Light-induced intrinsic defects in PLZT ceramics

This paper reports on an EPR study of a ferroelectric, 1.8/65/35, and an antiferroelectric, 2/95/5, of optically transparent Pb_1?y La_yZr_1?x Ti_xO₃ (PLZT) ceramics within a broad temperature range (20–300 K) after illumination at a wavelength of 365–725 nm. Illumination with ultraviolet light, whose photon energy corresponds to the band gap of these materials, at T<50 K creates a number of photoinduced centers: Ti³⁺, Pb⁺, and Pb³⁺. It is shown that these centers are generated near a lanthanum impurity, which substitutes for both the Pb²⁺ and, partially, Ti⁴⁺ ions through carrier trapping from the conduction or valence band into lattice sites. The temperature ranges of the stability of these centers are measured, and the position of their local energy levels in the band gap is determined. The most shallow center is Ti³⁺, with its energy level lying 47 meV below the conduction band bottom. The Pb³⁺ and Pb⁺ centers produce deeper local levels and remain stable in the 2/95/5 PLZT ceramics up to room temperature. The migration of localized carriers is studied for both ceramic compositions. It is demonstrated that, under exposure to increased temperature or red light, the electrons ionized into the conduction band from Ti³⁺ are retrapped by the deeper Pb⁺ centers, thus hampering the carrier drift in the band and the onset of photoconduction. The part played by localized charges in the electrooptic phenomena occurring in the PLZT ceramics is discussed.     

Electrical conduction in ordered defect compounds

A comparative study of the temperature dependence of electrical resistivity, carrier concentration and carrier mobility of the Ordered Defect Compounds (ODCs) CuIn₃Se₅, CuIn₃Te₅, and CuIn₅Te₈ with their corresponding normal 1:1:2 phase is reported. Relatively lower carrier concentration and higher activation energy observed in ODCs is explained on the basis that shallow acceptor or donor levels observed in 1:1:2 phase are partially annihilated in these compounds due to attractive interaction between V_Cu⁻¹ and In_Cu⁺² defect pair. In the activation regime, the mobility is explained by taking into account a scattering mechanism of the charge carriers with donor–acceptor defect pairs. The electrical data at lower temperatures is explained with the existing theoretical expression for the nearest neighbor hopping conduction mechanism.     

Pressure and temperature dependences of the ionic conductivities of cubic and orthorhombic lead fluoride (PbF2)

A detailed study of the effects of temperature and hydrostatic pressure on the ionic conductivity of PbF₂ in both the cubic (Fm3m-O_h⁵) and orthorhombic (Pmnb-V_2h¹⁶) phases was performed with some emphasis on the changes in conductivity accompanying the transition between the two phases. Both phases exhibit relatively high conductivities and become supersonic conductors at high temperatures. As a function of temperature, the conductivity in both phases exhibits a number of activated regions (or stages). Measurements on a variety of samples with different impurities, along with earlier published data, have allowed a determination of the conduction mechanism in the various stages. The activation energies for the motion of F^? ion vacancies and interstittals as well as the formation energies of Frenkel defects in the two phases were determined. These energies are relatively small, compared, e.g. with other crystals having the fluorite structure (Fm3m-O_h⁵), and this can be explained in terms of the large dielectric constants and relatively soft phonons in PbF₂. The conductivity decreases with pressure in all stages, primarily as a result of the increase in activation energies. The pressure results allow a determination of the activation volumes associated with the various conduction mechanisms. The magnitudes of these volumes (～2–7 cm³/mole) are consistent with values determined from either the strain energy model or an approximate dynamical model. Differences in the activation volumes for the different conduction mechanisms and between the two phases can be qualitatively understood on the basis of the details of the crystal structures.     

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.     

Excitation and Emission Spectra of Cs2NaLnCl6 Crystals Using Synchrotron Radiation

ABSTRACT

The visible emission and vacuum ultraviolet excitation spectra of the series Cs₂NaLnCl₆ (Ln = Y, Nd, Sm, Eu, Tb, Er, Yb) and Cs₂NaYCl₆:Ln³⁺ (Ln = Sm, Er) have been recorded using synchrotron radiation at room temperature, and in some cases at 10 K. The excitation spectra comprise features associated with charge transfer, excitation from the valence to conduction band, and impurity bands. No d–f emissions were observed for these Ln³⁺ ions, so that the emission bands comprise intraconfigurational 4f ^N –4f ^N transitions and impurity bands, whose natures are discussed. Theoretical simulations of the f–d absorption spectra have been included. The comparison with data from the synchrotron at Desy enables a comprehensive account of the ground (or vibrationally excited ground for Ln²⁺) states of the Ln³⁺ 4f ^N , Ln³⁺ 4f ^N?15d, and Ln²⁺ 4f ^N+1 configurations relative to the valence and conduction bands of Cs₂NaLnCl₆, for which the band gaps are between 6.6 and 8.1 eV.     

