Luminescence spectroscopy and electronic structure of ZrP2O7 and KZr2(PO4)3 crystals

The photoluminescence (PL) of ZrP₂O₇ and KZr₂(PO₄)₃ phosphate crystalline micro-powders grown by spontaneous crystallization method is studied under vacuum ultra-violet (VUV) synchrotron radiation excitations (4–20 eV region of excitation photon energies) in 8–300 K temperature region. The electronic structures (partial densities of states) and optical absorbance spectra of the crystals are calculated by the Full-Potential Linear Augmented Plane Wave Method. Both phosphate crystals reveal PL emission band in the UV spectral region peaking near 300 and 295 nm for ZrP₂O₇ and KZr₂(PO₄)₃ respectively. The spectral profile of the band weakly depends on temperature. The excitation spectra of the UV emission in each crystal contain intensive excitation band peaking at 189 and 182 nm for ZrP₂O₇ and KZr₂(PO₄)₃ respectively. The excitation band of the UV emission is related to band-to-band electronic transitions with charge transfer from O 2p to Zr 4d states. The energy band gaps E_g of ZrP₂O₇ and KZr₂(PO₄)₃ are estimated as 6.7 and 6.6 eV respectively.     

Dielectric properties of (NH4)2SO4 crystals in the range of electronic excitations

Spectra of the real and imaginary parts of the pseudo‐dielectric permittivity, 〈?₁〉(E) and 〈?₂〉(E), of ferroelectric ammonium sulfate crystals, (NH₄)₂SO₄, have been measured in the range of electronic excitations 4.0 to 9.5 eV by ellipsometry using synchrotron radiation. Temperature dependences of the corresponding susceptibilities, 〈χ₁〉(T) and 〈χ₂〉(T), obtained for the photon energy E = 8.5 eV, related to excitations of oxygen p‐electrons, reveal sharp peak‐like temperature changes near the Curie point T_C = 223 K. The large temperature‐dependent increase of the imaginary part of the susceptibility χ₂(T), together with a simultaneous decrease of the real part of the susceptibility χ₁(T), take place at the phase transition. These anomalies have been ascribed mainly to the SO₄ group of the crystal structure.     

Effect of electron and gamma irradiation on elastic characteristics of KTiOPO4 crystals

The elastic moduli C ₁₁ and C ₃₃ of KTiOPO₄ crystals unirradiated and irradiated by electrons and gamma quanta in the temperature range 100–330 K have been measured by the echo-pulse technique. It has been shown that C ₁₁ < C ₃₃ and, with increasing temperature, their values smoothly decrease; moreover, in the temperature range of the second-order phase transition at T ～ 281 K, the curves C ₁₁ = f(T) and C ₃₃ = f(T) exhibit anomalies in the form of a kink. It has been established that, under electron irradiation, the elastic moduli decrease and the phase transition temperature increases. Irradiation of KTiOPO₄ crystals by gamma quanta with a dose of 10⁷ R has no substantial effect on the dynamic characteristics of this crystal.     

Multiplication of anion and cation electronic excitations in luminescent wide-gap ionic crystals

The spectra of intrinsic luminescence excitation by synchrotron radiation (6–32 eV) at 8 K have been analyzed for NaCl, KCl, RbCl, KBr, RbBr, CsBr, MgO, CaO and YalO₃ crystals. In all crystalsv (except MgO and CaO) the process of multiplication of electronic excitations (MEE) causes a sharp increase of the intensity of self-trapped exciton emission, but leads (in KBr and NaCl) to the decrease of intra-band luminescence efficiency. The analysis of the intensity ratio spectra for two components of exciton emission allows us to separate the process of secondary exciton creation by hot photolectrons (NaCl, KBr, YAlO₃). The threshold energies of excitonic and electron-hole mechanisms of MEE are compared for a number of alkali halides.     

Anomalies of heat capacity and spontaneous polarization of nonstoichiometric KTiOPO4 crystals in the low-temperature region

The data of experiments that characterize the dependences of the unit cell volume, heat capacity, and spontaneous polarization of a nonstoichiometric KTiOPO₄ sample are presented for the low-temperature region. It is shown that the influence of the electric field leads to variation in the sample nonstoichiometry, which is characterized by the appearance of anomalous behavior of spontaneous polarization in the region below 30 K. This experimental fact is associated with the appearance of the donor-acceptor pairs possessing the dipole moment. As the temperature increases, they gradually dissociate with the subsequent appearance of the cationic component of conduction.     

