Protonic conduction in substoichiometric SrZrO3-based ceramics

The transport properties of strontium zirconate based materials were investigated using different characterization techniques. The electrical conductivity is mainly protonic below 610°C, while the contribution of electron holes increases with temperature and oxygen partial pressure. Under extreme reducing conditions, the conductivity is dominated by protons and oxygen ions. Polarization results are consistent with the results obtained. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Oxygen diffusion in C60 films

We have performed detailed resistivity measurements as a function of temperature in the range from 12 to 300 K on oxygen loaded C₆₀ films. We observe that two ordering phase transitions (i.e.,T ₀=260 K andT _g =90 K) are present in (T), which, in addition, strongly depends on the oxygen content. We find a decrease of both ordering temperatures with increasing oxygen concentrations. The mechanisms of oxygen diffusion are greatly enhanced in the ordered phase on heating. Finally, the transition to a glassy state atT _g is detected as a point of reversibility of the resistivity curve as a function of temperature.     

Band structure and dielectric properties of orthorhombic SrZrO3

Ab initio density functional theory has been used to study the electronic band structure, $k=0$ (zone center) vibrational modes, and dielectric properties of the crystalline high-$\kappa$ perovskite oxide SrZrO₃. The frequencies of the $k=0$ normal modes are computed by the linear response technique and then grouped according to their symmetry. The dielectric intensity of each IR-active mode has been determined. It is found that the calculated orientationally averaged static dielectric constant ${\epsilon }^0=21.49$ is in good agreement with experiment.     

SrZrO3-based proton conducting materials with La additions

The behaviour of La-containing strontium zirconate based ceramics is revised. La additions contribute to improve the sinterability of these materials, but transport properties are also affected. Sr_1−xLa_xZrO_3+δ show some unusual changes in transport properties when samples are exposed to H₂-containing atmospheres and then reoxidized. Nevertheless, the transport properties of (Sr,La)(Zr,Y)O_3−δ, are still mainly dependent on Y additions, at least for cases when the fraction of Y exceeds the fraction of La. In addition, lanthanum causes significant changes in lattice parameters. A combination of conductivity measurements in different atmospheres, ion blocking experiments, and emf measurements has been used to demonstrate that electron hole conductivity increases with temperature, and the protonic contribution drops. The transport properties at temperatures lower than about 800 °C might be affected by structural changes. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Oxygen diffusion and thermal donor formation in silicon

The information available on the diffusion of oxygen and on the formation of thermal donors in silicon is critically reviewed. In this context the effects of intrinsic point defects on the diffusion-controlled growth of oxygen precipitates is investigated in some detail. Seemingly contradictory experimental results on the diffusivity of oxygen in silicon at temperatures around 400° C are explained in terms offast-diffusing gas-like molecular oxygen in silicon. The concept of molecular oxygen is also invoked in a newly suggested model of thermal donor formation in silicon. The diffusivity of molecular oxygen in silicon is estimated to be around 10^–9cm²s^–1 at 450° C, almost nine orders of magnitude higher than the diffusivity of atomic oxygen in interstitial position.     

Dielectric relaxation of protonic defects in hydrated and dehydrated SrZrO3:Yb

Dielectric relaxations of proton conductor Yb-doped SrZrO₃ have been measured as a function of temperature and frequency in different pretreatments with water vapor. Well defined two relaxation peaks were observed in the compounds doped with more than 1 mol% of Yb irrespective of annealing in WET (hydrate) or DRY (dehydrate) conditions. These two relaxations can be assigned to reorientations of Yb-proton dipole at an isolated [YbO₆]-octahedron and at a [YbO₆]–[YbO₆]–... cluster in the SrZrO₃ crystal (i.e. effectively negative charged Yb and positive charged proton). By DRY pretreatment, the magnitude of the dipole strength was almost fixed for the isolated Yb-proton dipole, while the magnitude became significantly decreased for the dipole associated with the Yb-cluster. It shows the proton associated with the isolated Yb is more stable than that with the Yb-cluster.     

