Vibrational spectrum and elastic properties of KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystals

The Raman spectra and elastic moduli of KPb₂Cl₅ crystals were studied experimentally. The results are interpreted using a parameter-free model of the crystal lattice dynamics with inclusion of the multipole moments of the electron shells of ions. The calculated and experimental results are in good agreement. It is shown that not only the halogen ions but also the heavy cations make a significant contribution to the eigenvectors of high-frequency lattice vibration modes, which accounts for the relatively low frequencies of these modes.     

Excitons and energy transfer in KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> and RbPb<Subscript>2</Subscript>Br<Subscript>5</Subscript> laser crystals

Excitonic states, radiative relaxation of electronic excitations, and energy transfer to luminescence centers in both undoped and rare-earth activated (Pr, Er, Nd, Ho, Tb, Tm) KPb₂Cl₅ and RbPb₂Br₅ crystals were studied using low-temperature (8 K) time-resolved VUV spectroscopy under selective photoexcitation by synchrotron radiation.     

High-frequency EPR of Tb<Superscript>3+</Superscript>-doped KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystal

High-frequency electron paramagnetic resonance (EPR) spectra of the KPb₂Cl₅:Tb³⁺ crystal have been investigated. Three types of spectra were observed in the frequency range of 74–200 GHz. The most intensive spectrum with the resolved hyperfine structure corresponded to transitions between sublevels of the¹⁵⁹Tb³⁺ ground quasi-doublet with the zero-field splitting (ZFS) close to 48 GHz. Experimental results were analyzed by the exchange charge model of the crystal field affecting terbium ions in low-symmetry Pb²⁺ positions with the chlorine sevenfold coordination and the charge compensating vacancy in the nearest potassium site. The calculated values ofg-factors and ZFS were in agreement with the experimental data. The nature of a broad EPR line with ZFS of about 180 GHz and of additional weak EPR lines observed as satellites of the main Tb³⁺ lines was discussed.     

Phase transition in a KPb<Subscript>2</Subscript>Br<Subscript>5</Subscript> crystal

Crystals of the KPb₂Br₅compound are investigated using polarized light microscopy and calorimetry. The birefringence and the angle of rotation of the optical indicatrix are measured in the temperature range 270–620 K. It is found that the KPb₂Br₅ crystal undergoes a first-order ferroelastic phase transition at temperatures T_0↑ = 519.5 K and T_0↓ = 518.5 K with a change in the enthalpy ΔH = 1300 ± 200 J/mol. This transition is accompanied by both twinning and the symmetry change mmm ? P2₁/c. It is revealed that the angle of rotation of the optical indicatrix exhibits an unusual behavior under variations in the temperature due to a strong temperature dependence of the birefringence.     

Transient hole-polaron optical absorption in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

Results of a study of transient optical absorption (TOA) and luminescence of lithium gadolinium orthoborate Li₆Gd(BO₃)₃ (LGBO) in the visible and UV spectral regions are presented. As revealed by absorption optical spectroscopy with nanosecond time resolution, the LGBO TOA derives from optical transitions in hole centers, with the optical density relaxation kinetics being mediated by interdefect tunneling recombination involving these centers and neutral lithium atoms acting as electronic Li⁰ centers. At 290 K, the Li⁰ centers are involved in thermostimulated migration, which is not accompanied by carrier transfer to the conduction or valence band. The slow components of the TOA decay kinetics, with characteristic times ranging from a few milliseconds to seconds, have been assigned to diffusion-limited annihilation of lithium interstitials with vacancies. The mechanisms responsible for the creation and relaxation of short-lived Frenkel defect pairs in the LGBO cation sublattice have been analyzed.     

Polarized optical absorption of MnGa<Subscript>2</Subscript>S<Subscript>4</Subscript> single crystals

Optical absorption of MnGa₂S₄ single crystals is studied at two light polarizations (E ||C and E⊥ C). The polarization splitting of the absorption edge points to a splitting of the valence band of MnGa₂S₄. A contribution to the crystal-field splitting is made by two factors, namely, by a difference in the pseudopotential of cationic sublattice atoms and by tetragonal compression of the lattice along the C axis. A scheme of optical transitions in MnGa₂S₄ in the Brillouin zone center is suggested, according to which the optical transitions Г₃ + Г₄ → Г₁ occur in the polarization E ⊥ C, and the Г₂ → Г₁ transitions occur in the polarization E || C.     

