Nonlinear optical properties of undoped and doped with Zr and Nb KTiOPO<Subscript>4</Subscript> crystals

The structure of the ferroelectric phase of undoped KTiOPO₄ and its solid solutions with zirconium and niobium is studied from first principles within the density functional theory. The second-order nonlinear susceptibility tensor and the spontaneous polarization of these materials are obtained. It is shown that an improvement in nonlinear optical properties of KTiOPO₄ upon doping it with Zr and Nb cannot be explained by a systematic change in the composition of crystals and is apparently associated with the occurrence of defects. Possible structures of such defects are discussed.     

Near-infrared properties of periodically poled KTiOPO<Subscript>4</Subscript> and stoichiometric MgO-doped LiTaO<Subscript>3</Subscript> crystals for high power optical parametric oscillation with femtosecond pulses

A thorough theoretical analysis of the near-infrared properties of periodically poled KTiOPO₄ (PPKTP) and stoichiometric MgO-doped LiTaO₃ (MgO:PPSLT) crystals for optical parametric oscillation with excitation at 1 μm is presented. To the best of our knowledge, the optical, phasematching, wavelength tuning, and dispersive properties of these crystals for parametric interactions are discussed in detail for the first time. In addition, a new design for high power parametric devices based on PPKTP or MgO:PPSLT crystals with ultrafast Yb-ion laser pump is proposed. The results form a useful reference for the selection of materials and operating conditions for the practical design of high power femtosecond optical parametric oscillators with excitation at 1 μm.     

Luminescence peculiarities and optical properties of MgMoO<Subscript>4</Subscript> and MgMoO<Subscript>4</Subscript>:Yb crystals

Magnesium molybdate is considered as a promising material for cryogenic scintillation bolometers. The luminescence properties of MgMoO⁴ have been investigated on single crystals grown from melts of stoichiometric and nonstoichiometric compositions and on crystals doped with Yb³⁺ ions. Their optical properties are interpreted taking into account the anisotropy of the MgMoO⁴ crystal structure.     

Crystal-Physical Model of Ion Transport in Nonlinear Optical Crystals of KTiOPO<Subscript>4</Subscript>

The ionic conductivity along the principal axes a, b, and c of the unit cell of the nonlinear-optical high-resistance KTiOPO₄ single crystals (rhombic syngony, space group Pna2₁), which are as-grown and after thermal annealing in vacuum, has been investigated by the method of impedance spectroscopy. The crystals were grown from a solution-melt by the Czochralski method. The as-grown KTiOPO₄ crystals possess a quasi-one-dimensional conductivity along the crystallographic c axis, which is caused by the migration of K⁺ cations: σ_║c = 1.0 × 10^–5 S/cm at 573 K. Wherein the characteristics of the anisotropy of ionic conductivity of the crystals is equal to σ_║c/σ_║a= 3 and σ_║c/σ_║b= 24. The thermal annealing at 1000 K for 10 h in vacuum increases the magnitude of σ_║c of KTiOPO₄ by a factor of 28 and leads to an increase in the ratio σ_║c/σ_║b= 2.1 × 10³ at 573 K. A crystal-physical model of ionic transport in KTiOPO₄ crystals has been proposed.     

Magnetic properties of DyFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The magnetic properties of an easy-axis trigonal DyFe₃(BO₃)₄ antiferromagnetic crystal have been theoretically studied. On this basis, recent experimental data [1] on the field and temperature dependences of magnetization and the temperature dependence of the initial magnetic susceptibility for three crystallographic directions in this antiferromagnet have been interpreted. The characteristics of the trigonal crystal field for the rare earth ion and the parameters of the Fe-Fe and Fe-Dy exchange interactions are determined. Limitations imposed by features of the magnetic characteristics (anisotropic magnetization in the three crystallographic directions, Schottky-type anomalies in the magnetic susceptibility, etc.) on the possible splitting of the ground-state multiplet in the crystal field and the splitting of the lowest doublet due to the f-d interaction for Dy³⁺ ions are established.     

Structural,elastic, electronic,optical and thermal properties of c-SiGe<Subscript>2</Subscript>N<Subscript>4</Subscript>

We have investigated the structural, elastic, electronic, optical and thermal properties of c-SiGe₂N₄ by using the ultrasoft pseudopotential density functional method within the generalized gradient approximation. The calculated structural parameters, including the lattice constant, the internal free parameter, the bulk modulus and its pressure derivative are in agreement with the available data. The independent elastic constants and their pressure dependence, calculated using the static finite strain technique, satisfy the requirement of mechanical stability, indicating that c-SiGe₂N₄ compound could be stable. We derive the shear modulus, Young’s modulus, Poisson’s ratio and Lamé’s coefficients for ideal polycrystalline c-SiGe₂N₄ aggregate in the framework of the Voigt-Reuss-Hill approximation. We estimate the Debye temperature of this compound from the average sound velocity. Band structure, density of states, Mulliken charge populations and pressure coefficients of energy band gaps are investigated. Furthermore, in order to understand the optical properties of c-SiGe₂N₄, the dielectric function, refractive index, extinction coefficient, optical reflectivity and electron energy loss are calculated for radiation up to 40 eV. Thermal effects on some macroscopic properties of c-SiGe₂N₄ are predicted using the quasi-harmonic Debye model in which the lattice vibrations are taken into account. We have obtained successfully the variations of the primitive cell volume, volume expansion coefficient, heat capacities and Debye temperature with pressure and temperature in the ranges of 0–40 GPa and 0–2000 K. For the first time, the numerical estimates of the elastic constants and related parameters, and the thermal properties are performed for c-SiGe₂N₄.     