Dielectric properties of SrZrO3 thin films prepared by pulsed laser deposition

SrZrO₃ (SZO) thin films have been prepared on Pt-coated silicon substrates and directly on Si substrates by pulsed laser deposition (PLD) using a ZrSrO target at a substrate temperature of 400 °C in 20 Pa oxygen ambient. X-ray –2 scans showed that the as-deposited films remain amorphous at a substrate temperature of 400 °C. The dielectric constant of SZO has been determined to be in the range 24–27 for the Pt/SZO/Pt structure. Capacitance–voltage (C–V) characteristics of a metal-oxide-semiconductor (MOS) structure for SZO films deposited in 20 Pa oxygen ambient and 20 Pa nitrogen ambient (SZON) indicated that incorporation of nitrogen during the substrate heating and film deposition can suppress the formation of an interfacial SiO₂ layer, and the SZON films have a lower equivalent oxide thickness (EOT) than that of the SZO films. However, the leakage current of the SZON films is larger than that of the SZO films. The EOT is about 1.2 nm for a 5-nm SZON film deposited at 400 °C. The leakage-current characteristics of as-deposited SZON films and SZON films post-annealed in oxygen ambient by rapid thermal annealing (RTA) have been studied comparatively. The films post-annealed with RTA have a lower leakage current than the as-deposited SZON films. Optical transmittance measurements showed that the band gap of the films is about 5.7 eV. It is proposed that SrZrO₃ films prepared at 400 °C are potential materials for alternative high-k gate-dielectric applications. PACS 77.84.Bw; 77.84.-s; 77.55.+f     

First-principles study of structural,electronic and optical properties of orthorhombic SrZrO3

We have investigated the structural parameters, electronic structure and optical properties of orthorhombic SrZrO₃ using the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory (DFT). Our calculated structural parameters are in good agreement with the previous theoretical and experimental data. Band structure, density of states and chemical bonding have been systematically studied. Furthermore, the complex dielectric function, refractive index, extinction coefficient, optical reflectivity, absorption coefficient, loss function and optical conductivity are calculated, which show an optical anisotropy in the components of polarization directions (100), (010) and (001).     

Lattice dynamics and the ferroelectric and antiferrodistorsive instabilities in a bulk crystal and thin films of SrZrO3

The lattice dynamics and energies of phases related to antiferrodistorsive and ferroelectric distortions of bulk crystals and thin films of the SrZrO₃ crystal have been calculated within the framework of the ab initio model of an ionic crystal. In the case of a bulk crystal, it has been found that the most energetically favorable phases are related to antiferrodistorsive lattice distortions. Ferroelectricity in the SrZrO₃ crystal is suppressed by structural lattice distortions. In the case of thin films, it has been found that the ferroelectric instability is retained after the ??rotation?? of the oxygen octahedron and the film remains polar both in the case of a free surface and with the inclusion of the SrTiO₃ substrate in the calculation. The spontaneous polarization of thin films of different thicknesses in the ferroelectric phase has been calculated.     

Energy storage properties of antiferroelectric 0.92NaNbO3-0.08SrZrO3 film on (001)SrTiO3 substrate

The present study demonstrates the fabrication of an antiferroelectric 0.92NaNbO₃-0.08SrZrO₃ film deposited on a SrRuO₃ coated (001)SrTiO₃ single crystal substrate by pulsed laser deposition. In the 0.92NaNbO₃-0.08SrZrO₃ film, the domain with its c-axis aligned with the out-of-plane direction contributed to the stabilization of an antiferroelectric phase under the high electric field. The film had an energy storage density of 2.9 J cm⁻³ and storage efficiency of 67% at room temperature, which kept at 2.5 J cm⁻³ and 50% at high temperature of 150 °C.     

