Phase transitions in the atomic, electronic, and magnetic subsystems of LaSrMnO films versus the synthesis temperature

The evolution of the cluster structure in amorphous LaSrMnO films as synthesis temperature T _s increases from 20 to 300°C is considered. Two order-disorder phase transitions with different scale parameters are observed. One of them, the aggregation of disordered atoms into small (～20 Å) amorphous clusters at T _s = 100°C, shows up as a sharp increase in the intensity of diffuse X-ray scattering (diffuse halo 1) with a simultaneous suppression of incoherent (background) scattering. At T _s > 150°C, disordering dominates (I _incoh = I _max) until the next stage of ordering sets in at T _s = 250?300°C. At this stage, the crystalline phase forms from large (>100 Å) crystalline clusters. This amorphous-crystalline phase transition is characterized by the appearance of Debye lines and a reduction of the halo intensity. The structural phase transition to long-range order is accompanied by a decrease in the LaSrMnO resistivity from 10¹⁰ to 10 Ω cm and a change from the tunneling mechanism of conductivity involving metallic clusters (which is typical of granulated systems) to the hopping mechanism with a hop variable length following the Mott law ρ ～ exp(T ^?1/4). In the magnetic subsystem, the paramagnetic-ferromagnetic phase transition occurs.     

On the decomposition of the transition rhombohedral phase in the Al-30 wt.% Zn alloy

The decomposition of the transition rhombohedral α′_R-phase at the temperatures between 85 and 250 °C was investigated by transmission electron microscopy and by X-ray diffraction on single crystals. Below 161 °C the direct decomposition of α′_R-phase into the equilibrium hexagonal β-phase without the formation of the transition cubic α′-phase was found. Both transformation sequences α′_R → β and α/′_R→α′ → β were observed in the temperature range from 161 to 180 °C whereas only the previously known sequence α′_R → α′ → β was detected on ageing the alloy between 180 and 250 °C. The precipitation process at the temperatures from 161 to 180 °C is characterized by the decomposition of α′_R-phase into the equilibrium β-phase prior to the formation of the transition α′-phase and by the increased rate of decomposition of α′-precipitate. The observed transformation processes are related to the variation of strains at the partially coherent interface between α′_R-phase and α-matrix with the temperature in correlation with the metastable α′_R-phase boundary. These considerations allowed to estimate the relative stabilities of precipitated phases and their activation energies of formation and thus to discuss the decomposition mechanism of α′_R-phase at various temperatures.     

Changes in the electronic,optical, and magnetic properties of LaSrMnO films upon transition from the rhombohedral phase to the orthorhombic phase

The properties of LaSrMnO films are investigated in the temperature range of the transition from the rhombohedral phase to the orthorhombic phase (600–650° C). It is shown that, with a variation in the growth temperature T_s, the change in the film properties is governed by the interaction of Mn-O metallic (ferromagnetic) clusters in the dielectric (antiferromagnetic) matrix. At T_s≤600°C, the low density of e _g states and the dielectric gap (E _g =0.3–0.5 eV) are responsible for the following features: (i) the optical transparency in the range ?ω=0.5–2 eV, (ii) the difference between the FC and ZFC magnetizations M(T), (iii) the high resistance, and (iv) the appearance of the portions R(T) ≈ const in the dependence R(T) due to the transformation of clusters into a system of tunnel-coupled quantum dots. At T_s≥650°C, the local increase in the atomic and electronic densities leads to a decrease in the optical transmission and the resistance by three to nine orders of magnitude, the appearance of a maximum and a minimum in the dependences R(T) of the LaSrMnO films, and an increase in the magnetization M(10 K) by one order of magnitude. The inference is drawn that magnetic ordering of the system of tunnel-coupled clusters encourages an increase in the cluster size and in the content of the metallic (ferromagnetic) phase.     

Spectroscopic diagnostics of R.F. discharges at moderate pressure and chemical applications—I. Pure nitrogen

A vibro-rotational analysis has been performed of the second positive system (SPS) of N₂ and of the first negative system (FNS) of N⁺₂ emitted by 35 MHz discharges in flowing nitrogen operated at pressures of 5–50 torr and power densities of the order of 1–10 W-cm^-3. The distributions of the vibrational and of the rotational levels follow Boltzmann's law in both the SPS and the FNS with T_v = 4000°K and T_R = 2800°K for the N₂(C³Π_u) state and T_v = 5100°K and T_R = 5800°K for the N⁺₂(B²Σ⁺_g) state and independent of pressure. Kinetic gas temperatures are between 1200 and 2000°K and increase with pressure; electron temperatures are in the range 15,000–9,500°K. The reversal of line intensities of the SPS and of the FNS observed with increasing pressure has been tentatively interpreted. Possible chemical implications of these results have been examined.     