The electronic structure of InAs/GaSb(001) superlattices-two dimensional effects

Detailed calculations of the two dimensional effects in the electronic structure of InAs/GaSb(001)superlattices are presented for the first time. Comparison of the calculated thickness dependence of the superlattice band gap with optical absorption measurements shows that, at the Γ-point, the conduction band edge of InAs lies about 60 meV below the valence band edge of GaSb. Eigenfunctions of the highest light and heavy hole bands, and the lowest two conduction bands exhibit spatially confined nature in the GaSb and InAs regions respectively, thus establishing the two-dimensional nature of these bands. The calculated conduction band effective mass in the plane of the superlattice near the Γ-point is found to be enhanced by a factor of 2.5 over the bulk InAs value and compares very well with the appropriate mass extracted from recent magnetoresistance measurements.     

The effect of average A-site cation radius on TC in perovskite manganites

Three series of samples Ln_0.7T_0.3MnO₃ (I), Ln_0.7T_0.3Mn_0.9Cr_0.1O₃ (II), and Ln_0.7T_0.3Mn_0.9Fe_0.1O₃ (III) (Ln=La, (La, Nd), (La, Y), T=Ca, CaSr, Sr) were prepared by sol–gel technique. The effect of the average A-site cation radius 〈r_A〉 on the ferromagnetic transition temperature T_C has been investigated. T_C was obtained from M–T curves measured by vibrating sample magnetometer. For a little Nd³⁺ doped at the A-site, the T_C of Ln_0.7T_0.3MnO₃ (I) drops linearly with decreasing 〈r_A〉 (1.18 Å<〈r_A〉<1.25 Å). Similar behavior has been observed in series II and III, which have lower T_C values than series I due to the weakening of the influence of double-exchange interactions upon substituting Fe and Cr for Mn.     

Efficient third-harmonic generation in partly periodically poled KTiOPO(4) crystal

A partly periodically poled KTiOPO(4) (KTP) crystal has been designed to integrate quasi-phase-matched second-harmonic generation (QPM SHG) with sum-frequency generation in one crystal for generating a third-harmonic beam. The highest conversion efficiencies of 45% and 3% have been achieved in our experiments for QPM SHG and third-harmonic generation, respectively, by use of picosecond laser pulses at 1.327 microm . We have also discovered that periodically poled KTP has slightly different indices (n(z)) from bulk KTP.     

Simultaneous femtosecond-pulse compression and second-harmonic generation in aperiodically poled KTiOPO(4)

We report both extracavity and intracavity simultaneous second-harmonic generation and compression of pulses at 1.25 mum from a synchronously pumped RbTiOAsO(4) -based optical parametric oscillator, using an aperiodically poled crystal of KTiOPO(4) . The 290-fs input pulses were temporally compressed to 120 fs, with average output powers as great as 120 mW. The experimental results are compared with a numerical model that uses data obtained by characterization of the input pulses by use of the frequency-resolved optical gating technique.     

Two-dimensional quasi-phase-matched multiple-cascaded four-wave mixing in periodically poled KTiOPO(4)

A two-dimensional quasi-phase-matched structure is realized in a noncollinear, nondegenerate periodically poled KTiOPO(4) parametric oscillator by utilizing the mutual coherence of two noncollinear pump beams. The mutually coherent pump beams form an interference pattern inside the crystal that is directed perpendicular to the existing quasi-phase-matched grating vector and acts as a parametric gain grating. The cavity itself supports two signal wavelengths around 1550 nm with tunable separation, while the gain grating reduces the operational threshold of the oscillator. Furthermore, with this two-dimensional quasi-phase-matched structure, we can demonstrate the generation of new spectral components through multiple chi((2)):chi((2))-cascaded four-wave mixing processes.     

High-power optical parametric oscillation in large-aperture periodically poled KTiOPO(4)

Electric field poling has been employed to fabricate 3-mm-thick periodically poled KTiOPO>(4) crystal for a high-power optical parametric oscillator. The maximum output power of the singly resonant optical parametric oscillator reached 13 mJ with 45% efficiency when the resonator was pumped with a 2.2-mm-diameter beam from a Q-switched Nd:YAG laser. The influence of the cavity design on the spectral and spatial qualities of the output parametric radiation is also discussed.     

The effect of halogen substitution on the structure and electronic spectra of fluorone dyes

By means of the B3LYP density functional method with the use of the polarized continuum model PCM, we have performed quantum-chemical computations of the electronic absorption and fluorescence spectra of fluorone dianions: fluorescein, dibromofluorescein, eosin, erythrosine, and Rose Bengal in vacuum and methanol. We have revealed conformational features of the structure of fluorone dianions (charge redistribution, changes in the bond lengths and angles between bonds) second by the halogen substitution, the transition from the ground state to an excited state, and the change of the solvent (vacuum-methanol). Absorption and fluorescence wavelengths, constant dipole moments, transition dipole moments, and oscillator strengths have been calculated. We have showed that, upon halogenation of fluorones, the absorption spectra are redshifted and the Stokes shift decreases, which is qualitatively consistent with experimental results.     

