Giant permittivity up to 100 MHz in La and Nb co-doped rutile TiO2 ceramics

Dielectric spectroscopy was carried out for reduced and stoichiometric La_0.0025Nb_0.0025Ti_0.995O₂ ceramics synthesized by sintering in different atmospheres. A giant permittivity (~1 × 10⁴) was obtained at a frequency of 100 MHz and temperature range from 170 to 350 K. Three dielectric relaxation mechanisms were observed within the temperature range of 10-300 K via dielectric spectroscopy. A low temperature dipole relaxation peak (in the temperature range of 10-30 K) in the spectra was identified to be associated with the giant permittivity specifically measured at 100 MHz. The origin of such giant permittivity was attributed to dipole orientation polarization. Hopping polaron and interfacial effect contributed to giant permittivity. After annealing treatment, all the relaxation contributions were weakened. Low dielectric loss was attributed to high resistance of grain and grain boundaries. Annealing in ambient conditions led to decreased relaxation times which gives the signature of decreased concentration of oxygen vacancies and Ti³⁺. Dipoles which were related to oxygen vacancies and Ti³⁺, resulted in giant permittivity up to 100 MHz.     

Influence of Cobalt Doping on the Physical Properties of Zn<Subscript>0.9</Subscript>Cd<Subscript>0.1</Subscript>S Nanoparticles

Zn_0.9Cd_0.1S nanoparticles doped with 0.005–0.24 M cobalt have been prepared by co-precipitation technique in ice bath at 280 K. For the cobalt concentration >0.18 M, XRD pattern shows unidentified phases along with Zn_0.9Cd_0.1S sphalerite phase. For low cobalt concentration (≤0.05 M) particle size, d _XRD is ~3.5 nm, while for high cobalt concentration (>0.05 M) particle size decreases abruptly (~2 nm) as detected by XRD. However, TEM analysis shows the similar particle size (~3.5 nm) irrespective of the cobalt concentration. Local strain in the alloyed nanoparticles with cobalt concentration of 0.18 M increases ~46% in comparison to that of 0.05 M. Direct to indirect energy band-gap transition is obtained when cobalt concentration goes beyond 0.05 M. A red shift in energy band gap is also observed for both the cases. Nanoparticles with low cobalt concentrations were found to have paramagnetic nature with no antiferromagnetic coupling. A negative Curie–Weiss temperature of −75 K with antiferromagnetic coupling was obtained for the high cobalt concentration.     

Temperature-dependent photoluminescence and decay times of different phases of grown TiO2 nanoparticles: Carrier dynamics and trap states

Three different phases, namely anatase, mixed and rutile phases of TiO₂ nanoparticles (NPs) were developed with varying temperatures from 400 to 900 °C and confirmed using various characterization techniques. The XRD analysis of TiO₂ NPs in temperature range of 290 to 77 K with no significant changes predict the thermally stable NPs. Photoinduced carrier dynamics of TiO₂ NPs were investigated by the temperature dependence (TD) photoluminescence (PL) and TD time-resolved PL (TRPL) decays. With varying temperatures from 290 to 77 K, the anatase phase exhibits an additional and dominant 530 nm PL band. However, the mixed and rutile phases show three well-resolved PL bands, including 420 nm, 530 nm and near-infrared (NIR) bands at 820 nm at a lower temperature. Again, 530 nm band dominated for mixed-phase.In contrast, for the rutile phase, the 820 nm band dominated at <100 K. The PL lifetime of the 420 nm band is nearly a single exponential for all the phases. And is also true for the 530 and 820 nm PL bands, but bi-exponential for ≤100 K. Both the PL and TRPL results predict the presence of trap states in TiO₂ NPs for anatase and rutile phases. The PL is originated due to donor-acceptor recombination, whereas oxygen vacancies served as donor and hydroxyl groups serve as accepter sites. The NIR band is attributed to the trapped electrons in rutile TiO₂, which recombine with free holes and intrinsic defects. Also, the trapped electrons were generated in one of two ways: direct trapping or trap-to-trap hopping. The carrier dynamic in NPs depends on the trap states as the photoexcited carriers transfer into surface sites which competes with non-radiative and radiative recombinations during the relaxation process. Thus, the findings show that the trap states in TiO₂ can significantly influence TiO₂ photocatalytic activity when exposed to appropriate light.     

