Structure and electrical behavior in air of TiO2-doped stabilized tetragonal zirconia ceramics

2 -doped YTZP ([%mol]3 Y₂O₃) compositions sintered in the temperature range of 1300 to 1450 °C, the tetragonal zirconia solid solutions field for the ZrO₂-Y₂O₃-TiO₂ system was established. The solubility of TiO₂ in YTZP was found to be about 12–[%mol]14 at 1450 °C. Structural characterization of the Ti-YTZP tetragonal zirconia solid solutions was carried out using X-ray absorption spectroscopy (EXAFS and XANES) to provide information on the environment of Ti atoms. The electrical behavior in air of the TiO₂-doped tetragonal zirconia solid solutions was studied by impedance spectroscopy in the temperature range of 300 to 800 °C, and it was found that the ionic conductivity decreases with increasing titania content. EXAFS and XANES results show that as the Ti⁴⁺ ions dissolve into the tetragonal zirconia YTZP matrix, a displacement of Ti ions from the center of symmetry takes place, leading to a non-random substitution of Ti⁴⁺ ions on Zr⁴⁺ lattice sites. Ti-O bond distances derived from EXAFS indicate that the Ti ion can be in a square-pyramidal arrangement, i.e., fivefold oxygen-coordinated. As a consequence two kinds of cation–oxygen vacancy associations are created; the high-mobility oxygen-vacancy–eightfold-coordinated cation (Zr⁴⁺) and the low-mobility oxygen-vacancy–fivefold-coordinated cation (Ti⁴⁺). This results in a decrease in the global concentration of moving oxygen vacancies and, therefore, in a decrease of the electrical conductivity. Received: 1 April 1998/Accepted: 28 September 1998     

Thermogravimetric and electrical study of non-stoichiometric titanium dioxide TiO2−x, between 800 and 1100°C

By means of thermogravimetrie and electrical measurements, it has been possible to give accurate informations on the nature of the defects produced by reduction of TiO₂ between 800 and 1100°C. For small partial pressures of oxygen P_o2. interstitial titanium Ti⁴_i prevails at temperature higher than 900°C. When P_O2 increases, oxygen vacancies are produced at first in the doubly ionized form V″_o and a progressive transition to singly ionized vacancies V″_o can be assumed. The formation enthalpies associated with these defects as calculated from our experimental results are 10.1 eV for Ti⁴_i, 4.6 eV for V″_o and 3.6–4.0 eV for V′_o. The electronic drift mobility μ is independent both of nature and concentration of the defects. The shape of its temperature dependence leads to conclude that the conduction in spite of the low μ value (0.06 cm² V^?1 s^?1 at 1100°C) is of the classical type for wide band semiconductors and not a hopping process.     

Generation of dangling bonds by high temperature annealing and hopping conduction in amorphous silicon films

By annealing evaporated a-Si films between 450°C and 620°C, it is found that new dangling bonds are generated. These dangling bonds can act as hopping centres. Quantitative analysis of experimental results on electrical resistivity and ESR measurements favours a conduction mechanism of hopping to nearest neighbours between room temperature and ?100°C. Films annealed just before crystallisation temperature have a density of states near Fermi level of about 3 × 10¹⁸ cm^?3 eV^?1.     

Stochastic PAC models for vacancy motions with trapping and detrapping

In order to explain PAC data for tetragonal zirconia at temperatures between 900 and 1300oC, we have developed a four-state stochastic model. The model simulates vacancies which trap and detrap at a PAC probe nucleus. While trapped, the vacancies hop around the probe in equivalent sites. The four states in this Winkler–Gerdau stochastic theory are three trapped states with equivalent electric field gradients (EFGs) of different orientations and a detrapped state with a weaker EFG whose axis of symmetry is oriented along the diagonal between the three trapped EFGs. There are three hopping rates in this model: w, the rate a trapped vacancy hops around the probe, w_D, the detrapping rate, and w_t, the trapping rate. We report results of calculations for values of these hopping rates implied by our tetragonal zirconia data, and we report heuristic fitting functions which summarize the computer results and can be used to fit data efficiently for a wide range of parameters. This revised version was published online in August 2006 with corrections to the Cover Date.     

