Second-harmonic scattering by domains in RbH2PO4 ferroelectrics

Second-harmonic scattering (SHS) of light by laminar ferroelectric domains of the orthorhombic phase of RbH₂PO₄ below T_c=147 K is studied in detail. CCD images of the far-field SHS pattern reveal up to six off-axis distinct intensity maxima in a plane normal to the ferroelectric axis c. These scattering maxima are interpreted on the basis of the quasi-phase matching (QPM) conditions for the three sets of polarizations allowed by the nonvanishing elements of the second-order nonlinear susceptibility tensor. On this assumption scattering angles of the three SHS modes calculated from crystal optics are shown to fit well the experimental data for any incidence of the pump beam normal to c. Scattering intensities of the two most intense modes are also measured versus the component of the wave vector perpendicular to the modulated structure. A stochastic model giving the intensity as a function of the density probability of domain widths is developed and is shown to give a good fit of the scattered intensity. Moreover, it permits the evaluation of the mean and dispersion of the ferroelectric domain widths, which are found to be, respectively, 2.6 and 0.7 μm in the crystal under study. This is consistent with the domain size of the ferroelastic counterpart revealed by polarization microscopy.     

Transverse piezoelectric properties of KH2PO4 type crystals

It is shown that the anomalous temperature dependence of the transverse piozoelectric constant d₁₄ for KH₂PO₄ type crystals is the result of the antiferroelectric-like properties along the x-axis.     

Dielectric properties of CsH2PO4 and CsD2PO4

Orthorhombic CsH₂PO₄ undergoes a ferroelectric transition at T_c = ?119.5°C, whereas the ferroelectric transition temperature in isomorphous CsD₂PO₄ is T_c = ?5.55°C. The transitions are of first order in both cases. The rather large isotope effect demonstrates the importance of the OHO bonds in the transition mechanism.     

Ultrasonic propagation near the ferroelectric phase transition temperature in RbH2PO4

Ferroelectric phase transition in RbH₂PO₄ is studied by the propagation of longitudinal ultrasonic waves along the polar axis. The velocity data are analyzed to obtain the temperature dependence of the soft mode frequency in the ferroelectric phase. Unlike KH₂PO₄ and KD₂PO₄, the attenuation in RbH₂PO₄ does not exhibit a relaxation type behaviour.     

Features of the behavior of longitudinal static and dynamic dielectric, piezoelectric, and elastic characteristics of KH2PO4 and NH4H2PO4 crystals

Along with their electromechanical coupling coefficients, the longitudinal dielectric, piezoelectric and elastic characteristics in ferroelectric KH₂PO₄ and antiferroelectric NH₄H₂PO₄ crystals are calculated using a modified proton ordering model that considers piezoelectric coupling and the four-particle cluster approximation. The possibility of detecting piezoactivity in solid solutions of K_{1 − x} (NH₄)xH₂PO₄ is substantiated.     

NH4H2PO4和ND4D2PO4晶体微结构的拉曼光谱研究

本文利用偏振拉曼光谱和第一性原理, 对磷酸二氢铵(NH₄H₂PO₄, ADP)和不同氘含量磷酸二氢铵DADP晶体的晶格振动模式进行了研究. 实验测得了不同几何配置、200–4000 cm^-1范围的偏振拉曼光谱, 分析在不同氘含量条件下921 cm^-1和3000 cm^-1附近拉曼峰的变化. 在ADP晶体中, 基于基本结构单元NH₄⁺ 和H₂PO₄^-基团的振动模, 用第一性原理进行了数值模拟, 进一步明确拉曼峰与晶体中原子振动的对应关系; 通过洛伦兹拟合不同氘含量DADP晶体的拉曼光谱中2000–2600 cm^-1处各峰的变化讨论了DADP 晶体的氘化过程, 结果表明氘化顺序是先NH₄⁺ 基团后H₂PO₄^-基团, 研究结果为今后此类材料的生长和性能优化奠定了基础.     

The antiferroelectric phase transition in TlH2PO4 and TlD2PO4

It is shown by X-ray diffraction measurements that the transitions at 230 K in TlH₂PO₄ and at ≈ 350 K in TlD₂PO₄ are structurally equivalent. In both cases, on cooling through the transition, new reflections appear at points ($\text{h +}\text{1}\text{2}$, $\text{k +}\text{1}\text{2}$, l) referred to the primitive monoclinic unit cell of the high-temperature phase. In TlH₂PO₄ some distinct but broadened scattering remains at the ($\text{h +}\text{1}\text{2}$, $\text{k +}\text{1}\text{2}$, l) points up to 10 K, or more, above the transition temperature.     

