Ionic conductivity and point defects in pure and doped MnF2 and MgF2 single crystals

Conductivity, σ, of MnF₂ and MgF₂ single crystals, pure and doped (with Li⁺, Na⁺, Y³⁺, Gd³⁺), has been measured, from room temperature to 500°C. Further, some crystals were contaminated with O^2? as an additional impurity. These tetragonal (rutile structure) crystals both behave like typical ionic conductors. Of particular interest is the existence of a large anisotropy, σ being largest when measured parallel to the c-axis. Study of the conductivity isotherms and anisotropy as functions of impurity concentration allows identification of the conduction mechanism in terms of the migration of two mobile defects: the fiuorine-ion vacancy, V_F, and interstitial, F_i. A value of 1.44 eV was obtained for the enthalpy of formation of the intrinsic anion Frenkel defect, 0.80 eV for the migration enthalpy of a V_F and 0.88 eV for an F₁ in MnF₂ parallel to the c-axis. Similar values were obtained for MgF₂. This work shows that more information about point defects can be obtained from conductivity measurements in non-cubic cyrstals than in cubic ionic crystals, because of the additional information from conductivity anisotropy.     

LISICON(锗酸锌锂)单晶的Li+离子电导

本文研究了Lisicon(锗酸锌锂)单晶的Li⁺离子电导率。发现各结晶学方向电导率之间的关系为σ_b≤σ_a≤σ_c≤σ_[110],但各向异性不强。晶体中Li含量对电导率有明显的影响,当Li/Zn比率由6.7变到9.2时,300℃a方向电导率由4.3×10^-2Ω^-1·cm^-1增加到1.25×10^-1Ω^-1·cm^-1,logσT对1/T的曲线显示出三个转变点,分别在～80℃,～140℃和～300℃。电导的激活能分别为0.50—0.58eV(25—80℃),0.92eV(～80—140℃),0.64eV(～140—300℃)和0.36eV(>300℃),极化实验表明单晶的电子电导可以忽略。 关键词：     

Preparation, crystal structure, and electrical properties of thallium monosulfide in the vicinity of high-temperature phase transitions

Single crystals of thallium monosulfide TlS with excess sulfur (4 at. %) are grown. The existence of monoclinic (of the TlGaSe₂ type), tetragonal ordered (of the TlS type), and subtetragonal phases of thallium monosulfide is revealed using x-ray powder diffraction. The temperature dependences of the electrical conductivity and permittivity of thallium monosulfide single crystals indicate that, in the temperature range 401–411 K, these crystals undergo a phase transition to a state with superionic conduction.     

Lattice defects in CaF2 and SrF2 after proton irradiation

The time differential perturbed angular distribution method (TDPAD) has been applied to investigate the electric field gradient produced by radiation induced defects in the cubic lattices of CaF₂ and SrF₂. In mixed crystals of the alkaline-earth difluorides CaF₂ or SrF₂ and the rare earth trifluorides PrF₃, NdF₃ or SmF₃ the amplitudesA ₂₂ ^exp in the TDPAD spectra strongly depend on the rare earth trifluoride concentration. From the fact that the observed amplitudes are well described by a simple statistical model the conclusion can be drawn that the defects produced in CaF₂ and SrF₂ after proton irradiation are F^? interstitials.     

The contribution of anion disorder to ionic conductivity on single crystals of β-PbF2

The effect of the different cooling processes on the disorder of flourine ions and ionic conductivity in β-PbF₂ has been studied by X-ray method and ionic conductivity measurements on single crystals below the transition temperature T_c. The spike-like diffuse scattering was observed along the <111>¹ directions around the Bragg reflections. The activation energies for the conduction process are 0.40 eV for the sample quenched from 970 K and 0.54 eV for the one from 720 K. The higher the quenching temperature is, the higher the conductivity and the lower the activation energy become. The dependence of conductivity on the different cooling processes is more evident in single crystals than in polycrystalline samples. The contribution of the different cooling processes to ionic conductivity can be quantitatively explained by the extent of ordering of mobile fluorine ions. Time dependence of ionic conductivity has not been observed.     

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.     

