The relation between crystal structure and the formation and mobility of protonic charge carriers in perovskite-type oxides: A case study of Y-doped BaCeO3 and SrCeO3

Proton conductivity phenomena in 10% Y-doped barium and strontium cerate are investigated experimentally and by quantum molecular dynamics simulations. In particular the impact of deviations from the cubic perovskite structure on the formation and mobility of protonic charge carriers is investigated. For Y: SrCeO₃, which shows a larger deviation from the ideal cubic perovskite structure, the concentration and mobility of protonic defects is significantly lower than for Y: BaCeO₃. The first is due to the decay of the oxygen position into two sites, only one of which is involved in the formation of protonic defects. The symmetry reduction also leads to the formation of different one-dimensional proton diffusion paths, and unfavourable jumps between such paths are supposed to control the macroscopic proton diffusion coefficient in Y: SrCeO₃. The analysis suggests the formation of strong but transient hydrogen bonds and inter-octa-hedra proton transfer between vertices for SrCeO₃ in contrast to just intra-octahedra proton transfer for BaCeO₃. Whereas for BaCeO₃ the proton transfer step is identified to be rate-limiting at T= 1000 K, for SrCeO₃ both proton transfer and reorientation are found to be of similar magnitude.     

Proton and electron conduction in polymer intercalated vanadium pentoxide xerogel

A comprehensive proton and electron conduction in vanadium pentoxide xerogel-conducting polymer nanocomposites are analyzed by the impedance spectroscopy. The complex impedance plots are used to estimate the proton and electron conductivity. Both protonic and electronic conductivities follow Arrhenius type behavior with temperature. Protonic conductivity increases with the increase of intercalated conducting polypyrrole. The highly ordered conducting polypyrrole (PPY) molecule enhances the diffusion of H₃O⁺ ions into the host lattice. Broad dielectric loss peaks are found in a wide range of frequency domain (KHz–MHz). The intercalated water within the oxide network of vanadium pentoxide remains supercooled up to lowest measured temperature 137 K.     

Diffusion of hydrogen and oxygen in the high temperature proton conductor srceo3 investigated by dynamic conductivity measurements

In SrCeO₃ the oxygen vacancy concentration at elevated temperatures depends on the oxygen partial pressure in the surrounding atmosphere. Changes of the oxygen vacancy concentration are accompanied by change in the hole concentration and therefore can be measured by electrical conductivity measurements. We apply a dynamic method for studying the diffusion of oxygen vacancies by measurements of the time dependence of the electrical conduction after a sudden change in the oxygen partial pressure has taken place.

In doped samples and under wet conditions the protonic charge carriers are mainly incorporated by a dissociative absorption of water and lead to a noticeable protonic conduction. The proton diffusion in SrCe_0.95 Y_0.05O₃ is determined by relaxation measurements at a polarised sample in wet and hydrogen containing atmosphere. The electrochemical cell discussed here is characterised by a combination of one reversible and one (hydrogen) ion blocking electrode. From the time dependence of the depolarisation process the hydrogen diffusivity is extracted.     

Relative humidity influence on the water content and on the protonic conductivity of the phosphatoantimonic acids HnSbnP2O3n+5, xH2O (n = 1, 3, 5)

The phosphatoantimonic acids H_nSb_nP₂O_3n+5, xH₂O (n = 1, 3, 5) have been prepared from the corresponding potassium compounds by ion-exchange in acidic medium. For n = 1 and 3 they are layered materials. When n = 5 the covalent framework is three dimensional with large interconnected channels. The title acids are all hydrated and their water content, lattice parameters and protonic conductivity have been studied at 20°C as a function of the relative humidity. When n = 1 a great part of the water content is physisorbed and the electrical behavior is that of a particle hydrate. For n = 3, the compound is a true lattice hydrate and the protonic conductivity is closely related to the water content. This is also the case when n = 5; however the contribution of surface water to the proton diffusion is clearly evidenced.     