High-pressure phases in nanocrystalline Co(C) films obtained by pulsed plasma vaporization

The phase composition of nanocrystalline Co(C) films obtained by a new pulsed plasma vaporization technique was found by studying their atomic structure and magnetic properties. The films deposited at the substrate temperature T=50°C were of heterophase structure and consisted of a supersaturated solid Co(C) solution and the metastable Co₃C carbide. The films obtained at T=150°C represented a mechanical mixture of the metastable Co₃C and Co₂C carbides. The metastable Co₃C and Co₂C carbides obtained in a nanocrystalline state were high-pressure phases (～100 kbar). The thermal stability ranges of these metastable phases were determined.     

Self-organization of the structure in the Cu60Fe40 composite during deformation-thermal treatment

The deformation-thermal stability of a clusterized amorphous-crystalline structure prepared from a Cu₆₀Fe₄₀ powder mixture at a logarithmic strain e = 4.6 and subjected to isochronous (40 min) annealings at T _a = 200–800°C has been investigated. Periodic changes (ΔT = 300°C) in the order and disorder with a maximum ordering at T _a = 300 and 600°C and a maximum disordering at T _a = 400 and 700°C have been observed. The periodicity of the dominant crystallographic order with a period ΔT = 400°C in the annealing temperature has been revealed for face-centered cubic copper phase planes separated by a singular point at T = 500°C characterized by the dominant body-centered cubic iron phase ordering. It has been shown that the sawtooth shape of the size distribution of strain clusters formed within the crystal structure of deformed samples slowly changes with increasing annealing temperature from exponential (T _a = 200–700°C) to linear (T _a = 800°C). This indicates a high density of internal local distortions in structural units.     

电子回旋共振氩等离子体中亚稳态粒子数密度及电子温度的测量

测量了电子回旋共振（ECR）氩等离子体中Ar的1s₅亚稳态粒子数密度，在气压 为02—0 8 Pa、功率为500—700W的范围内，利用吸收光谱法测量了Ar原子8115 nm谱线的吸收强 度，得到1s₅亚稳态粒子数密度为1×10¹⁵—4×10¹⁵ m ^-3.本文综合考 虑基态和1s₅亚稳态粒子的激发对Ar发射谱线强度的贡献后，用两条发射谱线强 度之比得 到电子温度.结果表明，计入了1s₅亚稳态激发的贡献后，所得到的电子温度与 只考虑基态的贡献得到的电子温度相比存在较大的差别. 关键词： 光谱法 亚稳态粒子数密度 电子温度 ECR等离子体源     

Effects of gas temperature on optical and transport properties of a-Si:H films deposited by PECVD

Effects of silane temperature (T _g) before glow-discharge on the optical and transport properties of hydrogenated amorphous silicon (a-Si:H) thin films were investigated. The optical measurements show that the refractive index increases with increasing T _g. The transport characterizations show that when T _g increases, the dark conductivity increases. However, the temperature coefficient of resistance decreases. In addition, after holding at 130°C for 20 h, the resistance variation, ΔR/R, of the films deposited at T _g = room temperature (10.8%) is much larger than those deposited at silane temperatures of 80°C (3%) and 160°C (2%). This can be attributed to different rates of defect creation in a-Si:H films caused by various T _g.     

Giant volume magnetostriction and colossal magnetoresistance in La0.7Ba0.3MnO3 at room temperature

In single-crystal La_0.7Ba_0.3MnO₃, giant volume magnetostriction was observed for the first time to reach 2.54 × 10^?4 at room temperature and a still larger level of 4 × 10^?4 at the Curie point T _C = 310 K in a magnetic field of 8.2 kOe. At the same temperatures and magnetic field, this effect is complemented by a colossal magnetoresistance of 15.2 and 22.7%, respectively. The volume magnetostriction ω and magnetoresistance Δρ/ρ follow similar patterns in the proximity of T _C; namely, ω and Δρ/ρ are negative, maxima are observed in the |ω|(T) and |Δρ/ρ|(T) curves, and the ω and Δρ/ρ isotherms do not saturate in the highest fields applied. These phenomena are assigned to the fact that, in the above composition, there exists a two-phase magnetic (ferromagnetic-antiferromagnetic) state induced by strong s–d exchange.     

Effect of radiation-induced defects on the dielectric response of lead scandoniobate ferroelectric ceramics

The effect of ionizing gamma irradiation on the frequency and temperature dependences of the permittivity ε’(T) for lead scandoniobate relaxor (disordered) ferroelectric ceramics before and after thermal annealing was investigated by low-and infralow-frequency dielectric spectroscopy. It was demonstrated that the irradiation leads to a shift in the temperatures of the maxima in the dependence ε’(T) and the temperatures of the maxima in the dependence of the dispersion depth Δε’(T) toward the high-temperature range, as well as to the suppression of high-temperature (～ 300–400°C) polarization relaxation. After annealing at a temperature T ～ 600°C, the properties of the material were partially recovered.     

