Photoluminescence and photoconductivity studies on NaBi(WO4)2 single crystals: A promising Cherenkov radiator

Results of photoluminescence in conjunction with photoconductivity properties of NaBi(WO₄)₂ crystal are presented and explained with the help of calculated electronic and optical properties. Crystals were annealed in air/vacuum to change the local environment near (WO₄)^2? complex and consequently two emission bands near 470 and 520 nm could be separated for excitation at different energies. The activation energy for thermal quenching of emission was calculated to be 160 meV. The role of excitons and localization of charge carriers is explained on the basis of photoconductivity of these crystals that has been observed only intrinsically in contrast to iso-structurally PbWO₄.     

Relaxation of electronic excitations in wide-gap crystals studied by femtosecond interferometry technique

Time-resolved interferometry with a 100-fs temporal resolution was applied for the first time to studying the relaxation of electronic excitations in complex oxides, namely, tungstates CDWO₄ with a crystal lattice of the wolframite-type and CaWO₄ with a scheelite-type lattice. Two stages of charge carrier relaxation, namely, very fast carrier trapping in 200 fs resulting in self-trapped exciton formation and a relatively slow picosecond relaxation process probably due to configurational relaxation within the oxyanion molecule and modification of the surrounding lattice, are revealed in tungstate crystals. Corresponding models of self-trapped exciton creation in tungstate crystals are discussed. The text was submitted by the authors in English.     

Thermoactivated spectroscopy of heterovalent impurity traps in CdWO4

Abstract

Recombination luminescence emission spectra, TSL and trap spectra estimated by fractional glow technique (FGT), in nominally pure and Li-, Bi- and Ho-doped CdWO₄, crystals are reported. According to the investigations by FGT heterovalent impurities Li, Bi and Ho causes localized electronic states which act as traps for charge carriers. It is shown that TSL results in emission of known blue-green luminescence band by emptying of the Li⁺-related traps in CdWO₄-Li and yellow luminescence band by emptying of the Bi³⁺-related traps in CdWO₄-Bi. It is proposed that blue-green and yellow luminescence occur by recombination correspondingly of free holes and free electrons at different intrinsic tungstate group related luminescence centers.     

Absorption,luminescence, and electron paramagnetic resonance of molybdenum ions in CdWO4

A single crystal of cadmium tungstate (CdWO₄) containing approximately 200 ppm of molybdenum was grown by the Czochralski method and then characterized in a series of optical absorption, photoluminescence (PL), photoluminescence excitation (PLE), and electron paramagnetic resonance (EPR) experiments. The Mo⁶⁺ ions substitute for W⁶⁺ ions and serve as recombination sites for electrons and holes when the crystal is exposed to ionizing radiation. A charge-transfer absorption band for the Mo⁶⁺ ions was observed near 320 nm at 10 K. The PL experiments, performed at low temperature with 325 nm excitation, showed a Mo-associated emission peaking near 680 nm. A direct correlation of the 680 nm emission and the 320 nm absorption band was established by the PLE data. When these doped CdWO₄ crystals are exposed at low temperature either to light that is near or above the band gap or to X-rays, the Mo⁶⁺ ions can trap an electron and form stable Mo⁵⁺ ions. The EPR spectrum of the Mo⁵⁺ ions was observed at temperatures near 15 K, and a complete set of parameters describing the g matrix was obtained from an angular dependence study.     

Modelling of decay kinetics of self-trapped exciton luminescence in CdWO4 under femtosecond laser excitation in absorption saturation conditions

The analytical expressions for the three-dimensional spatial distribution of excitons and luminescence decay kinetics of wide band-gap crystals were derived taking into account the saturation effect for absorption near the centre of the incident laser beam with Gaussian transversal profile. The model is verified for the excitonic emission of CdWO₄ crystals under excitation by ultra-short laser pulses in the region of weak excitonic absorption.     

Conductivity and dielectric relaxation phenomena in (NH4)2SO4 single crystal

AC impedance measurements have been carried out on (NH₄)₂SO₄ single crystals for the temperatures from 300 to 473 K and frequency range between 100 Hz and 4 MHz. The results reveal two distinct relaxation processes in the sample crystal. One is the dipolar relaxation with a peak at frequency slightly higher than 4 × 10⁶ Hz. The other is the charge carrier relaxation at lower frequencies. The frequency dependence of conductivity is described by the relation σ(ω) = Bωⁿ, and n = 1.32 is obtained at temperatures below 413 K. This value drops to 0.2 and then decreases slightly with increasing temperature. The dipolar response of the (NH₄)₂SO₄ single crystal under an ac field is attributed to the reorientation of dipoles. The contribution of charge carriers is increasing substantially with increasing temperature at temperatures above 413 K. The temperature variation of conductivity relaxation peaks follows the Arrhenius relation. The obtained activation energy for migration of the mobile ions for (NH₄)₂SO₄ single crystal was 1.24 eV in the temperature range between 433 and 468 K in this intrinsic region. It is proposed that the NH₄⁺ in the sample crystal has the contribution to the electrical conduction.     