181Ta gamma-gamma angular correlation study of oxygen self-diffusion in heavily defective oxides

The results of gamma-gamma angular correlation experiments performed on the ¹⁸¹Ta nucleus in calcia-and yttria-stabilized zirconias and in calcia-doped cerias between 20–1150°C are reported. At high temperatures, the angular correlation spectra indicate a relaxation of the ¹⁸¹Ta spins induced by the diffusive motions of oxygen vacancies. The slow and fast relaxation regimes are successively observed when the temperature is raised. The behaviour of the relaxation constant is fairly well reproduced by assuming the existence of fluctuations in the potential energy barrier which controls the migration of oxygen vacancies. For stabilized zirconias the mean activation energies deduced from angular correlation experiments agree with the conductivity data. The disagreement observed in doped cerias is attributed to impurity effects produced by the ¹⁸¹Ta probe itself. The local investigation of oxygen self-diffusion give evidence for the homogeneous behaviour of these highly defective oxides at a microscopic level. The ¹⁸¹Ta relaxation data, especially the comparison of the respective data relative to aged and deaged calcia-stabilized zirconia, strongly suggest the existence of short-range ordering phenomena in these solid solutions.     

Electrical characterization of porous La-doped BaSnO<Subscript>3</Subscript> using impedance spectroscopy

A few compositions in the system Ba_1???x La _x SnO₃ (x?=?0.00, 0.01, 0.05, and 0.10) have been synthesized via the solid state ceramic route. The synthesized powders have been characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, Raman spectroscopy, Fourier transformation infrared, thermogravimetrical analysis, and differential thermal analysis techniques. The powder X-ray diffraction pattern of the samples confirms the formation of a single-phase solid solution only up to 0.50?≤?x. It was found that all the samples have a cubic crystal structure. The electrical properties of La-modified BaSnO₃ were studied using ac impedance spectroscopy technique over a wide range of temperatures (50–650 °C) in the frequency range of 10 Hz–13 MHz. The complex impedance plots above 300 °C show that total impedance is due to the contributions of grain and grain boundaries. The resistance of these contributions has been determined. Variation of these resistances with temperature shows the presence of two different regions with different slopes. The nature of the variation of conductivity of the grain and grain boundaries is different in different regions. Based on the value of activation energy, it is proposed that conduction via hopping of doubly ionized oxygen vacancies (V_O ^??) is taking place in the temperature region of 300–450 °C, whereas in the temperature region of 450–650 °C, it is due to proton, i.e., OH^? ions, hopping.     

AC conductivity of BiFeO<Subscript>3</Subscript> ceramics obtained by spark plasma sintering of nanopowder

The structure and electrical properties of BiFeO₃ ceramics obtained by spark plasma sintering of a nanopowder are investigated. The nanopowder was synthesized by burning of an organic nitrate precursor. The ac conductivity was measured in a frequency range of 1 kHz–10 MHz in a temperature interval of 25–500°C. It is established that the temperature conductivity coefficients above and below ~350°C significantly differ with both alternating and direct currents. The frequency dependence of the conductivity obeys the Jonscher power law σ ~ ω ^s , where s < 1. The interpretation of this behavior is given in the framework of the model of correlated hops of charge carriers over potential barriers. It is assumed that the hopping mechanism is realized between Fe²⁺ and Fe³⁺ ions in ceramic grains. The role of oxygen vacancies in the conduction is also discussed.     

Studies on highly resistive ZnO thin films grown by DC-discharge-assisted pulsed laser deposition