Laser-induced synthesis of BaMoO<Subscript>4</Subscript> nanocolloidal suspension and its optical properties

Pulsed laser ablation in a liquid phase was successfully employed to synthesize a barium molybdate (BaMoO₄) nanocolloidal suspension. The nanocolloidal suspension was composed of well-dispersed and horizontally assembled BaMoO₄ aggregates. The BaMoO₄ aggregates showed predominantly elliptically shaped nanorods with sizes between 100 and 200 nm. The preferential elliptical growth was rationalized from the viewpoint of the intrinsic structure of BaMoO₄. The optical properties of the prepared BaMoO₄ colloidal nanoparticles were investigated using Raman spectroscopy, UV–vis spectroscopy and photoluminescence (PL) spectrophotometry. The optical band gap was estimated by Tauc and Menth’s law. The PL emission feature was decomposed into several individual Gaussian components, which could be interpreted by a Jahn–Teller splitting effect on the [MoO₄]^2- tetrahedron of the BaMoO₄ colloidal nanoparticles. PACS  42.62.-b; 82.70.Dd; 78.55.Hx; 81.07.Wx     

Bottom-up fabrication and piezoelectric properties of CaBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> micro-plateaus

CaBi₄Ti₄O₁₅ (CBTi144) micro-plateaus were fabricated on Si wafers and Pt foils using a self-assembled monolayer (SAM) and a complex metal alkoxide solution. The micro-plateaus are delineated by metal masks, which are used for shadowing against the ultraviolet (UV) irradiation for decomposition of SAM to make the surface hydrophilic. The micro-plateaus crystallized to a ferroelectric phase with random orientation. The crystallization depended on the SAM-derived ultra thin layers at the surface of the substrates. The primitive PFM measurements without any top electrodes confirmed that the micro-plateaus exhibited the piezoresponse behaviors. The piezoelectric constant, d₃₃, had some distribution, and the maximum d₃₃ was confirmed as about 45 pm/V, which is identical to the d₃₃ of the polar-axis oriented CBTi144 thin films. PACS 77.84.-s; 81.20.Fw; 77.65.-j     

Effect of pressure on the structure and the electronic properties of LiClO4, NaClO<Subscript>4</Subscript>, KClO<Subscript>4</Subscript>, and NH<Subscript>4</Subscript>ClO<Subscript>4</Subscript>

The effect of pressure on the structural and electronic properties of lithium, sodium, potassium, and ammonium perchlorates have been studied in terms of the density functional theory with allowance for the Van der Waals dispersion interaction. The pressure dependences of the geometric parameters, the band gaps, the densities of states, the charge distributions, and the atomic charges are calculated. The compressibilities of the perchlorates are found to be anisotropic, which is due to the differences of the lattice parameters and the nature of interatomic bonds. Ammonium cation is rotated under pressure around axis b at an angle of ~9°. The band gaps of the perchlorates are ~4.5–4.7 eV and increase with pressure.     

Optical properties of ZnCr<Subscript>2</Subscript>Se<Subscript>4</Subscript>

We studied the optical properties of antiferromagnetic ZnCr₂Se₄ by infrared spectroscopy up to 28,000 cm^-1 and for temperatures from 5 to 295 K. At the magnetic phase transition at 21 K, one of the four phonon modes reveals a clear splitting of 3 cm^-1 as a result of spin-phonon coupling, the other three optical eigenmodes only show shifts of the eigenfrequencies. The antiferromagnetic ordering and the concomitant splitting of the phonon mode can be suppressed in a magnetic field of 7 T. At higher energies we observed a broad excitation band which is dominated by a two-peak-structure at about 18,000 cm^-1 and 22,000 cm^-1, respectively. These energies are in good agreement with the expected spin-allowed crystal-field transitions of the Cr³⁺ ions. The unexpected strength of these transitions with d-d character is attributed to a considerable hybridization of the selenium p with the chromium d orbitals.     

Infrared optical properties of BiFeO<Subscript>3</Subscript> thin films prepared by chemical solution deposition

We report the electrical and optical properties of P-doped epitaxial ZnO thin films grown heteroepitaxially on sapphire substrates or homoepitaxially on ZnO wafers grown by the hydrothermal method, respectively. As-grown heteroepitaxial thin films exhibit semi-insulating to strongly n-conducting behavior depending on the P-content and the oxygen partial pressure applied during deposition. New features are observed in the recombination spectra compared to nominally undoped ZnO thin films. The spectral position of these new features also depends on the growth conditions making a clear correlation between P-incorporation and particular spectral features feasible. For the homoepitaxially grown thin films lateral scanning capacitance microscopy measurements revealed areas of both n- and p-type majority carriers.     