The transverse dielectric properties of KH2PO4

We have measured the transverse dielectric constant of KH₂PO₄ crystal from liquid N₂ to room temperatures. Extending the Blinc-de Gennes' model in conjunction with a cluster approximation leads to a new independent determination of the Slater-Takagi parameters and improves significantly the fit of the model to the data.     

Detection and characterization of absorption heterogeneities in KH2PO4 crystals

The SOCRATE facility is used for the detection of heterogeneous absorption in large and rapidly grown KH₂PO₄ (KDP) crystals. The different regions are subsequently characterized by spectrophotometry and laser-damage measurement. In accordance with previous results from the literature we found that, by using the SOCRATE damage measurement set-up with a large beam (300 ∗ 600 μm²), the absorption level does not play a major role in the damage mechanism at 355 nm. However, by testing the damage resistance of the same KDP component with a focused beam (9 μm diameter) at 355 nm, we highlight for the first time significantly different damage resistances between highly and weakly absorbing regions from a KDP crystal. Indeed, with a focused beam, we demonstrate that the laser-damage threshold may be lower in some sectors cut in the pyramidal part than in sectors from the prismatic part. This means that the absorbing defects at high concentration are not the predominant damage precursors at 355 nm.     

Electric and electrochemical properties of solid LiH2PO4

Electrical and electrochemical properties of solid LiH₂PO₄ conductor were investigated in the temperature range from room temperature to 373 K. It was found that high conductivity throughout the temperature range, with activation energy 17.23 kJ/mol, originates from the movement of hydrogen ions (protons). The movement of protons in the correlation with phosphate groups rotation was considered. The slopes of Tafel lines and exchange current densities both for cathodic hydrogen and anodic oxygen evolution were determined (by means of usual electrochemical kinetic methods) at various temperatures. The energy of activation at the equilibrium potentials both for the cathodic and the anodic processes have been assessed to be 17.23 kJ/mol (0.18 eV) and 2.9 kJ/mol (0.03 eV), respectively.     

Impurities detection by optical techniques in KH2PO4 crystals

In this paper we examine how optical techniques can be used for impurities (or defects) detection and identification in KH₂PO₄ (KDP) components. This is important in so far as some of these defects are responsible for a much weaker than expected Laser-Induced Damage Threshold (LIDT) in these materials, i.e. for a weaker resistance to a laser shot. KDP materials are investigated by photothermal deflection, fluorescence and photoexcitation with the aim of localizing and identifying the laser-induced damage precursors. The rapidly grown KDP crystals are shown to be heterogeneous from the absorption, fluorescence and composition point of view. Impurities concentrations are measured directly by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) and tentatively correlated to some optical characteristics and to the LIDT of KDP materials.     

Electronic properties of Bi2Se3 crystals

Bismuth selenide crystals were grown from melts with liquid concentrations within 0·2 per cent of stoichiometry. The resulting crystals were examined structurally showing that single crystal samples could be cut for electronic property measurements. Samples were n-type and degenerate (n ～ 2 × 10²⁵ m^?3). Hall, magnetoresistance and Shubnikov-de Haas measurements confirm that the carriers lie in a single minimum located at the centre of the Brillouin Zone. The results are discussed in terms of a non-ellipsoidal band model, and the degeneracy discussed in terms of a defect model.     

Antiferroelectricity in TID2PO4

Polarization versus electric field double hysteresis loops along the b-axis of TID₂PO₄ were observed. From this fact and the permittivity versus temperature characteristic, the low temperature phase of TID₂PO₄ was confirmed to be antiferroelectric.     