Nuclear relaxation in normal and superconducting hydrogen alloys: Th4H15

T₁ measurements in the normal state show that the conduction electrons are responsible for the proton nuclear relaxation for T ? 300°K. an additional mechanism appears in the superconducting state.     

Measurement of line widths of CO of planetary interest at low temperatures

Self-broadened, air-broadened and CO₂-broadened half-widths of lines R(0) through R(0) in the CO fundamental have been measured at 100°K (self-broadening only), 200°K, 250°K and 300°K using the Ladenburg-Reiche curve-of-growth. The relation $\text{γ}{}^{\mathrm{°}}{}_{\mathrm{m}}\text{(T)}\text{γ}{}^{\mathrm{°}}{}_{\mathrm{m}}\text{(300°K)}\text{=(}\text{300}\text{T}\text{)}{}^{0.75}$, which we found previously for the nitrogen-broadened half-widths of R(0), R(8) and R(16), is shown to be valid for all of the line widths measured in the present study.     

Magnetic susceptibility and superconductivity of cubic vanadium nitrides

The superconducting transition temperature T_C and the magnetic susceptibility from 77 to 300°K have been measured on five cubic vanadium nitrides: VN, VN_0.91, VN_0.82, VN_0.84 and VN_0.75. The materials were carefully prepared to exclude oxygen and ferromagnetic impurities.The value of T_C, falls from 8.1°K for VN to 2.3°K for VN_0.75. The mass-susceptibility decreases from +3.94 × 10^?6e.m.u./g for VN to 1.88 × 10^?6e.m.u./g for VN_0.75 at 300°K. All samples showed a small positive slope for the susceptibility temperature curve.The results are discussed in terms of the rigid band model. The main features are a high density of states of d electrons, 2.4 states/atom eV for VN that drops off as the nitrogen content decreases, to 0.8 states/atom eV.Preliminary considerations indicate that many-body effects could reduce this density of states by as much as a factor of 2. Lack of experimental results on Knight shifts and low-temperature specific heats prevent a more quantitative estimate being made.     

Solvus line of the metastable rhombohedral phase in the Al-Zn system for Al-rich alloys

The X-ray diffraction on single crystals and on coarse-grained foils of Al-Zn alloys was used to determine the solvus temperatures of the metastable rhombohedral α′ _R -phase. The dissolution of α′ _R -phase was studied simultaneously by application of DTA technique. Results obtained from different heat-treatments of the investigated alloys were critically interpreted in terms of the nucleation theory. The dissolution of large α′ _R -particles was necessary to obtain the correct α′ _R -solvus line unaffected by the reversion of the solid solution below the solvus temperatures.     

Dependence of Tg and T ll on tacticity of PMMA by differential scanning calorimetry

A differential scanning calorimeter (DSC) investigation (heating rate 10 K/min) is presented on the multiple transition (relaxation) spectra of PMMA: T_β < T_g; T_g, T_ll > T_g; and T_lρ > T_ll, as a function of tacticity. Specimens are characterized by fractional triad content: isotactic (it-), Xii; syndiotactic (st-), Xss; and atactic (at-), Xis. Values for the seven specimens are it-, 1.0;, at-, 0.495 to 0.750; st-, 0.958. Results on T_β were inconclusive. Our T_g results clarify some discrepancies in the prior literature.

Linear least squares regression analyses give: T_g (°C) = 56.6 + 76.6 Xss (our data) T_g (°C) = 49.1 + 87.3 Xss (our data plus selected literature data)

Extrapolated T_g 's for Xss = 1 are 133.2°C and 136.1°C, respectively, in contrast to Thompson's extrapolated value of 160°C. Similarly T_g(°C) = 99.5 + 71.6 (1?Xii) for our DSC data. The extrapolated T_ll for Xss = 1 is 171.1°C. The intensity of T_ll is high for st-and it-, with a broad minimum over the at-region. A second liquid state process, T_lρ > T_ll, occurs at 149°C for it-, but is above the measured range for at-and st-. T_ll (at-) from DSC compares favorably with reported literature values by a variety of techniques. T_ll and T_lρ at all tacticities agree well with those from a companion study by the thermally stimulated current (TSC) technique on the same group of specimens, as reported elsewhere. This includes the influence of tacticity on intensity. These cross-comparisons by a variety of methods indicate that neither T_ll nor T_lρ is an artifact of our DSC technique. The Frenkel segment-segment contact hypothesis is favored to explain the molecular origin of T_ll Sequences longer than triads may be needed for improved correlations of T_g and T_lρ with tacticity.     

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.     

