Sensor Properties of Nanostructured Systems Based on Indium Oxide with Co<Subscript>3</Subscript>O<Subscript>4</Subscript> or ZrO<Subscript>2</Subscript> Additives

The effect of Co₃O₄ and ZrO₂ additives on the sensory response of In₂O₃-based nanostructured composites to H₂ and CO is studied. It is shown that the addition of small amounts of Co₃O₄ or ZrO₂ to In₂O₃ leads to a sharp increase in the sensory response to hydrogen. The maximum sensory response of the ZrO₂?In₂O₃ composite to 1100 ppm of hydrogen increases from 80 to 270 as the ZrO₂ content changes 0 to 20 wt %. The response to CO varies only slightly. For Co₃O₄?In₂O₃ composites, the maximum response to H₂ and CO increases with the Co₃O₄ content within 0?10 wt %. A further increase in the Co₃O₄ content leads to a significant decrease in the response, with composites containing ～60 wt % Co₃O₄ being characterized by a very low efficiency. In the Co₃O₄?In₂O₃ system with a content of up to 60 wt % Co₃O₄, electronic conduction is realized, which changes to hole conduction at Co₃O₄ within 80?100 wt %. In the ZrO₂?In₂O₃ system, electric current flows through In₂O₃ nanocrystals, i.e., n-type conduction takes place. Possible reasons for the observed effects are discussed.     

Exchange Bias in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite

It is established that excess oxygen content δ influences the exchange bias (EB) in layered GdBa-Co₂O_{5 + δ} cobaltite. The EB effect arises in p-type (δ > 0.5) cobaltite and disappears in n-type (δ < 0.5) cobaltite. The main parameters of EB in GdBaCo₂O_5.52(2) polycrystals are determined, including the field and temperature dependences of EB field H _EB , blocking temperature T _B , exchange coupling energy J _i of antiferromagnet–ferromagnet (AFM–FM) interface, and dimensions of FM clusters. The training effect inherent in systems with EB has been studied. The results are explained in terms of exchange interaction between the FM and AFM phases. It is assumed that the EB originates from the coexistence of Co³⁺ and Co⁴⁺ ions that leads to the formation of monodomain FM clusters in the AFM matrix of cobaltite.     

Two-band conductivity of ZrO<Subscript>2</Subscript> synthesized by molecular beam epitaxy

Using experiments on the injection of minority carriers from n-and p-type silicon, the contribution of electrons and holes to the conductivity of ZrO₂ in the Si/ZrO₂/Al structure is determined. It is found that electrons and holes make a contribution to the conductivity of ZrO₂, so that ZrO₂ exhibits two-band conductivity.     

Anisotropy of the Complex Permittivity of the Kagome-Staircase Compounds Co<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> and Ni<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript>: Experiment and Ab Initio Calculations

The anisotropy of the components of the complex permittivity of vanadate Co₃V₂O₈ and Co₃V₂O₈ single crystals in the paramagnetic phase are studied by optical ellipsometry in the spectral region 0.5–5.0 eV. Our experimental results support the weak anisotropy of the optical response detected earlier for axes a and c. The optical properties are also investigated along axis b. The properties of both compounds are compared. The optical spectra of both compounds along axis b are shifted toward low energies as compared to axes a and c. The maximum of the main interband absorption band of Co₃V₂O₈ is shifted toward low energies by 0.25–0.3 eV as compared to Co₃V₂O₈. The electronic structure parameters of both compounds are determined. Optical function spectra are analyzed using the results of ab initio band calculations.     

Influence of heat treatment process in In<Subscript>2</Subscript>O<Subscript>3</Subscript>-MWCNTs as photoanode in DSSCs

Indium oxide-multi-walled carbon nanotubes (In₂O₃-MWCNTs) were prepared by sol-gel method for DSSCs. The synthesis of indium oxide (In₂O₃) was carried out by dissolving indium chloride (InCl₃) in a solvent of 2-methoxyethanol. Different annealing temperatures of 400, 450, 500, 550, and 600 °C were proposed in this study. The changes in the structural properties were analyzed by means of X-ray diffraction (XRD) and atomic force microscopy (AFM) analysis. The XRD spectrum estimated the average crystallite sizes of 3 nm for each sample. AFM results indicated very rough surface area of the films where it increased linearly from 1.8 to 11 nm as the annealing temperature increases. The In₂O₃-MWCNTs-based DSSC exhibited good photovoltaic performance with power conversion efficiency (η), photocurrent density (J _sc ), open circuit voltage (V _oc ), and fill factor (FF) of 1.13 %, 5.5 mA/cm², 0.53 V, and 0.42, respectively. Even though the film annealed at 450 °C exhibited low τ _eff, it achieved the greatest D _eff of 29.67 cm² s^?1 which provides an efficient pathway for the photogenerated electrons with minimum electron recombination loss that increased the J _sc and V _oc in the DSSC. The obtained structural and electron transport analysis was proposed as a suitable benchmark for In₂O₃-MWCNTs-based dye-sensitized solar cell (DSSCs) application. Hence, this study suggests that the optimum temperature for In₂O₃-MWCNTs is at annealing temperature of 450 °C prepared via sol-gel method.     