IR-induced features of AgGaGeS4 crystalline semiconductors

Complex investigations of the photoconductivity and photoinduced absorption together with the piezoelectric features were performed for the AgGaGeS₄ semiconducting single crystals under the influence of 3.5 μs CO₂ (80 mJ) pulsed laser emitting at 10.6 μm. These crystals are transparent in the wide spectral range 0.4–17 μm, which allows operating due to their properties in the spectral range covering the excitation of the phonons and electron subsystem. The piezoelectric properties show substantial increment during illumination by microsecond CO₂ laser and irreversible relaxation after swathing off the laser excitation. The temperature dependent studies of absorption and photoconductivity confirm the main role of intrinsic defects forming the tails of electronic states below the bottom of conduction band gap. Principal role of IR-induced electron–phonon interactions in the observed changes of the piezoelectricity is demonstrated.     

Luminescent vacuum ultraviolet spectroscopy of Cr3+ ions in nanostructured aluminum oxide

Impurity Cr³⁺ centers in submicron and nanostructured Al₂O₃ crystals of different phase compositions at temperatures of 300 and 7.5 K were studied by a luminescent vacuum ultraviolet (VUV) spectroscopy method. Photoluminescence (PL) spectra and the energies of ²E, ⁴T₂, and ⁴T₁ excited states of Cr³⁺ ion depend on the type of crystalline samples phase. The PL excitation spectrum of R-line in α-Al₂O₃ nanoscale crystals is formed by intracenter transitions (2.5–5.5 eV region), by charge transfer band (6.9 eV) and by effective formation of impurity-bound excitons (9.0 eV region). Such impurity-bound excitons correspond to O₂p→Al₃s electron transition in surroundings of an impurity Cr³⁺ center. The efficiency of impurity-bound excitons formation decreases with the increase of the grain size above 100 nm. The size dependence is noticeably shown in PL excitation spectra in VUV region. Excitons bound to impurity centers do not appear in nanostructured δ+θ-Al₂O₃ crystals. The effect of the electron excitation multiplication is observed distinctly in nanostrucured α-Al₂O₃ at an excitation energy above 19 eV (more than 2E_g).     

Dielectric relaxation of CsHSeO4 above room temperature

Dielectric measurements of CsHSeO₄ show a distinct relaxation at low frequencies at several isotherms (T < 363 K). For example, the relaxation frequency is around 4 kHz at 323 K and increases to higher frequencies (~ 100 kHz) as the temperature increases. The relaxation has an activation energy of 0.8 eV, which is in close agreement with that associated with transport of charge carriers. We suggest that the observed dielectric relaxation could be produced by the H⁺ jump and SeO₄^? 2 reorientation that cause distortion and change the local lattice polarizability, inducing dipoles like HSeO₄^?.     

First-principles study on electronic states of SrWO4 crystals containing F-type color centers

The electronic structures of the SrWO₄ crystals containing F-type color centers are studied within the framework of the fully relativistic self-consistent Dirac–Slater theory using a numerically discrete variational (DV-X^α) method. The calculations indicate that either F or F⁺ center has donor energy level within the forbidden band. The electronic transition energies from the two donor levels to the bottom of the conduction band are 1.82 eV and 2.28 eV corresponding to the 685 nm and 545 nm absorption bands, respectively. It is, therefore, concluded that the 545–685 nm absorption bands are originated from the F and F⁺ center in SrWO₄ crystal respectively.     