Origin of the High Permittivity and Varistor Behavior in SnO2–Zn2SnO4 Composite Ceramics

SnO₂–Zn₂SnO₄ composite ceramics with a colossal dielectric permittivity and varistor behavior are prepared by traditional ceramic processing. By increasing bias voltage from 0 to 10 V at a low frequency (~10³ Hz) and at room temperature, the relative permittivity decreased rapidly from about 20 000 to several thousand, whereas the radius of the semicircle in the complex impedance decreased and the tail gradually disappeared. However, the peak height and the position of the imaginary part of the complex modulus in the spectra were independent of the applied DC voltage. The slope deduced from the bias voltage‐dependent straight lines of the double‐logarithmic imaginary permittivity spectra were constant with a value of ?0.63 at high frequencies and they decreased to ?1 at low frequencies. The results strongly indicate that a number of weekly trapped charges existed in the ceramic bulk. From the temperature‐dependent dielectric and electric modulus spectra, the trapped charge activation energy was about 0.32 eV, which may be associated with the oxygen vacancies. Based on the results, a modified equivalent circuit related to the colossal dielectric permittivity and varistor properties was proposed, in which a Warburg impedance was added in parallel with the resistance and capacitance.     

High-conducting Bi4V2−xFexO11-δ ceramics containing Fe2O3 nanocrystals: Structure and properties

The topography, structure, thermal, magnetic, and electrical properties of Bi₄V_2?xFe_xO_11-δ ceramics substituted with x = 0.5 and 0.7 Fe were studied. The microscope analysis showed the presence of iron-rich nanocrystals formed on the Bi-Fe-V-O grains. The X-ray diffraction studies confirmed that grains are built mostly of tetragonal Bi₄V_1.5Fe_0.5O_10.5 phase. Thermal properties analysis showed an order-disorder type γ ? γ? phase transition at a temperature of around 916 K, pronounced in samples doped with x = 0.5 Fe. The magnetic anomaly was observed in ceramics doped with x = 0.7 Fe which was assigned to Morin transition of Fe₂O₃. The conductivity was measured over a wide frequency range from 10 mHz to 1 MHz and at a wide temperature range from 373 to 923 K, using impedance spectroscopy. The D.C. conduction process was due to oxygen vacancies hopping while at low temperatures electron holes hopping is also possible.     

Mechanisms of the relaxations in (In + Nb) co-doped TiO2 ceramics

(In_0·5Nb_0.5)_0.1Ti_0·9O₂ ceramic sample was prepared by sol-gel method. The dielectric properties of this sample were investigated in a temperature range of 5–320 K. Two thermally activated relaxations were found. The low-temperature relaxation (P0-relaxation) appearing around 50 K follows the Vogel-Fulcher law and is ascribed to be a low-temperature Maxwell-Wagner relaxation caused by frozen electrons. The intermediate-temperature relaxation (P1-relaxation) occurring around 150 K obeys the Arrhenius law. Thermally activated depolarization current (TSDC) investigations reveal that it contains two relaxation processes (P1’ and P1 peaks). This relaxation was argued to be a polaronic relaxation caused by electrons hopping between Ti³⁺ and Ti⁴⁺ ions. TSDC also reveals a high-temperature relaxation (P2 peak) near room temperature, which is related to humidity sensing property.     

Influence of Co concentration on the structural,optical, morphological and photo-diode properties of cerium oxide thin films