Electrical instability of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

The temperature behavior of I-U curves and the field and temperature dependences of the electrical resistivity and dielectric permittivity of crystals of the LiCu₂O₂ phase have been studied. It was established that the crystals belong to p-type semiconductors and that their static resistivity in the range 80–260 K follows the Mott law ρ=Aexp(T₀/T)^1/4 describing variable-range hopping over localized states. At comparatively low electric fields, the crystals exhibit threshold switching and characteristic S-shaped I-U curves containing a region of negative differential resistivity. In the critical voltage region, jumps in the conductivity and dielectric permittivity are observed. Possible mechanisms of the disorder and electrical instability in these crystals are discussed.     

Properties of Ca-containing LiCoPO<Subscript>4</Subscript>-graphitic carbon foam composites

LiCo_1???x Ca _x PO₄–graphitic carbon foam composites are prepared using a sol–gel method. The structural analysis reveals LiCoPO₄ as major crystalline phase and Co₂P₂O₇ (for x?=?0.0) and Co₂P, Li₃PO₄, and (Ca,Co)₃(PO₄)₂ (for x?≥?0.05) as secondary phases. The morphology consists of microcrystalline “islands” with acicular crystallites (5–50 μm size). Transmission electron microscopy (TEM) of the powders showed that the Ca is incorporated into the crystal structure evoking exaggerated grain growth. The voltammetric profiles show a decrease of the voltammetric surface between anodic and cathodic sweeps and a shift of the reduction potentials toward higher values (～4.6 V, x?=?0.1). The electrochemical measurements, at a discharge rate of C/10 (room temperature), show an increase of the discharge-specific capacity from 100 mAhg^?1 for x?=?0.0 to 104 mAhg^?1 for x?=?0.1. The ac impedance spectroscopy data revealed an improvement of the Li-ion conductivity at high content of Ca ions (x?=?0.1).     

Transport properties of Co<Subscript>2</Subscript>CrAl Heusler alloy films

The effect of atomic disorder on the electron transport and the magnetoresistance (MR) of Co₂CrAl Heusler alloy (HA) films has been investigated. We show that Co₂CrAl films with L2₁ order exhibit a negative value for the temperature coefficient of resistivity (TCR) in a temperature range of 10 < T < 290 K, and the temperature dependence of electric conductivity varies as T ^3/2 similarly to that of the zero-gap semiconductors. The atomic or the site disorder on the way of L2₁ → B2 → A2 → amorphous state in Co₂CrAl HA films causes the deviation from this dependence: reduction in the absolute value of TCR as well as decrease in the resistivity down to ?(T = 293 K) ～ 200 μΩ cm in comparison to ?(T = 293 K) ～ 230 μΩ cm typical for the Co₂CrAl films with L2₁ order. The magnetic-field dependence of MR of the Co₂CrAl films with L2₁ order is determined by two competing contributions: a positive Lorentz scattering and a negative s-d scattering. The atomic disorder in Co₂CrAl films drastically changes MR behavior due to its strong influence on the magnetic properties.     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

Comparative study of solid-state reaction and sol-gel process for synthesis of Zr-doped Li<Subscript>0.5</Subscript>La<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> solid electrolytes