Structural evolution,growth mechanism and photoluminescence properties of CuWO4 nanocrystals

Copper tungstate (CuWO₄) crystals were synthesized by the sonochemistry (SC) method, and then, heat treated in a conventional furnace at different temperatures for 1 h. The structural evolution, growth mechanism and photoluminescence (PL) properties of these crystals were thoroughly investigated. X-ray diffraction patterns, micro-Raman spectra and Fourier transformed infrared spectra indicated that crystals heat treated and 100 °C and 200 °C have water molecules in their lattice (copper tungstate dihydrate (CuWO₄·2H₂O) with monoclinic structure), when the crystals are calcinated at 300 °C have the presence of two phase (CuWO₄·2H₂O and CuWO₄), while the others heat treated at 400 °C and 500 °C have a single CuWO₄ triclinic structure. Field emission scanning electron microscopy revealed a change in the morphological features of these crystals with the increase of the heat treatment temperature. Transmission electron microscopy (TEM), high resolution-TEM images and selected area electron diffraction were employed to examine the shape, size and structure of these crystals. Ultraviolet–Visible spectra evidenced a decrease of band gap values with the increase of the temperature, which were correlated with the reduction of intermediary energy levels within the band gap. The intense photoluminescence (PL) emission was detected for the sample heat treat at 300 °C for 1 h, which have a mixture of CuWO₄·2H₂O and CuWO₄ phases. Therefore, there is a synergic effect between the intermediary energy levels arising from these two phases during the electronic transitions responsible for PL emissions.     

A time-resolved luminescence spectroscopy study of non-linear optical crystals K2Al2B2O7

We report the results of complex study of luminescence and dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals obtained using low-temperature luminescence-optical vacuum ultraviolet spectroscopy with sub-nanosecond time resolution under selective photoexcitation with synchrotron radiation. The paper discusses the decay kinetics of photoluminescence (PL), the time-resolved PL emission spectra (1.2–6.2 eV), the time-resolved PL excitation spectra and the reflection spectra (3.7–21 eV) measured at 7 K. On the basis of the obtained results three absorption peaks at 4.7, 5.8 and 6.5 eV were detected and assigned to charge-transfer absorption from O^2? to Fe³⁺ ions; the intrinsic PL band at 3.28 eV was revealed and attributed to radiative annihilation of self-trapped excitons, the defect luminescence bands at 2.68 and 3.54 eV were separated; the strong PL band at 1.72 eV was revealed and attributed to a radiative transition in Fe³⁺ ion.     

Enhanced nonvolatile holographic properties in Zn,Ru and Fe co-doped LiNbO3 crystals

A series of LiNbO₃ crystals doped with various concentrations of ZnO and fixed concentrations of RuO₂ and Fe₂O₃ have been grown by the Czochralski method from the congruent melts. The type of charge carriers was determined by Kr⁺ laser (476 nm) and He–Ne laser (633 nm). The results revealed that the holes were the dominant charge carriers at blue light irradiation. Dual-wavelength and two-color techniques were employed to investigate the nonvolatile holographic storage properties of Ru:Fe:LiNbO₃ and Zn doped Ru:Fe:LiNbO₃ crystals. The essential parameters of blue nonvolatile holographic storage in Zn:Ru:Fe:LiNbO₃ crystals were enhanced greatly with the increase of Zn concentration. This indicates that the damage resistant dopants Zn²⁺ ions enhance the photorefractive properties at 476 nm wavelength instead of suppressing the photorefraction. The different mechanisms of blue photorefractive and nonvolatile holographic storage properties by dual wavelength recording in Zn:Ru:Fe:LiNbO₃ crystals were discussed.     

Optical investigation of strain-balanced superlattices

A series of strain-balanced GaInAs/AlInAs superlattices were investigated using optical spectroscopy. Three sets of excitonic Landau levels could be resolved in magneto-absorption spectra enabling estimates to be made for the reduced effective masses of the first and second electron to heavy hole (0.040±0.001m_eand 0.034 ± 0.002m_e) and the first electron to light hole (0.053 ±  0.002m_e) excitons. Enhancement in the light hole in-plane effective mass, relative to the heavy hole, is shown to result from the tensile strain in the quantum wells. Temperature-dependent photoluminescence measurements of these samples show evidence of thermal excitation of carriers between the first light and heavy hole states. The activation energy of this process compares well with the separation of the first heavy and light holes confined levels found from low-temperature absorption measurements in two structures with energy splitting of ∼40 meV and <10 meV respectively.     