Highly uniform and well-dispersed ring shaped particles of CDC (Cobalt doped cerium oxide) films are successfully deposited by Nebulizer Spray Pyrolysis (NSP) technique. The structural, morphological, optical and photo-diode properties of the films are investigated. Cubic fluorite crystallites are detected by X-ray diffraction pattern with preferred orientation along (111) direction. Co concentrations distress the crystallinity and structural parameters. The transmittance decreases with increasing Co concentration due to the presence of covalent bonds between cerium and oxygen. PL spectra revealed that three consistent sharp and broad peaks observed at 369 (3.31 eV), 394 (3.14 eV) and 425 nm (2.91 eV) correspond to near-band-edge emission (NBE) in UV region, deep level emission (DLE) in violet and blue of the visible region respectively. The deep level emissions result from the recombination of electrons with holes trapped in singly ionized oxygen vacancies (Vo+). Large agglomerated ring, button and spherical crystallites are obtained with the typical size in the range 83–207 nm. XPS analysis exhibits the presence of Ce, Co, O, C and Na in the films that indicates the non-stoichiometric behavior. I-V characteristics show the rectifying nature with a typical forward to reverse current ratio of ~7 in the range −4 to +4 V. The turn-on voltage of the hetero-junction is found to be ~1.7 V. The transient photocurrent behavior indicates that the device has a good stability and quick response to suggests that the prepared heterojunction device can be used as a white light photodetector and UV detector applications.     

Vibronic spectra of europium in the X-ray storage phosphor polycrystalline cesium bromide

Cesium bromide doped with europium is a second-generation X-ray storage phosphor used in radiographic imaging. X-irradiation generates free electrons and holes, some of which are trapped at lattice defects and impurities. Irradiation with visible (red) light frees the electrons from their traps and they can recombine with the trapped holes, with the energy of recombination appearing as blue luminescence from the europium ion. Although the electron trap is widely held to be a bromine vacancy, the nature of the hole trap is as yet undetermined. Here we report on the remarkable sharp-line photoluminescent emission of Eu²⁺ ions which appears below 50 K in activated europium-doped cesium bromide and comprises over 20 individually resolvable lines. These patterns of vibronics may give some insight into the nature of the hole trap. A detailed analysis shows that the vibronics comprise five separate patterns, but with a common vibrational frequency of ~123 cm ^{− 1}. The vibronic patterns are attributed to Br₂ ⁻ molecular ions adjacent to the europium ion. An interpretation of the observed spectra in terms of a Eu²⁺-Eu³⁺ ion pair charge compensated by two cation vacancies and a substitutional O^{2 −} ion is discussed.     

Origin of dielectric loss in Ba(Co1/3Nb2/3)O3 microwave ceramics

The microwave dielectric loss of stoichiometric and non‐stoichiometric Ba(Co_1/3Nb_2/3)O₃ ceramics have been measured from 2 to 300 K in magnetic fields ranging from 0 to 5 T using a dielectric resonator (DR) technique. The microwave absorption from spin excitations of unpaired d‐electrons in exchange coupled Co²⁺ ions dominate the loss of the Ba(Co_1/3Nb_2/3)O₃ ceramics at cryogenic temperatures. Two peaks in the loss tangent (tan δ) vs temperature relation from a distinctly different origin occur at 25‐30 K and 90 K, which increase in magnitude with increasing Co content in the bulk dielectric samples. Evidence that these peaks result from polaron conduction from hopping between Co²⁺ and Co³⁺ ions includes (i) the peak's observed temperature range; (ii) the decrease in peak intensity of approximately a factor of two in a large applied magnetic fields (5 T); and (iii) a strong correlation between the peak's magnitude and both the fraction of the minority Co³⁺ in the dominant Co²⁺ matrix and D.C. conductivity at elevated temperatures. A magnetic‐field independent high temperature peak with a maximum at 250 K dominates the room temperature microwave loss whose magnitude correlates with those of the low temperature peaks. This suggests that the defects responsible for carrier conduction play an important role in establishing the loss tangent at room temperature.     

High‐Temperature Dielectric Relaxation in Pb(Mg1/3Nb2/3)O3–PbTiO3 Single Crystals

We reported the dielectric properties of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ single crystal in the temperature range of 300–1073 K and the frequency range of 100 Hz–10 MHz. Our results showed the coexistence of both true‐ and pseudo‐relaxor behaviors in the crystal. The true relaxor behavior related to the paraelectric‐ferroelectric phase transition occurs at~423 K. The pseudo‐relaxor behavior appearing at~773 K was found to be related to oxygen vacancies. Further investigation reveals that the pseudo‐relaxor behavior has fine structure: it contains two oxygen‐vacancy‐related relaxation processes. The low‐temperature relaxation process is a dipolar relaxation created by the hopping motions of the oxygen vacancies, and the high‐temperature relaxation process is a Maxwell‐Wagner relaxation caused by the sample/electrode contacts.     