We investigated the synergistic influences of synthesis methods (solid-state reaction vs. sol-gel process) and Zr⁴⁺ doping on the structure and ionic conductivity of perovskite-structured Li_0.5La_0.5TiO₃ (LLTO) solid electrolytes. The lithium-ion conductivity of Li_0.5La_0.5Ti_1???x Zr _x O₃ ceramic specimens was evaluated as a function of x value and compared carefully between those two synthesis methods. Regarding the conductivity, sol-gel process is better for the synthesis of LLTO than solid-state reaction. As a result, the highest grain conductivity is obtained in the sol-gel-derived pure LLTO sample with x?=?0, reaching 1.10?×?10^?3 S?·?cm^?1. Partial substitution of Zr⁴⁺ enlarges the LLTO’s grain aggregate size and increases the total superficial area of aggregates. Consequently, Zr⁴⁺ substitution not only affects the grain (bulk) conductivity, but more importantly, also improves the grain boundary conductivity and the total conductivity. The highest total conductivity is 5.84?×?10^?5 S?·?cm^?1 with x?=?0.04 by sol-gel process.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Thermopower in the region of hopping conduction in TlNiS<Subscript>2</Subscript>

Samples of the composition TlNiS₂ in the hexagonal system with the unit cell parameters a=12.28 Å, c=19.32 Å, and ρ=6.90 g/cm³ are synthesized. The results of the investigation into the electrical and thermoelectrical properties of TlNiS₂ samples in the temperature range 80–300 K indicate that TlNiS₂ is a p-type semiconductor. It is found that, at temperatures ranging from 110 to 240 K, TlNiS₂ samples in a dc electric field possess variable-range-hopping conduction at the states localized in the vicinity of the Fermi level. The density of localized states near the Fermi level is determined to be N_F=9×10²⁰ eV^?1 cm^?3, and the scatter of the states is estimated as J≈2×10^?2 eV. In the temperature range 80–110 K, TlNiS₂ exhibits activationless hopping conduction. At low temperatures (80–240 K), the thermopower of TlNiS₂ is adequately described by the relationship α(T)=A+BT, which is characteristic of the hopping mechanism of charge transfer. In the case when the temperature increases to the temperature of the onset of intrinsic conduction with the activation energy ΔE=1.0 eV, there arise majority intrinsic charge carriers of both signs. This leads to an increase in the electrical conductivity σ and, at the same time, to a drastic decrease in the thermopower α; in this case, the thermopower is virtually independent of the temperature.     

Isotropic positive magnetoresistance in Co-Al<Subscript>2</Subscript>O<Subscript>n</Subscript> nanocomposites

The magnetotransport properties of Co_x(Al₂O_n)_{100 ? x} nanocomposites were studied in a wide concentration range (34 ≤ x ≤ 74 at %). Negative tunnel magnetoresistance reaching 6.5% in a field of 10 kOe was established. In addition to the negative magnetoresistance, the Co_x(Al₂O_n)_{100 ? x} composites were found to exhibit positive magnetoresistance reaching 1.5% in fields of 10 kOe over the concentration range corresponding to the percolation threshold (54 ≤ x ≤ 67 at %). The positive magnetoresistance is assumed to be due to the simultaneous existence in the composite structure of clusters and individual nanoparticles characterized by different values of the magnetic anisotropy and due to the dipole-dipole interaction between the clusters and nearest neighbor particles.     

Conductivity and spectroscopic studies of Li<Subscript>2</Subscript>O-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

Lithium vanadium-borate glasses with the composition of 0.3Li₂O–(0.7-x)B₂O₃–xV₂O₅ (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V₂O₅ concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO₄] structural units occur at V₂O₅ concentration of 45 mol%. It is established that the concentration of V⁴⁺ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li₂O-0.275B₂O₃-0.475V₂O₅ shows the highest electrical conductivity that has the value of 7.4?×?10^?5 S cm^?1 at room temperature.     

The magnetization reversal in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/CoFe<Subscript>2</Subscript> granular systems

The temperature-dependent field cooling (FC) and zero-field cooling (ZFC) magnetizations, i.e., M _FC and M _ZFC, measured under different magnetic fields from 500 Oe to 20 kOe have been investigated on two exchange–spring CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at a field-dependent irreversible temperature T _irr. For the sample with less CoFe₂, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad peak at an intermediate temperature T ₂ below T _irr , and the moments are suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the ?d(M _FC ? M _ZFC)/dT curves of the sample with more CoFe₂, besides a broad peat at an intermediate temperature T ₂, a rapid rise around the low temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