Hydrogen bond dynamics in dodecanoic acid studied by QNS and NMR

The dynamics of hydrogen atoms in the hydrogen bonds of molecular dimers in dodecanoic acid (c phase) have been studied by quasi-elastic neutron scattering and pulsed nuclear magnetic resonance. Q-dependence measurements of the intensity of the quasi-elastic peak have established that the hydrogen atoms move along a line connecting the two oxygen atoms in the hydrogen bond. The correlation time for this motion has been studied by temperature dependence measurements of the width of the quasi-elastic line and of the proton spin-lattice relaxation time,T ₁. These studies reveal the quantum mechanical nature of the dynamics in the low temperature region. The dynamical parameters which characterise the motion have been determined by fitting the data to a model which invokes phonon assisted tunnelling. The frequency dependence ofT ₁ at low temperature is anomalous because the gradient of the ln(T ₁) vs 1/T curve is dependent on the applied magnetic field.     

Etude par RMN de la structure dynamique de l'alanate Na3AlH6

A low temperature wide-line NMR study has allowed a determination of the AI-H bond lengths in cryolite-type Na₃AlH₆. It was found from the thermal behavior of the proton lines that the |AIH₆|^3? octahedra reorient around a C₄ axis. Starting below 170 K, this rotation can be hindered by lattice defects. Above room temperature it becomes isotropic, and a quick protonic exchange appears.The thermal narrowing of the linewidth and the T₁ and T_1ρ relaxation times lead to activation energies of about 0.38 eV for axial rotation and 0.51 eV for protonic exchange. The minimum in T₁ is in good agreement with the exchange model. Absorption phenomena, as well as partial decomposition of Na₃AlH₆ during the heat treatments, explain the presence of small amounts of mobil hydrogen.     

Reduction of low‐frequency noise in multilayer MoS2 FETs using a Fermi‐level depinning layer

Two‐dimensional transition metal dichalcogenides (TMDCs) are potential candidate materials for future thin‐film field effect transistors (FETs). However, many aspects of this device must be optimized for practical applications. In addition, low‐frequency noise that limits the design window of electronic devices, in general, must be minimized for TMD‐based FETs. In this study, the low‐frequency noise characteristics of multilayer molybdenum disulphide (MoS₂) FETs were investigated in detail, with two different contact structures: titanium (Ti) metal–MoS₂ channel and Ti metal–TiO₂ interlayer–MoS₂ channel. The results showed that the noise level of the device with a TiO₂ interlayer reduced by one order of magnitude compared with the device without the TiO₂ interlayer. This substantial improvement in the noise characteristics could be explained using the carrier number of fluctuation model. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Inelastic scattering of phonons by quadrupole defects with internal degrees of freedom

We solve the quantum mechanical problem of the inelastic scattering of phonons by a quadrupole defect in a crystal lattice for the case of solid parahydrogen whose matrix contains pair complexes of H₂ orthomolecules. By employing the pseudospin approximation for the operator of the energy of quadrupole-quadrupole interaction of the molecules in an orthopair we derive an effective Hamiltonian that describes the interaction of phonons with a pair quadrupole orthodefect in the lattice. We set up the scattering matrix and calculate the effective phonon relaxation time τ(ω, T) as a function of the frequency ω and the crystal temperature T. We also find that a pair quadrupole defect, which has a complicated system of levels, can be replaced by an effective two-level system with temperature-dependent parameters. The fact that a pair quadrupole orthocluster has internal degrees of freedom results in a resonant scattering peak near a certain critical temperature T ₀. Our estimates for H₂ yield T ₀≃ 6–7 K. Finally, we discuss the contribution of this mechanism to the low-temperature thermal conductivity of solid hydrogen. Zh. éksp. Teor. Fiz. 114, 555–569 (August 1998)     

Ternary mixed crystal effects on interface optical phonon and electron-phonon coupling in zinc-blende GaN/AlxGa1−xN spherical quantum dots

The theoretical investigations of the interface optical phonons, electron–phonon couplings and its ternary mixed effects in zinc-blende spherical quantum dots are obtained by using the dielectric continuum model and modified random-element isodisplacement model. The features of dispersion curves, electron–phonon coupling strengths, and its ternary mixed effects for interface optical phonons in a single zinc-blende GaN/Al_xGa_1−xN spherical quantum dot are calculated and discussed in detail. The numerical results show that there are three branches of interface optical phonons. One branch exists in low frequency region; another two branches exist in high frequency region. The interface optical phonons with small quantum number l have more important contributions to the electron–phonon interactions. It is also found that ternary mixed effects have important influences on the interface optical phonon properties in a single zinc-blende GaN/Al_xGa_1−xN quantum dot. With the increase of Al component, the interface optical phonon frequencies appear linear changes, and the electron–phonon coupling strengths appear non-linear changes in high frequency region. But in low frequency region, the frequencies appear non-linear changes, and the electron–phonon coupling strengths appear linear changes.     