Transient optical absorption and luminescence of lithium triborate LiB<Subscript>3</Subscript>O<Subscript>5</Subscript>

The transient optical absorption and luminescence of LiB₃O₅ (LBO) nonlinear crystals in the visible and UV spectral ranges were studied. Measurements made using absorption optical spectroscopy with nsscale time resolution revealed that the transient optical absorption (TOA) in LBO originates from optical transitions in hole centers and that the kinetics of optical density relaxation are rate-limited by interdefect nonradiative tunneling recombination involving these hole centers and the Li⁰ electronic centers, which represent neutral lithium atoms. At 290 K, the Li⁰ centers can migrate in a thermally stimulated, one-dimensional manner, a process which is not accompanied by carrier delocalization into the conduction or valence band. It is shown that the pulsed LBO cathodoluminescence kinetics is rate-limited by a recombination process involving two competing valence-band-mediated hole centers and shallow B²⁺ electronic centers. The radiative recombination accounts for the characteristic σ-polarized LBO luminescence in the 4.0-eV region.     

Transient optical absorption and luminescence in <Emphasis Type="Italic">A</Emphasis>Pb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> (<Emphasis Type="Italic">A</Emphasis> = K,Rb) crystals

This paper reports on a study of transient optical absorption and pulsed cathodoluminescence in APb₂Cl₅ (A = K, Rb) in the visible and ultraviolet spectral regions. The measurements performed by absorption optical spectroscopy with nanosecond time resolution showed the transient optical absorption of APb₂Cl₅ to derive from optical transitions in hole centers, and that the optical density relaxation kinetics is mediated by interdefect tunneling recombination in complementary pairs which involves Frenkel defects on the cation sublattice and self-trapped carriers. The slow components in the transient optical absorption decay kinetics, with characteristic times ranging from a few ms to seconds, have been assigned to diffusion-mediated annihilation of interstitial atoms with alkali metal vacancies. The mechanisms underlying creation and relaxation of the short-lived Frenkel defects on the cation sublattice and self-trapped carriers have been analyzed.     

Acoustic and optical phonons and their dispersion in model ferroelastics Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript>

Thefrequency dispersion curve of acoustic and optical phonons are calculated and constructed, and the density of states of the phonon spectrum is obtained for Hg₂Cl₂ crystals. The influence of the hydrostatic pressure on the frequencies of acoustic and optical phonons and their dispersion is analyzed theoretically. It is revealed that an increase in the pressure leads to a considerable softening of the slowest acoustic TA branch (soft mode) at the X point of the Brillouin zone boundary. This behavior is consistent with the phenomenological Landau theory and correlate with experiments.     

Repetitive low-pressure volume discharge induced by attachment instability in an Ar/Cl<Subscript>2</Subscript> mixture

Ignition conditions and the characteristics of a repetitive volume discharge with a spherical anode and plane cathode are investigated. The discharge was ignited in Ar/Cl₂ mixtures (P≤2.0 kPa) used in excimer halogen lamps operating on the ArCl (B-X) 175-nm, Cl₂(D′-A′) 257-nm, and Cl ₂ ^** 195-to 200-nm molecular bands. At an interelectrode distance of 3 cm and a dc anode voltage of U _ch ≤1 kV, a stable repetitive pulsed discharge with a repetition rate of 1–50 kHz was ignited in chlorine or (0.1–2.0)/(0.04–0.12)-kPa Ar/Cl₂ mixtures. The development of attachment instability in the discharge plasma, in which the processes of the formation, decay, and diffusion of the Cl ₂ ⁻ and Cl⁻ negative ions play an important role, leads to the formation of a solitary pearlike plasma domain with an average diameter of 0.2–3.5 cm.     