Thermal and optical properties of Tm<Superscript>3+</Superscript>:NaLa(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

A Tm³⁺-doped NaLa(WO₄)₂ single crystal with a dimension of Φ20 mm×40 mm was grown by the Czochralski method. Anisotropic thermal expansion coefficients of this crystal were investigated. Polarized absorption spectra, emission spectra and decay curve were recorded at room temperature. The absorption and emission cross-section were presented. Based on the Judd–Ofelt analysis, we obtained the three intensity parameters: Ω₂=10.21×10^-20, Ω₄=2.66×10^-20, and Ω₆=1.46×10^-20 cm². The radiative probabilities, radiative lifetimes, and branch ratios of Tm³⁺:NaLa(WO₄)₂ were calculated, too. Luminescence lifetime of the ³ H ₄ level was measured to be 220 μs. The stimulated emission cross-section for the ³ F ₄→³ H ₆ transition were determined using the reciprocity method, potential laser gain for this transition were also investigated, the gain curves implied that the tunable range is up to 200 nm. PACS 42.70.Hj; 78.20.-e     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

Electronic and optical properties of Fe<Subscript>2</Subscript>SiO<Subscript>4</Subscript> under pressure effect: ab initio study

We report first-principles studies the structural, electronic, and optical properties of the Fe₂SiO₄ fayalite in orthorhombic structure, including pressure dependence of structural parameters, band structures, density of states, and optical constants up to 30 GPa. The calculated results indicate that the linear compressibility along b axis is significantly higher than a and c axes, which is in agreement with earlier work. Meanwhile, the pressure dependence of the electronic band structure, density of states and partial density of states of Fe₂SiO₄ fayalite up to 30 GPa were presented. Moreover, the evolution of the dielectric function, absorption coefficient (α(ω)), reflectivity (R(ω)), and the real part of the refractive index (n(ω)) at high pressure are also presented.     

Magnetic circular dichroism and optical absorption in TmAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The polarized spectra of absorption and magnetic circular dichroism in a TmAl₃(BO₃)₄ single crystal are studied in the region of ³ H ₆ → ³ F ₄, ³ H ₆ → ³ F ₃, and ³ H ₆ → ³ F ₂ electronic transitions in the Tm³⁺ ion. The structure of the spectra is interpreted qualitatively. It is shown that the magnetic circular dichroism of the ³ H ₆ → ³ F ₄ transition is determined by the contribution from the splitting of the ground state, whereas the magnetic circular dichroism of the ³ H ₆ → ³ F ₃ transition is governed by the contribution from the splitting of an excited state in a trigonal crystal field.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Nonlinear optical properties of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> (LB4) crystal for the generation of tunable ultra-fast laser radiation by optical parametric amplification

Using a very simple and straightforward approach we derive the condition to be satisfied for achieving wavelength-insensitive broadband phase matching in a type-I noncollinear optical parametric amplifier (NOPA), required for the generation of ultra-fast laser radiation. Nonlinear optical properties of a relatively newly grown crystal Li₂B₄O₇ (LB4) have also been studied and we found that this crystal satisfies the condition required to realize the broadband phase matching and is suited for the generation of tunable visible–near-infrared ultra-fast laser radiation employed in a 395-nm-pumped type-I NOPA. The phase-matching bandwidths of type-I NOPAs in different borate-group crystals, such as BBO, CLBO, and KABO, are also numerically estimated. The values are 157, 164, 152, and 174 THz for 1-mm-thick BBO, CLBO, KABO, and LB4 crystals, with the noncollinear angles between the input pump and the signal beams 3.7°, 3.0°, 3.4°, and 2.9°, respectively, for the signal wavelengths centered at 630 nm. In addition to the largest bandwidth, LB4 crystal has several other attractive properties to be used in optical parametric applications, such as high laser damage threshold, wide optical transmission, easy crystal growth to excellent optical quality with large sizes, easy treatment of cutting and polishing, and nonhygroscopicity. PACS 42.65.Yj; 42.65.Re; 42.70.Mp     

Magnetic and thermal properties of single-crystal NdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The neodymium ferroborate NdFe₃(BO₃)₄ undergoes an antiferromagnetic transition at T _N = 30 K, which manifests itself as a λ-type anomaly in the temperature dependence of the specific heat C and as inflection points in the temperature dependences of the magnetic susceptibility χ measured at various directions of an applied magnetic field with respect to the crystallographic axes of the sample. Magnetic ordering occurs only in the subsystem of Fe³⁺ ions, whereas the subsystem of Nd³⁺ ions remains polarized by the magnetic field of the iron subsystem. A change in the population of the levels of the ground Kramers doublet of neodymium ions manifests itself as Schottky-type anomalies in the C(T) and χ(T) dependences at low temperatures. At low temperatures, the magnetic properties of single-crystal NdFe₃(BO₃)₄ are substantially anisotropic, which is determined by the anisotropic contribution of the rare-earth subsystem to the magnetization. The experimental data obtained are used to propose a model for the magnetic structure of NdFe₃(BO₃)₄.