Lattice dynamical study of body-centred tetragonal indium

The phonon dispersion curves, phonon frequency distribution function as well as the lattice specific heat of body-centred tetragonal indium have been deduced using a lattice dynamical model which includes central, angular and volume forces. Six elastic constants, four zone boundary frequencies and an equilibrium condition were used in the evaluation of the force constants. It is shown that this model is elastically consistent and satisfies the symmetry requirements of the lattice, the phonon frequencies of indium deduced from it are in very good agreement with the experimental values of Reichardt and Smith and the theoretical values of Garrett and Swihart, and theθ _D values compare well with the experimental values over a wide temperature range. The apparent discrepancies in the phonon dispersion curves and theθ _D-T curves obtained from deficient models, importance of umklapp processes and the significance of angular forces in the lattice dynamical models are discussed.     

Inelastic neutron scattering and lattice dynamics of NaNbO<Subscript>3</Subscript> and Sr<Subscript>0.70</Subscript>Ca<Subscript>0.30</Subscript>TiO<Subscript>3</Subscript>

NaNbO₃ and (Sr,Ca)TiO₃ exhibit an unusual complex sequence of temperature- and pressure-driven structural phase transitions. We have carried out lattice dynamical studies to understand the phonon modes responsible for these phase transitions. Inelastic neutron scattering measurements using powder samples were carried out at the Dhruva reactor, which provide the phonon density of states. Lattice dynamical models have been developed for SrTiO₃ and CaTiO₃ which have been fruitfully employed to study the phonon spectra and vibrational properties of the solid solution (Sr,Ca)TiO₃.      

石墨带的晶格动力学研究

基于晶格动力学理论,采用力常数模型,计算了石墨带的声子色散关系、振动模式密度和比热.计算结果表明,石墨带的声子谱特征介于一维碳纳米管和二维石墨片之间.扶手椅型和锯齿型石墨带的中、高频声子支分别与锯齿型和扶手椅型碳纳米管的类似.由于声子限域效应,低频声子支随着石墨带带宽的改变出现明显的频移现象.振动模式密度在高频区几乎不敏感于带宽,而低频区的峰位随着带宽的增加而逐渐向低频移动.此外,无论是在低温还是高温,比热都随着带宽的增加而逐渐降低,呈现量子尺寸效应.在300K时,比热可以拟合成C_V=C_Vg+A/n,其中C_Vg为石墨片的热容,而A/n项反映了石墨带中边缘效应对比热的影响. 关键词： 石墨带 声子色散关系 比热     

纤锌矿氮化物量子阱中光学声子模的三元混晶效应

本文先比较了几种常用方法(修正的无规元素等位移模型、虚晶近似和简化相干势近似等)对纤锌矿三元混晶体声子频率的拟合结果,再选用与实验数据接近的拟合方法,结合介电连续和单轴晶体模型导出含纤锌矿三元混晶In_xGa_1－xN和Al_xGa_1－xN单量子阱各类光学声子模的色散关系,进一步分析了声子模随组分的变化. 结果表明,修正的无规元素等位移模型对单模性纤锌矿     

Study of the diffusion of hydrogen in LaNi5+xH6 compounds by 1H NMR relaxation

The diffusion of hydrogen in LaNi_5+xH₆ (x=?0.2, 0.0, 0.2) has been investigated by NMR from 150 to 300 K. High-temperature data of the spin-spin relaxation time T₂ and the rotating frame spin lattice relaxation time T₁? are independent of stoichiometry but the data of the spin lattice relaxation time T₁ and low-temperature T₁? data are not, and they do not fit Torrey's relaxation model.     