Synthesis and photoluminescence characteristics of blue‐green luminescent aluminum oxynitride

Aluminum oxynitride (AlON), which can be regarded a nitrogen‐stabilized cubic γ‐Al₂O₃, has attracted attention in terms of its good mechanical, chemical, and optical stability. Because of its optical inertness, however, photoluminescence (PL) emission from nominally pure AlON has not been carefully investigated and evaluated. In this work, we prepared visibly luminescent AlON by nitridation of γ‐Al₂O₃ under N₂ atmosphere without adding aluminum nitride (AlN) using a high‐frequency induction heating unit. The resulting AlON exhibits a broad PL emission in the blue/green spectral region under excitation with light of ~260 nm. In the luminescent AlON sample, the excitation and emission events will occur at different sites; the electron transfer from the excitation site to the emission site is preceded by the radiative recombination process. It has also been found that the PL peak wavelength shows an anomalous blue shift by ~50 nm with increasing temperature from 78 to 500 K. The observed temperature dependent PL characteristics are governed by thermalization among multiple emitting levels. Aluminum vacancies and oxygen vacancies, both of which are introduced into the crystalline lattice during nitridation without the presence of AlN, are very likely candidates for the excitation and emission centers, respectively. Hence, the present direct nitridation method provides a simple and effective way to add an additional optical functionality to otherwise optically inactive AlON.     

Polarization Response and Thermally Stimulated Depolarization Current of BaTiO3‐based Y5V Ceramic Multilayer Capacitors

Polarization response and thermally stimulated depolarization current (TSDC) of BaTiO₃‐based ceramic multilayer capacitors with Y5V specification were studied. The temperature dependence of dielectric behavior shows that as the dc electric field increases, the polarization response in the whole measurement range (from ?125°C to +350°C) is suppressed. As the temperature rises to about 250°C, dielectric loss significantly increases and has a dependence on dc electric field, due to the leakage behavior at high temperature. According to the hysteresis loops, the calculated electrostatic energy density and energy efficiency are also closely related to polarization‐electric field. Utilizing a fixed measuring polarization condition, two TSDC relaxation peaks are observed and both are associated with oxygen vacancies. It is demonstrated that the weak peak originates from the in‐grain migration of oxygen vacancies and the strong peak with high relaxation temperature is caused by the across grain‐boundary oxygen vacancies. The activation energy estimated for the relaxation of oxygen vacancies across grain boundaries is about 0.78 eV. The main contribution for the leakage behavior is from the across grain‐boundary relaxation of oxygen vacancies. With increasing of temperature and electric field stress, the extrinsic oxygen vacancy defects show more fluent migration, which eventually leads to the resistance degradation and breakdown.     

Microstructure and superconducting properties of bulk EuBCO-Ag with and without holes

Bulk single-grain EuBCO-Ag superconductors with holes and without holes grown using a top-seeded melt-grow process are analysed. It turns out that the levitation force and the trapped magnetic field at 77 K are higher for the sample with holes (0,85 N and 1 T for the sample with a diameter of 28 mm and a height of 10 mm). Careful complex microstructural analyses undertaken by polarised light optical microscopy and scanning electron microscopy show that the reason for this behaviour is mainly the lower porosity of the sample with holes and the lower density of the of a/c-oxygenation cracks in non-porous areas along the holes. It also appears that other microstructural features, such as higher volume fraction of Eu₂BaCuO₅ particles in the a-growth sector than in the c-growth sector, uniform distribution of Ag particles in samples, presence of tetragonal EuBa₂Cu₃O_7?x regions are similar on both types of samples and cannot significantly affect macroscopic superconducting properties. The influence of porosity on the local critical current density and transition temperature is also illustrated.     