Anisotropy of the hopping conductivity in TlGaSe2 single crystals

The temperature dependences of the conductivities parallel and perpendicular to the layers in layered TlGaSe₂ single crystals are investigated in the temperature range from 10 K to 293 K. It is shown that hopping conduction with a variable hopping length among localized states near the Fermi level takes place in TlGaSe₂ single crystals in the low-temperature range, both along and across the layers. Hopping conduction along the layers begins to prevail over conduction in an allowed band only at very low temperatures (10–30 K), whereas hopping conduction across the layers is observed at fairly high temperatures (T?210 K) and spans a broader temperature range. The density of states near the Fermi level is determined, N _F=1.3×10¹⁹eV·cm³)^?1, along with the energy scatter of these states J=0.011 eV and the hopping lengths at various temperatures. The hopping length R along the layers of TlGaSe₂ single crystals increases from 130 Å to 170 Å as the temperature is lowered from 30 K to 10 K. The temperature dependence of the degree of anisotropy of the conductivity of TlGaSe₂ single crystals is investigated.     

Interplay of spin-allowed and spin-forbidden 5d–4f luminescence from rare earth ions

The conditions for co-existence of emissions from spin-allowed and spin-forbidden 5d–4f transitions in rare earth ions and for thermal quenching of these emissions have been analyzed by taking Tm³⁺ 5d–4f luminescence in LiYF₄:Tm³⁺ and Lu³⁺ 5d–4f luminescence in LuF₃ as examples. It is shown that temperature behavior of 5d–4f luminescence agrees with the common trends in decreasing energy splitting between the lowest high-spin and low-spin 5d levels as well as decreasing energy gap between the lowest 5d level and the bottom of the conduction band of the host crystal towards heavier rare earth ions (from Er³⁺ to Lu³⁺).     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.     

Electronic conductivity and thermopower of Ca2NaMg2V3O12−x garnet

Results are reported from conductivity and thermoelectric power measurements on partially reduced Ca₂NaMg₂V₃O_12?x, with x < 5.10^?2, at temperatures of 300–1100 K. The conductivity is thermally activated with activation energies 0.26 ? E_a ? 1.28 eV for differently reduced samples. The thermopower is temperature independent in the 300–800 K region. These results are shown to be consistent with the adiabatic hopping of small polarons localised on the vanadium sublattice, where defect interactions result in the formation of multiple conduction pathways.     

Experimental thermal performance study of natural graphite as sensible heat storage material using different heat transfer fluids

In this paper thermal performance of graphite-based sensible heat storage system with embedded helical coil in rectangular shell was studied. Plain water at four flow rates (0.25 LPM–1.0 LPM) and four inlet temperatures (60°C–90°C) was passed through the graphite bed and charging time was measured. Expanded graphite/water suspension and Al₂O₃/water nanofluid were also used to study charging behavior of graphite. Results showed that charging time of packed bed was reduced with increase in flow rate and inlet temperature of heat transfer fluid. Charging time using expanded graphite/water solution and nanofluid was 14.2% and 21.2% lesser than water.

Abbreviations: h_i: internal heat transfer coefficient (W m^?2 K^?1); HTF: Heat transfer fluid; h_o: External heat transfer coefficient (W m^?2 K^?1); LPM: liter per minute; k: thermal conductivity (W m^?1 K^?1); TSU: Thermal storage unit     

Microwave-assisted rapid synthesis of tetragonal Cu2SnS3 nanoparticles for solar photovoltaics

A simple and rapid process for the synthesis of Cu₂SnS₃ (CTS) nanoparticles by microwave heating of metal–organic precursor solution is described. X-ray diffraction and Raman spectroscopy confirm the formation of tetragonal CTS. X-ray photoelectron spectroscopy indicates the presence of Cu, Sn, S in +1, +4, ?2 oxidation states, respectively. Transmission electron microscopy divulges the formation of crystalline tetragonal CTS nanoparticles with sizes ranging 2–25 nm. Diffuse reflectance spectroscopy in the 300–2,400 nm wavelength range suggests a band gap of 1.1 eV. Pellets of CTS nanoparticles show p-type conduction and the carrier transport in temperature range of 250–425 K is thermally activated with activation energy of 0.16 eV. Thin film solar cell (TFSC) with architecture: graphite/Cu₂SnS₃/ZnO/ITO/SLG is fabricated by drop-casting dispersion of CTS nanoparticles which delivered a power conversion efficiency of 0.135 % with open circuit voltage, short circuit current and fill factor of 220 mV, 1.54 mA cm^?2, 0.40, respectively.     