Protonic conductivity in hydrates

The protonic conductivity of three acid hydrates, HUO₂PO₄·4H₂O, Ce(HPO₄)₂·nH₂O,V₂O₅·nH₂O has been studied as a function of the partial pressure of water. The evolution of their conductivity is related to experimental water adsorption isotherms and to the theoretical Brunauer adsorption isotherms. Conclusions can then be drawn about the origin of the conductivity (bulk-type or surface conductivity) and about the type of water molecules involved in the protonic diffusion process. These three compounds are each representative of a different class of protonic conductors, the lattice hydrates, the particle hydrates, and the swelling hydrates respectively.     

Optically stimulated proton hopping in oxides at low temperatures

This communication is inspired by recent results on the observation of “giant” rates for proton transfer in rutile TiO₂ at low temperatures in pump-probe experiments. An important point is that this is not a tunneling effect. We show that this classical looking effect has a quantum mechanical origin and may be called lattice-assisted hopping. To explore the possibility of formulating transport properties in terms of mode vibrations, we use a “quantum” fluctuation–dissipation theorem, thus providing a concept of dynamic activation energy for ion hopping, which had been used in the above experimental study, rather heuristically, to fit the low-temperature “over the barrier” motion data. The resulting expression of hopping activation energy is more general than the standard one defined in units of $k_{B}T$ and is able to describe the crossover from the high to low-temperature regime of proton jumps.     

Dilatometric and electrochemical studies on hydrogen transport through RuO2 coated on palladium

Combined electrochemical and dilatometry measurements were used to characterize the transport of hydrogen through thin RuO₂ layers coated on palladium wire electrodes. Hydrogen dissolved in aqueous solutions penetrated through the oxide in a pH-dependent mechanism that combined diffusion of molecular hydrogen and pH-dependent proton hopping through redox sites within the oxide lattice. When cathodically charged, hydrogen was generated and absorbed at the oxide-solution interface only after Ru (IV) reduction occurs, and then, transported into the metal.     

Isotope effect and cluster size dependence for water and hydrated hydrogen halide clusters: multi-component molecular orbital approach

In order to explore the proton/deuteron (H/D) isotope effect on the structures, wavefunctions, and size dependence of water clusters, both electronic and nuclear wavefunctions are determined simultaneously. The optimized centres and the exponents for the nuclear orbitals indicate the Ubbelohde effect, i.e. the deuteron has weaker hydrogen bonding than the proton. Calculations are made also of hydrogen halide water clusters, Such as HF(H₂O)_n, HB_r(H₂O)_n, (n = 0–4), and their deuterated species. Only the hydrogen transferred ring structure is optimized for the protonic HBr (H₂O)₃ cluster, while both the hydrogen transferred and the non-transferred structures are obtained for the deuterated DBr (H₂O)₃ cluster under the one-particle multi-component treatment. The proton in the HF molecule is localized more than those in the HCl and HBr molecules, and no hydrogen transferred structures are obtained for HF water clusters.     

Proton conducting ceramics: Recent advances

A general introduction into the field of high temperature ceramic proton conductors (HTPCs) is given. Results of two typical studies involving these HTPCs are discussed. In the first part a study of the processes occurring during water vapor exposure of bulk ceramic proton conductors, BaCe_0.9Y_0.1O_2.95 (BCY10) and BaCe_0.8Y_0.2O_2.9 (BCY20), is presented. A disc of a HTPC was connected to a mass spectrometer in a vacuum system permitting the identification of the species crossing the ceramic-vacuum interface. Exposing the other side of the sample to D₂O led to a strong signal of D₂O⁺ after a certain lag time. From these lag times the tracer diffusivity of hydrogen could be determined as a function of temperature. The permeation of steam consisted of two components: a fast component, given by the diffusivities of deuterons (protons), and a slow component, assigned to chemical diffusion of deuterons (protons) coupled to oxygen vacancies. The data also suggested the possibility of participation of even more complex defects in this chemical diffusion. Dilatometry measurements of different specimens of BCY10 and BCY20 also revealed quite clearly this two-phase pattern during protonation. Diffusion measurements on protonic ceramic membranes using H ₂ ¹⁸ O permitted the determination of the tracer diffusivity of oxygen. All of the above measurements were interpreted in the light of the chemical diffusion model developed by Kreuer et al. The second part deals with composites of proton conductors and inorganic compounds such as carbonates, hydroxides, chlorides, and fluorides following the work of B. Zhu. Conductivities of such composites are presented. Nernst potentials of various electrochemical cells with these composites are discussed. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.