The Urbach tails and optical absorption in layered semiconductor TlGaSe<Subscript>2</Subscript> and TlGaS<Subscript>2</Subscript> single crystals

TlGaSe₂ and TlGaS₂ single crystals were grown by the modified Bridgman-Stockbarger method. We report the result of an experimental study of the optical absorption of TlGaSe₂ and TlGaS₂ crystals. The absorption measurements were performed in steps of 10 K. The direct and indirect band gaps for TlGaSe₂ and TlGaS₂ samples were calculated as a function of temperature. The phonon energies in TlGaSe₂ and TlGaS₂ crystals were calculated as (39±4) and (9±4) meV at 240 K, respectively. At 10 K, direct and indirect band gaps were found as 2.294 and 2.148 eV for TlGaSe₂, 2.547 and 2.521 eV for TlGaS₂ crystals, respectively. The abrupt changes were observed in the direct and indirect band gaps in the some temperature ranges. These changes were interpreted as phase transformation temperatures. The steepness parameters and Urbach energy for TlGaSe₂ and TlGaS₂ samples increased with increasing sample temperature in the range (10–320) K.     

Spectroscopic studies of erbium-doped potassium-lead double chloride crystals KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript>:Er<Superscript>3+</Superscript>: 1. Optical spectra and relaxation of excited states of the erbium ion in potassium-lead double chloride crystals

Optical spectra, intensities of radiative and nonradiative transitions, and luminescence kinetics in erbium-doped potassium-lead double chloride crystals KPb₂Cl₅:Er³⁺s(KPC:Er³⁺) were investigated. The crystals were grown by the Bridgman-Stockbarger method. Their absorption and luminescence spectra were studied experimentally. The crystal-matrix absorption edge was determined at 80 and 300 K. Intensity parameters, radiative transition probabilities, branching ratios, and nonradiative relaxation rates were estimated by the Judd-Ofelt method. The luminescence kinetics from the emitting levels ⁴ G _11/2, ² G _9/2, ⁴ S _3/2, and ⁴ F _9/2 upon selective excitation was studied.     

Kinetics of the transient optical absorption in Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> and LiB<Subscript>3</Subscript>O<Subscript>5</Subscript> lithium borate crystals

This paper reports on a study of the kinetics of electron tunneling transport between electron and hole centers in Li₂B₄O₇ and LiB₃O₅ lithium borate crystals under the conditions where the mobility of one of the partners in the recombination process is thermally stimulated. A mathematical model has been proposed to describe all specific features in the relaxation kinetics of the induced optical density observed in Li₂B₄O₇ (LTB) and LiB₃O₅ (LBO) nonlinear optical crystals within a broad time interval of 10⁻⁸−1 s after a radiation pulse. The results of calculations have been compared with experimental data on transient optical absorption (TOA) of LTB and LBO crystals in the visible and ultraviolet spectral regions. The nature of the radiation defects responsible for TOA and the dependence of the TOA decay kinetics on temperature, excitation power, and other experimental conditions have been discussed.     

Lattice dynamics and baric behavior of phonons in Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript> crystals at high hydrostatic pressures

A theoretical model based on long-range dispersion corrections of the charge density functional is proposed for model Hg₂Cl₂ calomel crystals, typical representatives of molecular inorganic compounds where the intermolecular interaction is found to play an important role. This model successfully describes the electronic state and the phonon spectrum of the above crystal, predicts the earlier unstudied phase transition at high hydrostatic pressure. Study of the baric behavior of the phonon spectrum with Raman spectroscopy observes the soft mode in the low-symmetry orthorhombic phase with the frequency softening as the pressure rises. Pressures above 9 GPa considerably transform the Raman spectra, indicating a structural phase transition.     

Spectroscopic study of the behavior of the order parameter in model ferroelastic crystals of Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript>

Information is obtained about the temperature behavior of the order parameter of a phase transition by theoretical and experimental investigation of odd (acoustic and IR-active) phonons that appear in the Raman scattering spectra from the X points of the Brillouin zone (BZ) boundary in the paraphase of Hg₂Cl₂ crystals and are induced by the phase transition, unit-cell doubling, and the X → Γ folding in the BZ. The relevant critical exponents are determined, whose values are in agreement with the results of X-ray diffraction measurements and, within the Landau phenomenological theory of phase transitions, indicate that the phase transition in these crystals is close to the tricritical point.     