Influence of isomorphous cation and anion substitution on optical spectra of cobalt alkylaminehalide crystals

Based on data of spectral investigations of crystals with the group A₂CoCl₄ (A=NH₂(C₂H₅) ₂ ⁺ , N(C₂H₅) ₄ ⁺ , N(CH₃) ₄ ⁺ ) and [N(C₂H₅)₄]₂CoCl₂Br₂, the identification of absorption bands corresponding to internal electron transitions in a Co²⁺ ion has been carried out. The values of the crystalline field force Dq for the above-indicated materials at room temperature have been determined. The regularities of the change in the given parameter with change in the temperature and isomorphous cation-anion substitution have been established. It is shown that substitution of chlorine ions by bromine ions in the [N(C₂H₅)₄]₂CoCl₂Br₂ solid solution leads to the formation of distorted tetrahedral complexes CoCl₂Br₂. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 91–95, January–February, 2000.     

Analysis of the electronic structure of crystals through band structure unfolding

In this work, we consider an alternative implementation of the band structure unfolding method within the framework of the density functional theory, which combines the advantages of the basis of localized functions and plane waves. This approach has been used to analyze the electronic structure of the ordered CuCl_xBr_1–x copper halide alloys and F⁰ center in MgO that enables us to reveal qualitatively the features remaining hidden when using the standard supercell method, because of the complex band structure of systems with defects.     

Efficient femtosecond traveling-wave optical parametric amplification in periodically poled KTiOPO(4)

We report, for the first time to our knowledge, high-power femtosecond traveling-wave optical parametric amplification by use of periodically poled KTiOPO(4) . With a single pass through a 4-mm-long sample of 1.23-mm thickness we achieved 40% internal conversion efficiency and 5microJ of single-pulse idler energy near 3.8microm , using only 75microJ of energy from the output of a conventional 1-kHz Ti:sapphire regenerative amplifier. The 210-fs-long idler pulses were almost transform limited. We discuss the specific problems encountered in high-power parametric conversion, such as unwanted quasi-phase-matched upconversion processes for polarization configurations that utilize the largest (d(33)) nonlinear coefficient and the related formation of color centers (gray tracking) in KTiOPO(4) .     

Ultraviolet generation by first-order frequency doubling in periodically poled KTiOPO(4)

First-order quasi-phase-matched frequency doubling at 780 nm in a 1-mm-thick periodically poled KTiOPO(4) crystal with an inverted-domain period of 2.95 microm has been demonstrated for the first time to the authors' knowledge. A normalized conversion efficiency of 1.1%W(-1) cm(-1) has been obtained in cw mode. Experiments show that group-velocity walk-off prevents efficient frequency doubling of femtosecond pulses in KTiOPO(4) in the UV spectral range. However, because of the large optical nonlinearity, periodically poled structures can be efficiently used for frequency doubling of cw and pulsed lasers with pulse lengths as short as ~1 ps .     

The growth and electronic structure of azobenzene-based functional molecules on layered crystals

In?situ ultraviolet photoelectron spectroscopy is used to study the growth of ultrathin films of azobenzene-based functional molecules (azobenzene, Disperse Orange 3 and a triazatriangulenium platform with an attached functional azo-group) on the layered metal TiTe(2) and on the layered semiconductor HfS(2) at liquid nitrogen temperatures. Effects of intermolecular interactions, of the substrate electronic structure, and of the thermal energy of the sublimated molecules on the growth process and on the adsorbate electronic structure are identified and discussed. A weak adsorbate-substrate interaction is particularly observed for the layered semiconducting substrate, holding the promise of efficient molecular photoswitching.     

Tunneling spectroscopic study of the electronic structure in TTF-TCNQ single crystals

The electronic structure near the Fermi-level in a TTF-TCNQ single crystal was experimentally determined using a tunneling spectroscopical technique. It was found that the electronic state-density at the Fermi-level in a TTF-TCNQ crystal is non-zero at room temperature, and this fact is consistent with its metallic nature.     

Tuning electrochemical potential of LiCoO2 with cation substitution: first-principles predictions and electronic origin

With a goal to improve the performance of LiCoO₂ as a cathode material in Li-ion batteries, we simulate substitution of various elements (X = Be, Mg, Al, Ga, Si and Ti) for Co using first-principles density functional theory and predict changes in its electrochemical potential. While the electrochemical potential of LiCoO₂ is enhanced with substitution of Be, Mg, Al and Ga for Co, an opposite effect is predicted of Si and Ti substitution. We determine the electronic origin of these changes in electrochemical potential using (a) Bader method of topological analysis of charge density, (b) partial density of electronic states to estimate oxidation states of metal and oxygen, and charge re-distribution upon lithiation. We find that the distribution of electronic charge donated by Li is influenced by the nature of the X–O bond. A larger electron transfer to O (in XO₆ octahedron) upon lithiation leads to stronger Li intercalation and thereby higher electrochemical voltage. Our findings provide a platform for a rational design of cathode materials in Li batteries with enhanced voltage.