature of 400°C are studied. The elemental and chemical compositions of the films are analyzed by in situ high-resolution X-ray photoelectron spectroscopy using synchrotron radiation, and their magnetic properties are determined using the magnetic linear dichroism effect in the angular distribution of Fe 3p and Co 3p electrons. It is shown that, when iron is first deposited, the formed structure consists of the layers of FeSi, Fe₃Si, Co-Si solid solution, and metallic cobalt with segregated silicon. The structure formed in the alternative case consists of the layers of CoSi, Co-Si solid solution, Co, Fe-Si solid solution, and Fe partly covered by silicon. All layers (apart from FeSi, CoSi) form general magnetic systems characterized by ferromagnetic ordering. Annealing of the structures at temperatures above 130dgC (for the Co/Fe/Si system) and ～200°C (for Fe/Co/Si) leads to the formation of nonmagnetic binary and ternary silicides (Fe _x Co_{1 ? x} Si, Fe _x Co_{2 ? x} Si).     

Formation of boride phases from individual powder components during the mechanical synthesis of Ni<Subscript>80</Subscript>Mo<Subscript>7</Subscript>B<Subscript>13</Subscript> alloy

Ni₈₀Mo₇B₁₃ nanocrystalline alloy containing a Ni(Mo,B) face-centered cubic (FCC) solid solution of the substitutional-interstitial type was obtained by high-energy ball milling of the component mixtures. In the temperature range 400–700°C, the metastable solid solution Ni(Mo,B) decomposes, leading to the formation of metastable FCC Ni(Mo) and HCP MoB₄ phases. Upon isothermal annealing at 1000°C for1 h, the alloy transforms into the stable state and contains the equilibrium phases FCC Ni(Mo), cubic Ni₂₁Mo₂B₆, and orthorhombic Ni₃B.     

Structure of (Ba0.7Sr0.3)TiO3 films prepared by chemical solution deposition on sapphire substrates

Barium strontium titanate (BST) films on single-crystal sapphire substrates are prepared by chemical solution deposition upon annealing at temperatures T = 700, 850, and 1000°C. The structure of the BST films is investigated using transmission electron microscopy, high-resolution electron microscopy, and x-ray diffraction. It is established that, upon annealing at T = 700 and 850°C, the film crystallizes in the tetragonal phase of the (Ba_0.7Sr_0.3)TiO₃ perovskite without texture and transition layers. The mean grain sizes are 17 and 37 nm, respectively. However, an increase in the annealing temperature to 1000°C brings about a decrease in the mean grain size to 25 nm and the appearance of additional phases due to the interaction at the film-substrate interface.     

Coexistence of resistive switching and magnetism modulation in sol-gel derived nanocrystalline spinel Co3O4 thin films

We report the coexistence of resistive switching and magnetism modulation in the Pt/Co₃O₄/Pt devices, where the effects of thermal annealing and film thickness on the resistive and magnetization switching were investigated. The sol-gel derived nanocrystalline Co₃O₄ thin films obtained crack-free surface and crystallized cubic spinel structure. The 110 nm Co₃O₄ film based device annealed at 600 °C exhibited optimum resistive switching parameters. From I–V curves fitting and temperature dependent resistance, the conduction mechanism in the high-voltage region of high resistance state was dominated by Schottky emission. Magnetization-magnetic field loops demonstrated the ferromagnetic behaviors of the Co₃O₄ thin films. Multilevel saturation magnetization of the Co₃O₄ thin films can be easily realized by tuning the resistance states. Physical resistive switching mechanism can be attributed to the rejuvenation and annihilation of conductive filament consisting of oxygen vacancies. Results suggest that Pt/Co₃O₄/Pt device shows promising applications in the multifunctional electromagnetic integrated devices.     