Ionic conductivity study of CaF2: Nd single crystals

The electrical ionic conductivity of unirradiated and irradiated CaF₂: Nd crystals in the range of 60 to 800°C has been measured. The conductivity plot is basically divided into four parts, i.e., intrinsic and extrinsic unassociated, extrinsic associated, and extrinsic segregated regions. Activation energy (for unirradiated samples) in the extrinsic unassociated region is in the range of 0.69 to 1.20 eV depending on the doping concentration while for the intrinsic region, it is of the order of 1.89 eV. The conductivity in the extrinsic unassociated region increases with increase of Nd content in the sample. Also, the conductivity in the extrinsic region forγ-irradiated sample is higher than that for unirradiated one. In the intrinsic region, however, the conductivity is independent of dopant concentration orγ-irradiation. From these results it is surmised thatF ⁻ interstitials are the charge carriers in this region for CaF₂: Nd³⁺ system.     

Phase transitions in CuBiP2Se6 crystals

Investigation results of dielectric (20?Hz–1?MHz) properties of layered CuBiP₂Se₆ crystals are presented. The temperature dependence of the static dielectric permittivity reveals the first-order “displacive” antiferroelectric phase transition at T _c?=?136?K. In the paraelectric phase, at low frequencies, dielectric spectra are highly influenced by the high ionic conductivity with the activation energy of 2473?K (0.21?eV). In the antiferroelectric phase the electrical conductivity and its activation energy (531.1?K (0.045?eV)) are considerably smaller. At low temperatures, the temperature behaviour of the distribution of relaxation times reveals complex freezing phenomena. A part of long relaxation time distribution is strongly affected by external direct current (DC) electric field and it is obviously caused by antiferroelectric domain dynamics.     

Thermally stimulated depolarization currents and ionic conductivity of cubic lead fluoride containing small rare earth ions

Abstract

This work is concerned with thermally stimulated depolarization current (TSDC) and ionic conductivity studies in lead fluoride containing the small rare earths Dy, Ho, Er and Yb. The TSDC scans from 80 to 300 K show two peaks. For Pb_1?xEr_xF_2+x one is located at 106 K, and another, which is much stronger, occurs at about 160 K. The former is associated with a dipolar defect containing at least two rare earths and the latter is attributed to the development of F^? space charge during polarization of the sample. The activation energies obtained from both the high temperature TSDC peak and the ionic conductivity are the same, which corroborates the latter assignment. In addition, the ionic conductivity is shown to be independent of concentration. Those results can be understood of rare earth clustering, which is either absent or is unobservable dielectrically for large rare earths such as lanthanum, occurs extensively even at very low concentrations of the small rare earths. The explanation is that the majority of fluorine charge compensators are trapped by clusters.     

Ionic conductivity in the single crystals of non-stoichiometric fluorite phases M1−xRxF2+x (M=Ca,Sr, Ba; R=Y,La-Lu)

The ionic conductivity has been measured of single crystals of rare earth fluoride solid solutions in Ca, Sr and Ba fluorides described by the formula M_1?xR_xF_2+x (M=Ca, Sr, Ba; R=Y, La-Lu). The measurements have been done using dc and ac within the temperature range 300–850 K. With the increase of RF₃ concentration up to x=0.05–0.15 (in different systems) conductivity steeply increases. With the further concentration growth the conductivity increases only slightly, reaching saturation value for the solid solution Ba_1?xR_xF_2+x. The dependence of solid solution conductivity on the chemical composition has been studied for isoconcentrates M_0.9R_0.1F_2.1. It has been established that in CaF_2- based series the crystals with R=Gd, Tb possess maximum conductivity and minimum activation energy. For SrF₂ and BaF₂-based series the highest conductivity was observed for crystals containing LaF₃. It has been established that for all the crystals, independent of the chemical composition and defect concentration, the conductivity logarithm at definite temperature linearly depends on the activation energy. Within the investigated class of substances the optimum composition for solid electrolytes is Sr_0.69La_0.31F_2.31.     