Impurity absorption and luminescence of CuGaSe<Subscript>2</Subscript> crystals

A comparison of the experimental and calculated absorption spectra of CuGaSe₂ crystals revealed the existence of two acceptor levels with ionization energies of 66 and 167 meV in the samples under study. It was found that the luminescence spectra of CuGaSe₂ measured at 77 K exhibit four impurity-band transitions with impurity ionization energies of 66, 99, 136, and 190 meV. An analysis of the temperature dependence of the luminescence intensity in the temperature range 11–77 K revealed a band peaking at 1.671 eV due to the radiation of donor-acceptor pairs. The calculated sum of the ionization energies of the impurities responsible for the formation of donor-acceptor pairs and the temperature dependence of the relative intensities of impurity-band emission were used to determine the ionization energies of the corresponding donor and acceptor.     

Magnetic and structural phase transitions in YMn<Subscript>2</Subscript>O<Subscript>5</Subscript> ferromagnetoelectric crystals induced by a strong magnetic field

Magnetic, magnetoelectric, and magnetoelastic properties of YMn₂O₅ ferromagnetoelectric single-crystals are investigated in strong pulsed magnetic fields of up to 250 kOe and in static magnetic fields of up to 12 kOe. It is found that, in YMn₂O₅ at T < T_N=42 K, a transverse weakly ferromagnetic moment of σ ₀=0.8 G cm³/g exists that is oriented along axis a and is attributed to the magnetoelectric interaction. When a magnetic field is directed along axis b, which is likely to be the axis of antiferromagnetism, a spin-flop transition is observed that is accompanied by jumps in magnetostriction and electric polarization. When a magnetic field is directed along axis a, the temperature of ferroelectric transition shifts from 20 to 25 K at H≈200 kOe. A theoretical analysis of the experimental results is given within phenomenological theory with regard to the fact that a YMn₂O₅ compound belongs to noncollinear antiferromagnetic crystals even in the exchange approximation.     

Dielectric constant anomalies of an improper Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript> ferroelastic near the phase-transition temperature

The temperature dependence of the permittivity of a Hg₂Cl₂ crystal has been investigated within the Landau phenomenological theory. At T < T _C, the linear permittivity has a singularity in the form ～(T _C?T)^1/2; however, this anomaly may disappear in a multidomain sample. The nonlinear permittivity also has an anomaly near T _C but of stronger type: ～(T _C ? T)^?1/2.     

EPR and optical absorption studies of Cu<Superscript>2+</Superscript> ions in [ZnPd(CN)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O<Subscript>2</Subscript>)] single crystals

A Cu²⁺-doped single crystal of catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-m-cyanopaladate(II) [ZnPd(CN)₄(C₄H₁₂N₂O₂)] complex has been investigated by electron paramagnetic resonance (EPR) technique at room temperature. EPR spectra indicate that Cu²⁺ ions substitute for magnetically equivalent Zn²⁺ ions and form octahedral complexes in [ZnPd(CN)₄(C₄H₁₂N₂O₂)] hosts. The crystal field affecting the Cu²⁺ ion is nearly axial. The optical absorption studies show two bands at 322 nm (30864 cm⁻¹) and 634 nm (15337 cm⁻¹) which confirm the axial symmetry. The spin Hamiltonian parameters and the relevant wave function are determined.     

Longitudinal rf discharge in Xe/Cl<Subscript>2</Subscript> mixtures

Results are presented from the studies of the electrical and emission characteristics of the low-temperature plasma of a longitudinal rf (f₀=1.76 MHz) discharge in Xe/Cl₂ mixtures at pressures of 100–800 Pa. The discharge was ignited in a cylindrical quartz tube with an inner diameter of 1.4 cm and interelectrode distance of 3.0 cm. The discharge emission within the spectral range of 190–670 nm is studied. The dynamics of the discharge current and discharge emission at different pressures and compositions of a Xe/Cl₂ mixture are investigated. It is shown that a discharge in a Xe/Cl₂ mixture acts as a wideband excimer-halogen lamp with a cylindrical output aperture emitting in the spectral range of 220–320 nm. The broad plasma emission spectrum is formed due to the overlap of the XeCl(D, B-X; B, C-A) bands that are broadened at low working-gas pressures. The composition of the working mixture is optimized to achieve the maximum power of the wideband UV plasma emission. Longitudinal rf discharges in low-pressure Xe/Cl₂ mixtures are of interest for developing small-size wideband (Δλ=220–450 nm) cylindrical-aperture lamps, whose efficiency can, on average, exceed the efficiency of conventional hydrogen lamps by more than one order of magnitude.