It was found that by changing the substrate temperature from room temperature to ～850 °C, ZnO thin films with widely varying resistivity values could be grown on sapphire substrates using DC-discharge-assisted pulsed laser deposition (PLD) in oxygen ambient. The resistivity of the film grown at room temperature was too high to measure using our existing setup. However, as the growth temperature was increased from 550 °C to 750 °C, the resistivity first decreased slowly from ～14.0 to 4.4 Ω?m and then dropped suddenly to get saturated at ～2.0×10^?3 Ω?m as the growth temperature was further increased. In contrast to these, when there was no DC-discharge, the variation of resistivity for ZnO thin films grown by PLD was marginal up to the substrate temperature of ～850 °C. The reason for these observations was found to be the combined effects of reduction in donor defect densities like oxygen vacancies and zinc interstitials, introduction of acceptor type defects like interstitial oxygen and zinc vacancies, and the resultant poor carrier mobility at lower growth temperatures. At higher growth temperatures (800 °C and above), the appearance of oxygen vacancies and increase in mobility due to better crystalline quality were found to be responsible for reducing the resistivity. The PL of these films had significant emission in the green and red regions of the spectrum due to the aforesaid defect related transitions. Such highly resistive and luminescent films might be suited for applications such as resistive RAM, UV-photo detector, TFT, piezoelectric, transparent phosphor, and broadband LED applications.     

Annealing effect on transport properties of Nd0.67Sr0.33MnO3 thin films

Annealing dependence of the lattice parameter, resistivity, magnetoresistance and thermopower have been studied on Nd_0.7-Sr_0.33MnO₃ thin films deposited on LaAlO₃ and alumina substrates by pulsed laser ablation. Upon annealing at 800°C and 1000°C the lattice constant of the LaAlO₃ film tends toward that of the bulk target due to reduction in oxygen vacancies. This results in a metal-insulator transition at temperatures which increase with progressive annealing along with a decrease in the observed low temperature MR. Using a magnon scattering model we estimate the e _g bandwidth of the film annealed at 1000°C and show that the magnon contribution to the resistivity is suppressed in a highly oxygen deficient film and gains prominence only upon subsequent annealing. We also show that upon annealing, the polaron concentration and the spin cluster size increases in the paramagnetic phase, using an adiabatic polaron hopping model which takes into account an exchange dependent activation energy above the resistivity peak.     

The unusual variations of photoluminescence and afterglow properties in monoclinic ZrO2 by annealing

The raw ZrO₂ is annealed at 600–1550 °C for 6 h. It is found that the emission at 492 nm increases greatly when the annealing temperature is higher than 1200 °C and its afterglow shows a small improvement at 1200–1450 °C and a large enhancement after annealing at 1550 °C. The results that are obtained indicate that the impurity Ti⁴⁺ in ZrO₂ is efficiently reduced to Ti³⁺ when the temperature is higher than 1200 °C, and the increase of Ti³⁺ centers contributes to the large improvement of emission at 492 nm. The thermoluminescence shows that at least two types of traps with different depths (0.65 eV and 1.46 eV) corresponding to oxygen vacancies exist in monoclinic ZrO₂. After annealing at 1200–1450 °C, some new trap clusters related to oxygen vacancies and Ti³⁺ form and causes the small improvement of afterglow at 1200–1450 °C. The large improvement of afterglow after annealing at 1550 °C originates from the sharp increase of proper shallow traps (0.65 eV) in ZrO₂. Accordingly, we present the feasible interpretations and luminescence mechanisms of monoclinic ZrO₂ for our observations.     

Unusual structural phase transition in nanocrystalline zirconia

The present work is the first example demonstrating that a hydrous zirconia formed by precipitation can yield a nearly pure nanocrystalline monoclinic zirconia at a temperature as low as 320 °C. The X-ray diffraction pattern of the hydrous zirconia heated to 310 °C shows that diffraction peaks begin to emerge and reveals a just crystallized mixture of predominantly monoclinic zirconia (70%) with some tetragonal zirconia(30%). In other words, the hydrous zirconia formed in the present work yields the predominantly monoclinic structure coexisting with the tetragonal one as soon as crystallization starts at low temperature (310 °C). This is an important exception to the general principle that amorphous zirconia precursors first convert to the tetragonal structure of zirconia with increasing calcination temperature and then transform to the monoclinic one at a higher temperature (∼600 °C). At the crystallization temperature (310 °C), the monoclinic crystallite size is about 17 nm and the tetragonal one 28 nm. The monoclinic crystallite is much smaller than the tetragonal one with which it co-exists. This result is also not consistent with the traditional view that a critical particle size effect is responsible for the stability of the tetragonal and monoclinic structures. When the temperature (310 °C) is slightly raised to 320 °C, the XRD pattern shows a nearly pure monoclinic zirconia. The crystallite size of the monoclinic zirconia is around 15 nm, and it does not change appreciably as calcination temperature is increased from 320 to or above 400 °C. The unusual structural phase transition has been investigated by several complementary experimental tools: X-raydiffraction and surface analyses, and infrared and Raman spectroscopies. PACS 81.07.-b; 64.70.Nd; 82.80.-d; 78.67.-n; 81.05.Je     