Femtosecond laser ablation of cadmium tungstate for scintillator arrays

Ultrafast pulsed laser ablation has been investigated as a technique to machine CdWO₄ single crystal scintillator and segment it into small blocks with the aim of fabricating a 2D high energy X-ray imaging array. Cadmium tungstate (CdWO₄) is a brittle transparent scintillator used for the detection of high energy X-rays and γ-rays. A 6 W Yb:KGW Pharos-SP pulsed laser of wavelength 1028 nm was used with a tuneable pulse duration of 10 ps to 190 fs, repetition rate of up to 600 kHz and pulse energies of up to 1 mJ was employed. The effect of varying the pulse duration, pulse energy, pulse overlap and scan pattern on the laser induced damage to the crystals was investigated. A pulse duration of ≥500 fs was found to induce substantial cracking in the material. The laser induced damage was minimised using the following operating parameters: a pulse duration of 190 fs, fluence of 15.3 J cm⁻² and employing a serpentine scan pattern with a normalised pulse overlap of 0.8. The surface of the ablated surfaces was studied using scanning electron microscopy, energy dispersive X-ray spectroscopy, atomic force microscopy and X-ray photoelectron spectroscopy. Ablation products were found to contain cadmium tungstate together with different cadmium and tungsten oxides. These laser ablation products could be removed using an ammonium hydroxide treatment.     

Excitonic magnetic polaron dynamics of MBE grown CdTe/Cd1 − xMnxTe,Cd1 − xMnxTe/Cd1 − vMgyTe single quantum wells in magneti fields

Excitonic lifetimes in Cd_1 − xMn_Ue2Te, Cd_1 − xMg_xTe epilayers and CdTe/Cd_1 − xMn_xTe, Cd_1 − xMn_xTe/Cd_1 − vMg_yTe single quantum wells with different well widths and Mn, Mg compositions are investigated. The excitonic lifetimes are found to reduce drastically by applying external magnetic fields to samples with giant Zeeman splittings. The observed phenomenon is interpreted in terms of the PL decay time contribution from the long-life dark excitons which can convert to excitons for recombinations by a spin-flip process. We attribute the lifetime reduction to the depletion of dark excitons due to their crossing over the exciton energies for dipole allowed transitions in magnetic fields.     

X‐ray‐excited optical luminescence and X‐ray absorption fine‐structures studies of CdWO4 scintillator

X‐ray‐excited optical luminescence (XEOL) emission and excitation spectra as well as the EXAFS signal of CdWO₄ were measured in the energy region of the Cd and W absorption edges. From EXAFS refinement, structural parameters such as number of atoms, distance from the absorbing atom and width of coordination shells in the W neighborhood were determined. The role of W–O interactions on the intrinsic luminescence of CdWO₄ is discussed. The efficiencies of conversion, transfer and emission processes involved in the scintillation mechanism showed to be high when self‐trapped excitons are formed locally by direct excitation of W ions. Annihilation of these excitons provides the characteristic scintillation of CdWO₄, a broad band emission with maximum at 500 nm. The presence of two energetically different O positions in the lattice gives rise to the composite structure of the luminescence band, and no influence of extrinsic defects was noticed. A mismatch between the X‐ray absorption coefficient and the zero‐order luminescence curves corroborates that the direct excitation of Cd ions induces secondary electronic excitations not very effective in transferring energy to the luminescent group, WO₆.     

Effect of a Mo impurity on the luminescence properties of CdWO4, ZnWO4, and CaWO4

The thermoluminescence, the spectral composition of the x-ray luminescence and the thermoluminescence, the short-wave absorption, and the luminescence-excitation spectra were studied for ZnWO₄, CdWO₄, and CaWO₄ single crystals with and without molybdenum impurities. The thermal-activation energies were found for radiationless transitions for all these crystals from the temperature dependence of the steady-state x-ray luminescence. A qualitative explanation for the results is offered.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 10, pp. 72–77, October, 1970.Deceased.     

Photoluminescence characterization of beryllium-implanted 6H–silicon carbide

Beryllium has been implanted into both n- and p-type 6H–SiC with post-implantation annealing at 1600 °C. Photoluminescence (PL) measurements have been performed, and PL lines at 420.5, 431 nm, and a broad band at around 505 nm have been observed. The line at 420.5 nm is attributed to an intrinsic defect D_II-center induced by beryllium implantation. The effects of excitation intensity and temperature during the PL experiments are investigated. Based on the excitation laser dependence PL result, the new doublet lines at around 431 nm are thought to be associated with beryllium related bound excitons. The broad band corresponding to the green luminescence at room temperature has been attributed to the recombination of free carriers to beryllium bound levels.     

Vortex structure in Sr2RuO4

The vortex structure in p-wave superconductors is investigated by the Bogoliubov–de Gennes theory on a tight-binding model. We calculate the temperature dependence of the electronic state at each site in the vortex lattice state, and show the difference between sin p_x+i sin p_y-wave and sin p_x−i sin p_y-wave superconducting state. Furthermore the relation of the electronic structure and the site-dependence of the nuclear magnetic relaxation time is also discussed.