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Graphical abstract CoFe₂O₄/CoFe₂ composites with different relative content of CoFe₂ were prepared by reducing CoFe₂O₄ in H₂ for 4 h (S4H) and 8 h (S8H). The temperature-dependent FC and ZFC magnetizations, i.e., M _FC and M _ZFC, under different magnetic fields from 500 Oe to 20 kOe have been investigated. Two samples exhibit different magnetization reversal behaviors. With decreasing temperature, a progressive freezing of the moments in two composites occurs at field-dependent irreversible temperature T _irr. For the S4H sample, the curves of ?d(M _FC ? M _ZFC)/dT versus temperature T exhibit a broad and field-dependent relaxing peak at T ₂ below T _irr (figure a), and the moments were suggested not to fully freeze till the lowest measuring temperature 10 K. However, for the S8H sample, it exhibits the reentrant spin-glass state around 50 K, as evidenced by a peak in the M _FC curve (inset in figure b) and as a result of the cooperative effects of the random anisotropy of CoFe₂O₄, exchange–spring occurring at the interface of CoFe₂O₄ and CoFe₂ together with the inter-particle dipolar interaction (figure c); in ?d(M _FC ? M _ZFC)/dT curves, besides a broad relaxing peat at T ₂, a rapid rise around the low-temperature T ₁~15 K is observed, below which the moments are suggested to fully freeze. Increase of magnetic field from 2 kOe leads to the shift of T ₂ and T _irr towards a lower temperature, and the shift of T ₂ is attributable to the moment reversal of CoFe₂O₄.

     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.     

Internal friction of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> single crystals

This paper reports on the results of measurements of the internal friction Q^?1 and the shear modulus G of Li₂B₄O₇ single crystals along the crystallographic directions [100] and [001] in the temperature range 300–550 K for strain amplitudes of (2–10)×10^?5 at infralow frequencies. The anomalies observed in Q^?1 and G in the temperature range 390–410 K are due to thermal activation of the mobility of lithium cations and their migration from one energetically equivalent position to another. A jump in the internal friction background is revealed in the vicinity of the Q^?1 and G anomalies for the Li₂B₄O₇ crystal. The magnitude of this jump depends on the crystallographic direction.     

Charge transport in PbMoO<Subscript>4</Subscript> crystals

Dc and ac electrical conductivity of lead molybdate crystals is studied in the temperature range 300–550 K. The electrical conductivity was shown to have electronic (hole) impurity character. The I–V characteristics are typical of a space charge-limited current. The carrier mobility was estimated to be 10^?5 cm² V^?1 sat T=300 K. The results of the study suggest the hopping mechanism of conduction in PbMoO₄ crystals.     

Evolution of the phase composition and physicomechanical properties of ZrO<Subscript>2</Subscript> + 4 mol % Y<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics

The evolution of the phase composition and physicomechanical properties of ZrO₂ + 4 mol % Y₂O₃ ceramics subjected to hot isostatic pressing and subsequent calcining in air is investigated. It is found that hot isostatic pressing results in the formation of an easily transformed phase T_et with a degree of tetragonality c/a=1.035, which determines high fracture toughness. After calcining in air, the phase T_et decomposes to form a nontransformed phase T′ with a degree of tetragonality c/a=1.005, which determines low fracture toughness.     

Mechanisms of low-temperature high-frequency conductivity in systems with a dense array of Ge<Subscript>0.7</Subscript>Si<Subscript>0.3</Subscript> quantum dots in silicon

High-frequency (HF) conductivity in systems with a dense (with a density of n = 3 × 10¹¹ cm^?2) array of self-organized Ge_0.7Si_0.3 quantum dots in silicon with different boron concentrations n_B is determined by acoustic methods. The measurements of the absorption coefficient and the velocity of surface acoustic waves (SAWs) with frequencies of 30–300 MHz that interact with holes localized in quantum dots are carried out in magnetic fields of up to 18 T in the temperature interval from 1 to 20 K. Using one of the samples (n_B = 8.2 × 10¹¹ cm^?2), it is shown that, at temperatures T ≤ 4 K, the HF conductivity is realized by the hopping of holes between the states localized in different quantum dots and can be explained within a two-site model in the case of

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, where ω is the SAW frequency and τ₀ is the relaxation time of the populations of the sites (quantum dots). For T > 7 K, the HF conductivity has an activation character associated with the diffusion over the states at the mobility threshold. In the interval 4 K < T < 7 K, the HF conductivity is determined by a combination of the hopping and activation mechanisms. The contributions of these mechanisms are distinguished; it is found that the temperature dependence of the hopping HF conductivity approaches saturation at T* ≈ 4.5 K, which points to a τ₀ ≤ 1. A value of τ₀(T*) ≈ 5 × 10^?9 s is determined from the condition ωτ₀(T*) ≈ 1.