Ionic conductivity of lithium nitride doped with hydrogen

Lithium ionic conductivity of Li₃N single crystals is reported for temperatures from 120 K to 350 K. The intrinsic ionic conductivity is rather small (< 10^?6 Ω^?1 cm^?1 at 300 K) and shows no strong anisotropy. The activation energy is near 0,6 eV. It is shown that hydrogen is the critical impurity in the crystals grown and studied at this laboratory. The relative impurity concentration is determined from infrared transmission measurements near 3130 cm^?1. An estimate for absolute values is obtained from dielectric studies. Increases in ionic conductivity with hydrogen doping by a factor 5000 are reported for E⊥c but no significant effects are found for E6c. The proposed defect is an impurity-vacancy complex consisting of an NH^?? and a lithium vacancy.     

Synthesis and ionic conduction of apatite-type materials

Apatite is a mineral with general formula M₁₀(XO₄)₆Z₂, where M are metallic elements such as Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ln³⁺ etc.; X=P, V, S, Si, Ge, Re, Cr etc; Z=F⁻, Cl⁻, I⁻, OH⁻, O²⁻, S²⁻ etc. Some materials with apatite structure (S.G. P6₃/m) exhibit quite high cationic (Li⁺, H⁺ etc.) and/or anionic (F⁻, Cl⁻ etc.) conduction. Recently, it was reported that some rare earth silicates, e.g., La₁₀(SiO₄)₆O₃, exhibit quite high oxide-ion conductivity. In this paper, we discuss chemical composition, structure, synthetic procedure and ionic conduction of apatite-type materials. Recent improvements are briefly reviewed. High ionic conductivity has been observed for both cation deficient, oxygen stoichiometric La_9.33(SiO₄)₆O₂ and cation stoichiometric, oxygen excess La₁₀(SiO₄)₆O₃ compositions. Grain boundary conductivity is usually low, which tends to dominate the impedance response. The resistance, particularly the grain boundary resistance is also found to depend on pO₂. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

纳米CaF2和纳米Ca0.75La0.25F2.25的结构对离子电导率的影响

用惰性气体蒸发和真空原位加压方法制备了两种具有清洁界面的纳米离子固体CaF₂(平均粒度为16nm)和Ca_0.75La_0.25F_2.25(平均粒度为11nm),在31℃至530℃详细测量了其复阻抗谱。结果表明:1)在300—530℃两种纳米离子导体都很好地遵从Arrhenius方程式;2)纳米CaF₂的离子电导率比多晶CaF₂约高1个数量级、比单晶CaF₂     

Luminescence and ionic conductivity of bariumfluorochloride

The luminescence and ionic conductivity of pure and doped BaFCl crystals are reported. The ionic conductivity occurs mainly via chloride ion vacancies, whereas the efficient, yellow luminescence is ascribed to oxygen impurities (O′_F).     

Conductivity enhancement in fluorite-structured Ba1−xLaxF2+x solid solutions

The ionic conductivity of single crystals of the fluorite-structured solid solutions Ba_1?xLa_xF_2+x(10^?3 <×<0.45) has been studied as a function of temperature and composition in the range 300–900 K. Three regions can be discerned in the concentration dependence of the ionic conductivity: a dilute concentration region (x<10^?3), where classic relations between solute content and ionic conductivity hold; an intermediate concentration region (10^?3<x?5×10^?2), where large changes occur in the conductivity activation enthalpy and the magnitude of the conductivity; and a concentrated solid solution region (x?5×10^?2) characterized by enhanced ionic motion. In the dilute region the migration enthalpy for interstitial fluoride ions is determined to be 0.714 eV, while a value of 0.39 eV is found for the (La_BaF_i)^X association enthalpy. The defect chemistry in the intermediate concentration region is shown to be controlled by a superlinear increase of the concentration of mobile defects, while in the concentrated solid solution region a composition-independent amount of ≈1 mole% of interstitial fluoride ions with enhanced mobility, carry the current.     