Oxygen diffusion in uranium dioxide in the temperature range of phase transitions

The structure of and oxygen diffusion in UO₂ are studied by the molecular dynamics method in the range of transition to the superionic state (melting of the oxygen sublattice) and near the melting point of UO₂. The temperature dependence of the diffusion coefficient of a doubly charged oxygen ion in UO₂ is constructed. In the crystalline state at temperatures between 1800 and 2600 K, this dependence is described by an exponential dependence with a diffusion activation energy of 2.6±0.2 eV. In the superionic state (2600–3100 K), the activation energy of diffusion of an oxygen anion decreases to 1.88±0.13 eV. In melt (3100–3600 K), the exponential dependence of the diffusion coefficient of O^2- persists but the activation energy of diffusion decreases still further, to 0.8±0.2 eV. Our experimental results agree (within the limits of experimental error) with data on oxygen diffusion in the crystalline phase obtained by other researchers.     

Substitution and proton doping effect on SrZrO3 behaviour: high‐pressure Raman study

The high‐pressure Raman studies of pure, Yb‐modified, protonated and non‐protonated SrZrO₃ dense ceramics were performed between 0.1 and 40 GPa using a diamond anvil cell. Lanthanide‐modified, protonated SrZrO₃ perovskites are potential materials for electrolytic membrane in fuel cells and electrolysers working at medium temperature. The comparison of the Raman spectra shows important differences in the pressure behaviour between the pure and Yb‐modified SrZrO₃ ceramics. SrZrO₃ exhibits a rigid structure without any structural modification, whereas for both SrZr_0.93 Yb_0.07 O_2.965 and SrZr_0.93 Yb_0.07 O_2.962 H_0.003 a sequence of structural modifications at 10, 20 and 35 GPa is revealed. The character of these structural modifications is very similar to that observed as a function of the temperature (orthorhombic Pnma 750 °C → pseudo‐tetragonal Imma 840 °C → tetragonal I4/mcm 1070 °C → cubic Pm3m), which suggests that they can be considered as the phase transitions. Despite the low level of proton content (0.3% mole/mole), significant difference between protonated and non‐protonated compounds is observed for the 700–750 cm⁻¹ doublet assigned to the Zr O octahedron stretching mode, perturbed by an oxygen atom vacancy and/or neighbouring Yb ion. The location of proton is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Oxygen ion diffusion in perovskite-type oxides determined by permeation and by relaxation measurements

Oxygen ion diffusion in oxides of the perovskite-type structure was determined by two methods of measurement: i) stepwise change of temperature or oxygen partial pressure of the gaseous environment of a ceramic sample, and measurement of the relaxation of electrical conductivity or oxygen content, ii) oxygen permeation through a gas dense oxide ceramic pellet from air to argon. The experimental problems and sources of errors, calculation methods of chemical diffusion coefficients and oxide ionic conductivities from these two modes of investigation are discussed. The comparison of relaxation and permeation measurements on 10 oxides of the type A_1−aA′_aM_1−bM′_bO_3−σ (A=La, Pr, Ce; A′=Sr, Ca; M=Mn, Fe; M′=Co, Ni) show advantages of the relaxation method in relation to the experimental performance and possible errors.     

Oxygen diffusion through thin Pt films on Si(100)

We have investigated the diffusion of oxygen through evaporated platinum films on Si(100) upon exposure to air using substrates covered with Pt films of spatially and continuously varying thickness (0–500 Å). Film compositions and morphologies before and after silicidation were characterized by modified crater edge profiling using scanning Auger microscopy, energy-dispersive X-ray microanalysis, scanning tunneling microscopy, and transmission electron microscopy. We find that oxygen diffuses through a Pt layer of up to 170 Å forming an oxide at the interface. In this thickness range, silicide formation during annealing is inhibited and is eventually stopped by the development of a continuous oxide layer. Since the platinum film consists of a continuous layer of nanometer-size crystallites, grain boundary diffusion of oxygen is the most probable way for oxygen incorporation. The diffusion constant is of the order of 10^–19 cm²/s with the precise value depending on the film morphology.