Structure and magnetic properties of Co3O4/SiO2 nanocomposite synthesized using combustion assisted sol-gel method

This paper reports on novel cobalt oxide nanoparticles (NPs) embedded in an amorphous silica (SiO₂) matrix, synthesized using a modified sol-gel method. SEM and TEM images show as-synthesized particles to aggregate in the shape of spheres and less than 5 nm in size, while XRD and SAED analysis both point to well crystallized cubic spinel cobalt oxide phase with an average crystallite size of about 4.6 nm. Raman analysis confirms the formation of cobalt (III) oxide (Co₃O₄) NPs. As-synthesized Co₃O₄ single-nanocrystallite has magnetic properties that correlate with finite size effects and uncompensated surface spins. Temperature dependence of ZFC-FC magnetization curves reveals a sharp peak around 10 K which corresponds to the blocking temperature. A Curie-Weiss behavior of magnetization above 25 K shows lower Néel temperature of the sample compared with its bulk counterpart T_N=40 K (possibly due to crystal defects and nano-dimensionality of the particles). The magnetic measurements exhibit high magnetization at low temperatures (M_S=54.3 emu/g) which can be associated with random canting of the particles’ surface spins and uncompensated spins in the core which tends to interact ferromagnetically at low temperatures. The initial magnetization curve falls out from the hysteresis loop at 5 K, which could be also the effect of surface spins.     

Synthesis and microstructure of single-crystalline cobalt oxyhydroxide and topotactic transformation to cobalt oxide

Plate-like cobalt oxyhydroxide (β-CoOOH, heterogenite) single crystals, with a width of ~5 mm and a thickness of ~100 μm, were successfully synthesized using a simple method of heating a mixture of Co₃O₄ and NaOH in air at 650°C, and then soaking the resultant crystals in water at room temperature. The crystals were topotactically formed from sodium cobalt oxyhydrate (Na_0.2(H₃O)_0.54CoO₂·0.48H₂O) by ion exchange between Na⁺ and H₃O⁺, and by intercalation of water molecules in the as-grown NaCoO₂ crystals. The sodium cobalt oxyhydroxide crystals had spherical nanopores with diameters of ~5 nm.     

Oxygen-vacancy-mediated microstructure and thermophysical properties in Zr3Ln4O12 for high-temperature applications

Yttria-stabilized zirconia (YSZ) has been considered as state-of-the-art material for high-temperature thermal barrier coatings, which provide thermal insulation to the superalloy components in gas turbines and jet engines. Oxygen vacancies induced by yttria substitutions are believed to be mainly responsible for the low thermal conductivity of YSZ due to their phonon scattering effect. However, high mobility of oxygen vacancies in YSZ leads to a rapid oxygen diffusion at high temperatures, therefore accelerates the failure of coatings by grain coarsening, sintering, and simultaneous oxidation of the underlying metallic bondcoat. In the present research, we further explored in the ZrO₂–Ln₂O₃ binary phase diagram and synthesized a series of ceramic materials with the chemical formula of Zr₃Ln₄O₁₂ (Ln = La, Gd, Y, Er, and Yb), in which more oxygen vacancies were involved and extremely low phonon thermal conductivities (1.3-1.6 W/m·K) were obtained, even approaching to the theoretical minimum. In addition, the mobility of these oxygen vacancies was remarkably suppressed by the lattice ordering with the decrease of Ln³⁺ radius, as confirmed by X-ray diffraction, Raman and transmission electron microscopy. Thus, the oxygen barrier property and sintering resistance were significantly enhanced accordingly, which makes Zr₃Ln₄O₁₂ compounds promising thermal barrier coating materials for next generation gas turbines and jet engines.     

The influence of processing methods on the dielectric properties of BaTi1-xGdxO3-x/2 - Based materials

In this study, the intermediate rare-earth oxide Gd₂O₃ (Gd) was substituted in different amounts (x = 0.2–2 mol%) for the formulation of BaTi_1-xGd_xO_3-x/2 (BTG_x) dielectric materials. The effect of B-site substitution was confirmed by the additional Raman active A_1g octahedral peak at ~835cm^-1 strengthened at x ≥ 0.4 mol%. Additionally, properties of 0.9BTG_0.007-0.1BA dielectric ceramics were analysed based on the influence of various processing methods as a function of sintering temperature. The focal samples were labelled Method-A (direct-mix) and Method-B (indirect-mix). As the sintering temperature (1075–1200 °C) increased, the 1 kHz response of the ε–T curves of Method-A samples transformed from a single peak to broad-narrow double peaks of high dielectric loss tangent (tan δ). Nonetheless, samples of Method-B possessed a clearly defined transmission electron microscopy (TEM) core-shell structure, flattened double-peak ε-T curves, optimised dielectric properties (ε = ~1563–1851 and tan δ < 1.5% at room temperature), and a wide-ranging temperature behaviour that meets the X8R dielectric standards (ΔC/C_25°C < ±15%). The maximum dielectric breakdown strength of Method-B samples reached ~131 kVcm, while the energy storage density was ~0.726 J/cm³ at a maximum efficiency of ~80% at 1100 °C. Thus, exhibiting good potentials for balancing temperature stability with energy storage applications.     