Different modes and consequences of electron transfer in intercalation compounds

Intercalation reactions form one of the most versatile types of solid-state reactions known. Considering the layered host lattices they form an interesting access to artificial multilayers of very different properties. Many of these reactions are connected with redox processes. After a very short and general overview on the intercalation chemistry in layered host lattices, three different types of charge transfer accompanied with intercalation will be considered in detail and the consequence for the properties of the products will be discussed: (a) by means of electrointercalation into conducting host lattices (e.g. 2H-TaS₂) electrons are transferred to the conduction band of the host accompanied with the simultaneous uptake of cations (here organic cations like methylene blue, methylviologen) in the interlayer space. Potential vs. time curves give valuable information about two-phase regions, homogeneity ranges and deviations from equilibrium. The consequence for the superconducting properties is shown; (b) treating the graphite intercalation compound C₂₄(HSO₄)(H₂SO₄) with strong oxidants leads to graphite oxide (GO). The oxidant is directly attached to the carbon network forming C–OH and C–O–C functions. Applying ¹³C MAS NMR of GO (and derivatives) we could identify the ether function as epoxide groups. This result has strong implications for the chemical behaviour of GO and could lead to new carbon networks; (c) clay minerals containing iron in the octahedral layers can undergo changes of the oxidation state of Fe-ions. We have found in vermiculites from Spain that Fe²⁺ can be oxidized completely to Fe³⁺, whereas the degree of reduction of the Fe³⁺ is rather restricted but varies with the composition of the clay. However, the extent of reduction can be strongly increased by heating the reduced samples.     

Electrical conduction and thermoelectric properties of perovskite-type BaBi1−xSbxO3

To elucidate the thermoelectric properties at high temperatures, the electrical conductivity and Seebeck coefficient were measured at temperatures between 423 K and 973 K for perovskite-type ceramics of BaBi_1?xSb_xO₃ solid solutions with x=0.0–0.5. All the ceramics exhibit p-type semiconducting behaviors and electrical conduction is attributed to hopping of small polaronic holes localized on the pentavalent cations. Substitution of Bi with Sb causes the electrical conductivity σ and cell volume to decrease, but the Seebeck coefficient S to increase, suggesting that the Sb atoms are doped as Sb⁵⁺ and replace Bi⁵⁺, reducing 6s holes conduction from Bi⁵⁺(6s⁰) to Bi³⁺ (6s²). The thermoelectric power factor S ²σ has values of 6×10^?8–3×10^?5 W m^?1 K^?2 in the measured temperature range, and is maximized for an Sb-undoped BaBiO_3?δ, but decreases upon Sb doping due to the decreased σ values.     

Charge transfer in TlFeS2 and TlFeSe2

The temperature dependences of the conductivity and the thermoelectric coefficient in TlFeS₂ and TlFeSe₂ samples have been investigated in the temperature range 85–400 K. The variable-range hopping conduction has been established. It is found that the density of localized states N _F near the Fermi level is 1.7×10¹⁸ and 3.3×10¹⁸ eV^?1 cm^?3, and the average hopping length R is 109 and 104 Å for TlFeS₂ and TlFeSe₂, respectively. The non-Arrhenius (activationless) behavior of the hopping conductivity is established in the temperature region T<200 K for TlFeS₂ and T<250 K for TlFeSe₂.     

Multiphonon relaxations in Ho3+:LaF3 single crystal

The mulliphonon transition rates in Ho³⁺:LaF₃ are estimated from the observed fluorescence decay rates of the states ⁵F₃ and (⁵F₄, ⁵S₂), in the temperature interval 80–675°K. The data is analyzed in terms of the existing theoretical models. The analysis indicates that the high energy phonons play a dominant role in these multiphonon transitions.     