Observation of metastable phase separation and amorphous phase in Fe67Co33 alloy thin films synthesized by pulsed laser depositions

Pulsed laser deposition technique has been used to manipulate the structural order of Fe₆₇Co₃₃ films grown at various substrate temperatures. Films deposited at room temperature exhibited two phases including the stable crystalline phase embedded in the amorphous phase. The crystalline phase separated into two distinct bcc phases as evident from the splitting of (110) reflections, as compared to the bulk counterpart which crystalize into the single phase bcc structure. Both crystalline phases and the amorphous phase were metastable. Films prepared at higher substrate temperatures (∼500 °C), crystallized into the single stable equilibrium bcc structure. Orientation dependent magnetic properties are also presented for the films prepared at both room temperature and higher substrate temperatures. As expected, the easy axes lie parallel to the plane of the substrate due to shape anisotropy. Out of plane magnetization for the films which exhibited short range ordering is found to saturate at smaller field compared to films where single phase bcc structure is stabilized.     

Phase transformation and magnetic properties of SmCo7−xBx alloys prepared by mechanical alloying

The phase transformation and magnetic properties of SmCo_7−xB_x (x=0, 0.2, 0.5 and 1) alloys prepared by mechanical alloying have been investigated systematically. The coercivities of the alloys without B increase with increasing annealing temperature, as a consequence of complete crystallization of TbCu₇-type phase. The substitution of B for Co is favorable to the formation of Th₂Zn₁₇- and CaCu₅-type phases when annealed at 650°C, accompanied by the enhancement of the coercivities. Increasing the annealing temperature causes the formation of soft magnetic phase Sm₂Co₁₄B in the B-substituted alloys. In the alloys with x=0.5 and 1 annealed at 850°C, the major phase is Sm₂Co₁₄B, which degrades the magnetic properties sharply. A remanence enhancement has been observed in the SmCo_7−xB_x alloys due to the exchange coupling of the nanoscale structure.     

Nanocrystallization process and ferromagnetic properties of amorphous (Fe0.99Mo0.01)78Si9B13 ribbons

The nanocrystallization process of soft ferromagnetic (Fe_0.99Mo_0.01)₇₈Si₉B₁₃ ribbons has been studied in detail. Microstructural and ferromagnetic properties are examined by transmission electron microscopy (TEM), X-ray diffraction (XRD), Mössbauer spectroscopy (MS), differential scanning calorimetry (DSC) and magnetization measurements. The Curie and crystallization temperatures are determined to be T_C=665 K and T_x=750 K, respectively. The T_x value is in well agreement with DSC measurement results. XRD patterns had shown two metastable phases (Fe₂₃B₆, Fe₃B) which were formed under in situ nanocrystallization process. These metastable phases embedded in the amorphous matrix have a significant effect on magnetic ordering. The ultimate nanocrystalline (NC) phases of α-Fe(Mo, Si) and Fe₂B at optimum annealing temperature had been observed respectively. It is notable that the magnetization of the amorphous phase decreases more rapidly with increasing temperature than those of NC ferromagnetism, which suggest the presence of the distribution of exchange interaction in the amorphous phase or high metalloid contents.     

Formation and electronic properties of oxide and sulphide films of Co,Ni and Mo studied by XPS

Dry O₂ oxidation up to 400°C, water immersion at room temperature or H₂S sulphidation at 400°C forms oxide or sulphide films on polycrystalline Co and Ni foils. X-ray photoelectron spectra (XPS) of the Co 2p and Ni 2p core levels and valence band (VB) structure changes allow the identification of the chemical state of such films and their electronic properties. They are compared with the films obtained on Mo in similar conditions. Ni appears less reactive than Co during O₂ or water oxidation and is considered as a more noble metal. Dry oxidation mainly induces CoO while water immersion induces formation of CoO(OH). For Ni, phases like Ni₂O₃, Ni(OH)₂ and/or NiO(OH) are the most probable products, respectively. H₂S sulphidation always produces a sulphur-rich Co or Ni phase. The VB response to sulphidation of the three studied metals shows that Co or Ni sulphides are potential electron-donors to MoS₂. Such results are relevant to the synergy observed in hydrotreating catalysis with these sulphides.