Time-dependent density functional theory study on electronic excited states of the hydrogen-bonded solute-solvent phenol-(H2O)n (n=3-5) clusters

The solute-solvent interactions of hydrogen-bonded phenol-(H₂O)_n (n=3-5) clusters in electronic excited states were investigated by means of the time-dependent density functional theory (TDDFT) method. The geometric structures and IR spectra in ground state, S₁ state, and T₁ state of the clusters, were calculated using the density functional theory (DFT) and TDDFT methods. Only the ring form isomer, the most stable one of the cluster, was considered in this study. Four, five and six intermolecular hydrogen bonds were formed in phenol-(H₂O)₃, phenol-(H₂O)₄, and phenol-(H₂O)₅ clusters, respectively. Based on the analysis of IR spectra, it is revealed that the “window region” between unshifted and shifted absorption bands in both S₁ and T₁ state becomes broader compared with that in ground state for the corresponding clusters. Furthermore, two interesting phenomenon were observed: (1) with the anticlockwise order of the ring formed by the intermolecular hydrogen bonds in the H-bonded phenol-(H₂O)_n (n=3-5) clusters, the strengths of the intermolecular hydrogen bonds decrease in all the S₀, S₁ and T₁ states; (2) upon electronic excitation, the smaller the distance between phenol and water is, the larger the change of intermolecular hydrogen bonds strength is. Moreover, the intermolecular hydrogen bond (phenolic OH is the H donor) is strengthened in excited state compared with that in ground state. But the intermolecular hydrogen bond (phenolic OH is the H acceptor) is weakened in excited state.     

A Variable Temperature X- and W-Band EPR Study of Fe-Doped SiCN Ceramics Annealed at 1000, 1100, and 1285 °C: Dangling Bonds,Ferromagnetism and Superparamagnetism

Polymer-derived SiCN ceramics, annealed (also referred to as pyrolyzed) at 1000, 1100, and 1285 °C, and doped with Fe(III) acetylacetonate, are investigated by electron paramagnetic resonance (EPR) from 4 to 120 K at X-band (9.425 GHz). In addition, the SiCN ceramic, annealed at 1100 °C, was studied by EPR at 300 K at W-band (93.96 GHz). There was observed a significant increase in EPR linewidth due to dangling bonds (g = 2.001) below 20 K at X-band. The low-field X-band FMR line (g ≈ 12) indicated the presence of ferromagnetic Fe₅Si₃ crystallites. There were found two EPR lines due to carbon-related dangling bonds: (1) those present as defects on the surface of the free-carbon phase (as sp² carbon-related dangling bonds with g = 2.0011) and (2) those present within the bulk of carbon phase (as sp³ carbon-related dangling bonds with g = 2.0033). On the other hand, the intense low-field EPR signal observed at X-band was not observed at W-band. As well, there was observed splitting of the single broad EPR signal observed at g = 2.05 at X-band into two signals at W-band at g = 1.99 and g = 2.06, due to two different Fe-containing superparamagnetic nanocrystallites. Two new EPR signals, not observed at X-band, were observed at W-band, namely at g = 2.28 and g = 3.00, which are also due to g_∥ of these superparamagnetic nanocrystallites.     

Low-temperature spray-pyrolysis of FeS2 films and their electrical and optical properties

Iron disulfide (FeS₂) films with a wide range of electrical resistivities 100 Ω cm ? ρ ? 800 kΩ cm, a high adhesion to the substrate, and a resistance to aggressive media have been prepared by the spray pyrolysis of aqueous solutions of the salts FeCl₃ · 6H₂O and (NH₂)₂CS at low temperatures in the range 250°C ? T _S ? 400°C. It has been found that the FeS₂ films have a high transmittance T ≈ 60–70% and are characterized by a sharp transmission edge. It has been shown that the optical band gap for direct (E _g ^op = 2.19–2.78 eV) and indirect (E _g ^′op = 1.26–1.36 eV) optical transitions depends on the conditions of film preparation.     

Phase transition study in α-Fe2WO6 compound by EPR

The temperature dependence of the EPR spectrum for the α-phase of iron tungstate has been investigated in the temperature range of 40–260 K. At temperatures betweenT ₁ ≈ 250 K andT ₂ ≈ 205 K where the antiferromagnetic phase transition occurs, a relatively narrow EPR line arising from the dominant iron(III) species has emerged, gaining intensity with the temperature increase. Its linewidth temperature evolution could be described by Huber equation, with T_N = 200 K, which is consistent with the peak seen in magnetic susceptibility measurements, while the correspondingg-factor shifts to higher fields reflecting the build-up of internal field emerging from increasing shortrange order in the spin system. At temperatures lower than T₂, a very broad and distorted EPR line with temperature dependentg-factor and linewidth has been observed reflecting the corresponding rise of the magnetic susceptibility below the antiferromagnetic phase transition, presumably arising from magnetic clusters embedded in the antiferromagnetic background.