Electrical transport characteristics of ZnO–Bi2O3–B2O3 glasses

Optically clear glasses in the ZnO–Bi₂O₃–B₂O₃ (ZBBO) system were fabricated via the conventional melt-quenching technique. Dielectric constant and loss measurements carried out on ZBBO glasses unraveled nearly frequency (1 kHz–10 MHz)-independent dielectric characteristics associated with significantly low loss (D?=?0.004). However, weak temperature response was found with temperature coefficient of dielectric constant 18?±?4 ppm °C^?1 in the 35–250 °C temperature range. The conduction and relaxation phenomena were rationalized using universal AC conductivity power law and modulus formalism respectively. The activation energy for relaxation determined using imaginary parts of modulus peaks was 2.54 eV which was close to that of the DC conduction implying the involvement of similar energy barriers in both the processes. Stretched and power exponents were temperature dependent. The relaxation and conduction in these glasses were attributed to the hoping and migration of Bi³⁺ cations in their own and different local environment.     

On the effect of SHI irradiation on dielectric properties of Y3+xFe5−xO12 (x=0.0–0.6) system

The present work aims to investigate the pre- and post-effect of 50 MeV Li³⁺ ion irradiation at a fluence of 5×10¹³ ions/cm² on the dielectric properties of Y_3+xFe_5?xO₁₂, x=0.0, 0.2, 0.4 and 0.6, garnet system over broad temperature, 300–673 K, and frequency, 100 Hz–13 MHz, ranges. Thermal variation of ac resistivity measurements suggests that the mechanism responsible for conduction in the system is polaron hopping. The observed modifications in dielectric properties after swift heavy ion irradiation are mainly due to the modifications of the metal–insulator contacts due to radiation damage-induced disorder and irradiation-induced point/cluster of defects in the material and also compressive strain generated in the lattice structure. The electric modulus presentation and the complex impedance spectral analysis have been employed to study the relaxation process. The YFeO₃ phase is found to be irradiation hard phase as compared with the garnet phase.     

Energy levels of rare-earth ions in Gd<Subscript>2</Subscript>O<Subscript>2</Subscript>S

The energies of the ground 4f ⁿ levels of tri- and divalent rare-earth ions with respect to the conduction and valence bands of Gd₂O₂S crystal has been determined. It is shown that the Pr³⁺, Tb³⁺, and Eu³⁺ ions can be luminescence centers in Gd₂O₂S. The levels of the Nd³⁺, Dy³⁺, Er³⁺, Tm³⁺, Sm³⁺, and Ho³⁺ ions lie in the valence band; therefore, these ions cannot play the role of activators. The ground 4f level of the Ce³⁺ ion is near the midgap, due to which Ce³⁺ effectively captures holes from the valence band and electrons from the conduction band and significantly decreases the afterglow level of the Gd₂O₂S:Pr and Gd₂O₂S:Tb phosphors.     

On the correlation between the magnetic structure and the electrical properties of EuB6

Single crystals of EuB₆ were prepared by the floating-zone method. Magnetic and electric measurements on these crystals in the temperature range 1.6–300 K revealed that the pure EuB₆ is an antiferromagnet with a Néel temperature of 5–6 K and has a carrier concentration of 4.2 × 10²⁰ cm^-3. It was found that in polycrystalline sample, defects of Eu ions reduce the carrier concentration and make the sample ferromagnetic. It is suggested that the conduction electrons in pure EuB₆ originate from the overlap of the 4f band tail and the conduction band.     

Effect of Li2O on the structure,electrical and dielectric properties of xLi2O·(20−x)CaO·30P2O5·30V2O5·20Fe2O3 glasses

Glasses of the general formula xLi₂O·(20?x)CaO·30P₂O₅·30V₂O₅·20Fe₂O₃ with x=0, 5, 10, 15 and 20 mol% were prepared; IR, density, electrical and dielectric properties have been investigated. Lithia-containing glasses revealed more (P₂O₇)^4?, FeO₆, V–O^? and PO^? groups and mostly have lower densities than those of lithia-free ones. The electrical properties showed random behavior by replacing Li₂O for CaO, which has been assigned to the change of the glass structure. The results of activation energy and frequency-dependent conductivity indicate that the conduction proceeds via electronic and ionic mechanisms, the former being dominant. The mechanism responsible for the electronic conduction is mostly thermally activated hopping of electrons from Fe(II) ions to neighboring Fe(III) sites and/or from V⁴⁺ to V⁵⁺. The dielectric constant (ε′) showed values that depend on the structure of glass according to its content of Li₂O. The (ε′) values are ranging between 3 and 41 at room temperature for 1 kHz, yet at high temperatures, glass with 20 mol Li₂O exhibits values of 110 and 3600 when measurement was carried out in the range 0.1–1 kHz, and at 5 MHz, respectively.