Dielectric spectroscopy study of the new compound [C<Subscript>12</Subscript>H<Subscript>17</Subscript>N<Subscript>2</Subscript>]<Subscript>2</Subscript>CdCl<Subscript>4</Subscript>

The temperature dependence of the electrical conductivity of the compound 2,4,4-trimethyl-4,5-dihydro-3H-benzo[b] [1,4] diazepin-1-ium tetrachlorocadmiate in the different phases follows the Arrhenius law. The imaginary part of the permittivity constant is analyzed with the Cole–Cole formalism. In the temperature range 348–394 K, the activation energy of conductivity obtained from complex permittivity in regions I and II are, respectively, 1.03 and 0.33 eV, and E _m (in regions I and II are, respectively, 0.97 and 0.36 eV) obtained from the modulus spectra is close, suggesting that the ion transport is probably due to a hopping mechanism. The Kohlrausch–Williams–Watts function, j(t) = exp( - ( \fractt_\textKWW )^b ) \varphi (t) = \exp \left( { - {{\left( {\frac{t}{{{\tau_{\text{KWW}}}}}} \right)}^\beta }} \right) , and the coupling model are utilized for analyzing electric modulus at various temperatures. The decreasing of β at 373 K is due to approaching the temperatures of change in the conduction mechanism of the sample.     

One-dimensional ionic conduction in solid Ag2 Tl6I10

The ionic and electronic conductivities of Ag₂Tl₆I₁₀ single crystals have been studied as a function of crystallographic orientation and temperature from 20 to 135°C. EMF as well as AC and DC techniques have been employed. The highly anisotropic material is predominantly an Ag⁺-ion conductor parallel toc-direction, with the Ag⁺ ions moving through linear channels that are not interconnected. The conductivity σ_‖c =1.6×10⁻⁷Ω⁻¹cm⁻¹ at 25°C, with an activation enthalpy for σ_‖c of 0.38 eV. The conduction perpendicular toc-direction has been found to be predominantly electronic with a value of σ_⊥c =3×10⁻⁹Ω⁻¹cm⁻¹ at 25°C and an activation enthalpy for σ_⊥c of 0.64 eV. This is the first observation of one-dimensional Ag⁺ conduction and this type of orientation-dependent change from ionic to electronic conduction. On leave from Institute of Physics, Academia Sinica, Peking, China.     

Electrical properties of heavily doped fluorite-structured BaF2:RF3 (R=La, Pr, Nd, Gd, Tb, Y, Sc) single crystals

The superionic conductivity and dielectric response of heavily doped fluorite-structured Ba_1−xR_xF_2+x (R=La, Pr, Nd, Gd, Tb, Y, Sc; x=0.005–0.45) crystals are reported. The highest ionic conductivity is found for R=Sc and x=0.1. Upon ScF₃ doping, small Sc³⁺ ions rearrange their surroundings, create excessive fluoride interstitial ions and bring about a high ionic conductivity. For each dopant, the concentration dependence of the ionic conductivity is non-linear. A monotonous concentration dependence of the ionic conductivity is found only for La³⁺ doping. Upon doping with Nd³⁺, Gd³⁺, Tb³⁺, Y³⁺ and Sc³⁺ ions, a conductivity maximum is observed at x=0.1–0.2. Upon Pr³⁺ doping, this maximum is split. The influence of defect clustering on the concentration dependence of the conductivity is discussed. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Anisotropic properties of self-flux grown LiB3O5 single crystals

In this paper, we report the existence of anisotropic behavior along the crystallographic axes in optical, electrical and thermal properties of lithium tri borate, a recently developed vacuum UV-NLO material. The variation of refractive index with the wavelength along the crystallographic axes was investigated by prism coupling method. The results of impedance spectroscopy measurement reveal the presence of a strong anisotropy in ionic conductivity and dielectric constant along the axes and also show the super-ionic conduction behavior along the c-axis with the activation energy of Δ∼0.20 eV. A thermo-mechanical study in the temperature range of 300-900 K indicates the existence of a strong variation in the linear thermal expansion coefficient (positive value along the a-axis, and negative value along the c-axis) of LiB₃O₅ crystals.     

Electrical and optical properties of CuIn5S8 single crystals

Summary Several transport and optical properties have been studied onn-type CuIn₅S₈ single crystals. The energy gap at 0 K was determined from the electrical measurements to be 1.4 eV. An anisotropy of the magnetoresistance effect was found and it was suggested that the minima of the conduction band were located at points along the [100] directions ink-space. An optical-absorption band was found in an infrared region of (1÷1.6) μm and was attributed to the transitions from the lowest conduction band situated along the [100] directions to an upper conduction band. Paper presented at the ?V International Conference on Ternary and Multinary Compounds?, held in Cagliari, September 14–16, 1982.