Positron annihilation studies of defects in 3CSiC hot-implanted with nitrogen and aluminum ions

2 ⁺ and Al⁺ at temperatures from room temperature (RT) to 1200 °C at doses of 10¹³ and 10¹⁵/cm². It is found from Doppler broadening spectra of annihilation gamma-rays obtained by varying the incident positron energy that hot-implantation gives rise to clustering of vacancies, whereas it suppresses amorphization and diminishes the thickness of damaged layers. The average size of such clusters increases with increasing implantation dose and temperature. Vacancy clustering by hot-implantation can be interpreted by the combination of vacancies during implantation. Vacancy type defects in the low-dose (10¹³/cm²) implanted samples are found to be removed by annealing at 1400 °C, whereas large vacancy clusters still remain after 1400 °C annealing in the high-dose (1 0¹⁵/cm²) implanted samples. It is also derived from the depth profile of positron diffusion length that positron scattering centers are produced after annealing at 1400 °C in all implanted samples. Received: 7 March 1997/Accepted: 6 May 1997     

Ionic conductivity of sodium beta″-alumina

Measurements of the electrical conductivity of Na ß″-alumina show that the low-temperature activation energies are 0.3337 ± 0.0055 eV for MgO stabilized crystals grown at 1700°C, 0.275 ± 0.015 eV for crystals with the same starting composition position grown at 1650°C, and 0.1716 ± 0.0093 eV for crystals stabilized with ZnO and grown at 1700°C. The conductivities of almost all crystals at 500°C were found to be 1.3 ± 0.6 Ω^?1 cm^?1. In addition to the growth conditions, the presence of a dc electric field, the type of electrode material, the type of conducting ion, and the concentration of stabilizing ion are important in determining the electrical conductivity. These factors are believed to affect the nature of the ordering of vacancies in the ß″-aluminas, leading to variations in the activation energy.     

Impedance spectroscopy and dielectric analysis in KH2PO4 single crystal

Optical observation, differential scanning calorimetry, thermogravimetric analysis, and differential thermogravimetric measurements have been carried out on KH₂PO₄ single crystals. As compared with the optical observation of crystal under polarizing microscope, the dehydration process occurred gradually over the crystal surface at temperatures above 195 °C and then the interior of the sample. The ac impedance measurements were performed as a function of both frequency and temperature. The electrical conduction and dielectric relaxation have been studied. The activation energy of migration is 1.02 eV in the temperature range between 150 and 179 °C. The conduction mechanism in this temperature range is attributed to the hopping of proton among hydrogen vacancies. At temperatures above 186 °C, a higher conductivity activation energy with 2.94 eV is obtained. In addition to the proton conduction, the migration of the heavier ions (such as potassium ion) is also suggested.     

Defect and photoluminescence profiles from thermally converted Cr-doped GaAs

Specimens of Cr-doped semi-insulating (SI) GaAs have been annealed in quartz ampoules under vacuum at elevated temperatures. Some samples, depending on temperature and time of anneal, were partially or wholly converted to p-type. In these cases CV measurements have been combined with serial sectioning to produce carrier concentration profiles. The As overpressure dependencies indicate acceptors to be associated with Ga vacancies. The diffusion coefficient of the Ga vacancies was estimated to be about 3.35 × 10^-14cm²sec^-1 at 950°C. Low temperature photoluminescence on the converted samples show a reasonably good correspondence between carrier distribution profile and the intensity of copper luminescence peak on photoluminescence spectra taken at various depth in the crystals.     