Mechanism and Kinetics of Oxidation of ZrN Ceramics

Oxidation of ZrN ceramics from 973–1373 K under static conditions reveals parabolic rate behavior, indicative of a diffusion‐controlled process. In‐situ high temperature powder XRD found the oxidation mechanism begins with destabilization of ZrN through formation of a ZrN_1?x phase with oxide peaks initially detected at around 773 K. The zirconium oxide layer was found to be monoclinic by in‐situ XRD with no evidence of tetragonal or cubic polymorphs present to 1023 K. Bulk ceramic samples oxidized at 1173 and 1273 K underwent slower oxidation than those oxidized at 973 and 1073 K. This change in oxidation rate and hence mechanism was due to formation of a denser c‐ZrO₂ polymorph stabilized by nitrogen defects. This N‐doped dense ZrO₂ layer acts as a diffusion barrier to oxygen diffusion. However, at an oxidation temperature of 1373 K this layer is no longer protective due to increased diffusion through it resulting in grain boundary oxidation.     

Magnetic and phonon transitions in B-site Co doped BiFeO3 ceramics

Magnetic susceptibility and phonons have been characterized in multiferroic Bi(Fe_1−xCo_x)O_3−δ ceramics for x=0.0, 0.05, and 0.10 (BFO100xCo) as functions of temperature. A preferred (100) crystallographic orientation and increasing average oxygen vacancies were observed in BFO5Co and BFO10Co. The Fe and Co K-edge synchrotron X-ray absorptions revealed mixed valences of Fe³⁺, Fe⁴⁺, Co²⁺, and Co³⁺ ions in BFO5Co and BFO10Co, which exhibit a ferromagnetic (or ferrimagnetic) phase below room temperature due to appearance of ferromagnetic B–O–B (B=Fe and Co) superexchange interactions. Field–cooled (FC) and zero–field–cooled (ZFC) magnetic susceptibilities exhibit a significant spin-glass splitting below room temperature in BFO5Co and BFO10Co. Two Raman-active phonon anomalies at ~170 K (or 200 K) and ~260 K were attributed to the Fe³⁺–O–Co³⁺ and Co³⁺–O–Co³⁺ magnetic orderings, respectively. This work suggests that the low-spin Co²⁺–O–Co²⁺, Fe³⁺–O–Fe³⁺ (or Fe⁴⁺), and high-spin Co²⁺–O–Co²⁺ superexchange interactions are responsible for phonon anomalies at ~290 (or ~300 K), ~400, and ~470 K (or ~520 K) in BFO5Co and BFO10Co.     

Radioluminescence,thermoluminescence and dosimetric properties of ZnO ceramics

Two types of ZnO ceramics were fabricated and characterized by XRD, SEM methods. The radioluminescence spectra were measured within the 300–550 K range. The defect luminescence band peaking at ~2.35 eV is the dominant one in radioluminescence spectra in both of the fabricated ceramics. The thermostimulated luminescence (TSL) glow-curves were measured after X-ray irradiation at 300 K. It was concluded that the complex overlapping peak within the 320–450 K temperature range consists of two components (~360–375 K and 400–420 K). The ratio of component intensities differs in both ceramics. The positions of high temperature TSL components (480–520 K) also differ in both samples; therefore not only sintering conditions but also the properties of the initial powder are very important for characteristics of TSL. A linear dependence of peak intensity on irradiation dose was observed up to ~3 kGy for ceramic 1 and up to 9 kGy for ceramic 2.