Electronic structure of non-centrosymmetric AgCd2GaS4 and AgCd2GaSe4 single crystals

X-ray photoelectron core-level and valence-band spectra for pristine and Ar⁺-ion irradiated (0 0 1) surfaces of AgCd₂GaS₄ and AgCd₂GaSe₄ single crystals grown, respectively, by the Bridgman method and the method of direct crystallization have been measured in the present work. The X-ray photoelectron spectroscopy (XPS) results reveal high chemical stability of (0 0 1) surfaces of AgCd₂GaS₄ and AgCd₂GaSe₄ single crystals. Electronic structure of AgCd₂GaS₄ has been calculated employing the full potential linearized augmented plane wave method. For the AgCd₂GaS₄ compound, the X-ray emission bands representing the energy distribution of the valence Ag d-, Cd d-, Ga p- and S p-like states were recorded and compared on a common energy scale with the XPS valence-band spectrum. The theoretical and experimental data regarding the occupation of the valence band of AgCd₂GaS₄ were found to be in excellent agreement to each other. Second harmonic generation (SHG) efficiency of AgCd₂GaS₄ by using the 320 ns CO laser at 5.5 μm has been recorded within the temperature range 80–300 K. Substantial increase of the photoinduced SHG which in turn is substantially dependent on the temperature has been detected for the AgCd₂GaS₄ compound.     

Raman spectral of low-lying longitudinal mode of KH2PO4 and KD2PO4 in ferroelectric phase

The origin of the low-lying modes of KH₂PO₄ and KD₂PO₄ in the ferroelectric phase has been clarified by the z(xy)z? Raman scattering experiments. The “S-mode”, which has been usually assigned to the proton tunneling mode in KH₂PO₄ at T<T_c, has been found in the z(xy)z? spectrum of KD₂PO₄ in contrast to the x(xy)y spectrum. It has been found that the frequency of the “S-mode” of KD₂PO₄ is higher than that of KH₂PO₄. These results have shown that the “S-mode” is far from the proton tunneling mode nor the proton/deuteron mode at all. From the present Raman spectroscopy, it is concluded that the “S-mode” is assigned to the libration mode of the PO₄ tertahedrons.     

Electronic and thermodynamic and elastic properties of pyrite RuO2

This paper calculates the elastic,thermodynamic and electronic properties of pyrite (P a3ˉ) RuO2 by the plane-wave pseudopotential density functional theory (DFT) method.The lattice parameters,normalized elastic constants,Cauchy pressure,brittle–ductile relations,heat capacity and Debye temperature are successfully obtained.The Murnaghan equation of state shows that pyrite RuO2 is a potential superhard material.Internal coordinate parameter increases with pressure,which disagrees with experimental data.An analysis based on electronic structure and the pseudogap reveals that the bonding nature in RuO2 is a combination of covalent,ionic and metallic bonding.A study of the elastic properties indicates that the pyrite phase is isotropic under usual conditions.The relationship between brittleness and ductility shows that pyrite RuO2 behaves in a ductile matter at zero pressure and the degree of ductility increases with pressure.     

Low-frequency models in KH2PO4-type crystals

The phonon responses along the three crystallographic orientations of KH₂PO₄, 90% deuterated K(H_1–xD_x)₂ PO₄ and NH₄H₂PO₄, deduced from the best fit of the factorised form of the dielectric function to the infrared reflectivity spectra, are compared. Results evidence the activity of a low-frequency heavily damped extra-mode in both directions parallel and perpendicular to the c axis, due to the coupling of an internal mode with the inter-site protonic motion and external models.     

Superprotonic solid solutions between CsHSO4 and CsH2PO4

Solid solutions of (CsHSO₄)_1 − x(CsH₂PO₄)_x (x = 0.25-0.75) were synthesized by mechanical milling method over a wide range of compositions. Superprotonic cubic phase was confirmed for all these samples between 293 and 420 K depending on its composition. These superprotonic phases have primitive cubic structure similar to that of CsH₂PO₄. The kinetic stability of the supercooled cubic phase depends both on the composition x and the humidity of surrounding atmosphere. The most stable composition of the cubic phase was found around x = 0.67 and could be maintained for several days even under ambient atmosphere. The ionic conductivities of these superprotonic phases reached 10^− 2–10^− 3 S∙cm^− 1 at 450 K. With increasing x the ionic conductivity at the superprotonic phase decreased continuously associated with the increase of the activation energy. These findings suggest that the average number of the hydrogen bonds between XO₄ (X = S, P) units plays an important role on the stability of the cubic phase and also on the conductivity.     

Positron annihilation in KH2PO4

A positron annihilation study of KH₂PO₄ provides new evidence of a high temperature phase transition at 447 K. The results suggest the formation of a long lived positron or positronium state which could be associated with bond defects.