Study of the effect of precipitant on the high-temperature phase stability of SrO-ZrO2 prepared by n-butanol soft-template method

SrO doped zirconia (20%) was synthesized by n-butanol soft-template method using both NaOH and ammonia solution as precipitants. The high-temperature phase stability was investigated following further heat treatment at 1000°C for 2 h. XRD and Raman spectra were used to characterize the crystal form of zirconia. In addition, TEM was used to characterize the dispersibility of SrO doped zirconia. The results indicated that the concentration of OH^? introduced into the ZrO₂ lattice was the main factor controlling the crystal form of nanosized zirconia. The NaOH solution precipitant could improve the dispersibility of SrO doped t-ZrO₂, and could also prevent the phase transformation of zirconia from t-ZrO₂ to m-ZrO₂ effectively.     

Thermal expansion measurements for estimating vacancy concentration in X-ray irradiated KCl single crystals

A sensitive capacitance technique is used for measuring changes in length (Δl) of KCl single crystals with temperature in the region 30–300°C. These measurements have been taken on KCl in (i) as-cleaved (ii) X-ray irradiated (iii) quenched and X-ray irradiated conditions (X-ray irradiation was always done at room temperature (≈ 30°C). The linear coefficient of thermal expansion (α) of the as-cleaved sample is 40.8 × 10^-6°C^-1. Variation of Δl with temperature in X-ray irradiated crystal shows two regions: (a) 30–180°C where α is 48.1 × 10^-6°C^-1, (b) 180–300°C where α is 40.4 × 10^-6°C^-1. Similar behaviour is exhibited by quenched and later X-ray irradiated KCl the first region is up to 140°C, beyond which the second region takes over. From these data, concentration of vacancies in X-ray irradiated KCl at room temperature is calculated to be 3.4 × 10¹⁷ cm^-3 which is in fairly good agreement with the value obtained from F-band absorption measurements on the sample. An attempt has been made to understand these results.     

Drift mobility measurements in melt-grown baryum titanate

Drift mobility measurements in melt-grown BaTiO₃ single crystal have been performed using the Spear method. The mobility of (3 ± 1) × 10^?3 cm²V^?1 sec^?1 at room temperature is found to be thermally activated, with an activation energy of 0.15 ± 0.04 eV. Two interpretations are investigated to explain these results: trapping effects due to oxygen vacancies or small polaron hopping.     

Size-dependent phase transformations in nanoscale pure and Y-doped zirconia thin films

Phase stability in nanoscale pure zirconia and 9.5 mol.% yttria-doped zirconia (YDZ) thin films was studied by in-situ transmission electron microscopy. Oxygen vacancies are found to play a significant role in determining the microstructure and phase evolution. Pure zirconia thin films of ～52 nm thickness were stabilized without any dopants at room temperature, whereas they transformed into a tetragonal phase upon heating to 400°C. On the other hand, 9.5% yttria doping enables stabilization of the cubic structure regardless of grain growth. Annealing of amorphous YDZ films in air (oxygen-rich) leads to tetragonal phase formation, whereas ultrahigh vacuum (oxygen-deficient) annealed samples display a cubic phase at high temperature. Detailed discussions on the effects of initial microstructure, oxygen deficiency, aliovalent doping and thickness are presented.     

PAC experiments for a short range study of the Zr(10%Pr)O2 solid solution

A Zr(10 mol % Pr)O₂ powder obtained by high-energy ball milling has been investigated at nanoscopic scale using primarily the Perturbed Angular Correlations technique. The aim has been to determine the nanoconfigurations around Zr⁴⁺ cations present in the solid solution and their thermal evolution with the intention of providing knowledge on the stability of the system. Results indicate that the milled product is a substitutional cubic solid solution described by two hyperfine interactions: a highly disordered interaction due to oxygen vacancies located very close to Zr⁴⁺ and an ordered interaction probably depicting a charge distribution including Pr³⁺ as nearest neighbor to Zr⁴⁺ probes. On cooling from high temperatures, monoclinic zirconia appears mostly at the expense of the oxygen defective cubic form. A gradual cooling indicates that destabilization of the solid solution takes place around 500°C. Thermal cycling leads to increasing amounts of the monoclinic phase.