Effect of Fast Electron Irradiation and Annealing on the Luminescence in GaAs(Zn) crystals. Irradiation-induced 1.26 and 1.39 eV Emission Bands

The effect of 2.2 MeV electron irradiation and subsequent annealings on the photoluminescence in zinc-doped p-type GaAs crystals is studied and analyzed. Rather strong emission bands peaked at hv_m (77 K) near 1.26 eV (induced by electron irradiation) and 1.39 eV (induced by annealing of irradiated crystals) are observed. Evidence is presented that the 1.26 and 1.39 eV emission bands occur due to radiative electronic transitions in As_iZn_Ga and V_AsZn_Ga pairs induced by irradiation and annealing of irradiated crystals, accordingly. The observed variations in the intensities of the 1.26 and 1.39 eV emission bands upon irradiation and subsequent annealings of GaAs(Zn) crystals are explained in terms of irradiation and annealing-induced variations in the amount of 1.26 and 1.39 eV radiative centres resulting from: a) the effective interaction of mobile radiation-induced defects in the arsenic sublattice with zinc atoms leading to the formation of As_iZn_Ga and V_AsZn_Ga pairs; b) the thermal dissociation of As_iZn_Ga and V_AsZn_Ga pairs on individual components.     

Stability of Electronic Colour Centres in NaF:Li Single Crystals

The influence of the lithium impurity on the formation and the stability of electronic colour centres is studied in NaF crystals. It is found that F- and M-absorption bands are somewhat displaced to the long wavelengthes when doping with lithium owing to the overlapping with F_A- and M_A-absorption bands. It is shown that the lithium impurity is stabilising one for the charged M-centres though their accumulation in the doped crystals occurs slower. The activation energy is determined for the thermal destruction of M⁺- centres. Thermal destruction of M⁺-centres assumed to be resulting from the anion vacancy removal.     

Investigation of the optical properties of KGd(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Nd<Superscript>3+</Superscript> crystals with allowance for absorption

The optical properties of a biaxial absorbing KGd(WO₄)₂:Nd³⁺ crystal have been investigated. The main refractive indices were measured in the visible spectral range and the absorption and transmission spectra of samples of these crystals were studied. The changes in the refractive indices were in the region of the absorption bands with the use of the Kramers-Kronig relation. Conoscopic pictures of this crystal in the regions of transparency and absorption bands were calculated and are presented.     

Infrared photoluminescence from TlGaS2 layered single crystals

Photolimuniscence (PL) spectra of TlGaS₂ layered crystals were studied in the wavelength region 500‐1400 nm and in the temperature range 15‐115 K. We observed three broad bands centered at 568 nm (A‐band), 718 nm (B‐band) and 1102 nm (C‐band) in the PL spectrum. The observed bands have half‐widths of 0.221, 0.258 and 0.067 eV for A‐, B‐, and C‐bands, respectively. The increase of the emission band half‐width, the blue shift of the emission band peak energy and the quenching of the PL with increasing temperature are explained using the configuration coordinate model. We have also studied the variations of emission band intensity versus excitation laser intensity in the range from 0.4 to 19.5 W cm^‐2. The proposed energy‐level diagram allows us to interpret the recombination processes in TlGaS₂ crystals. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoluminescent properties and Raman spectra of ZnO-based scintillating glasses

Glasses in SiO₂–ZnO–BaO system with the different ZnO/BaO ratio were studied. In some cases, BaF₂ was introduced to substitute for BaO on the equal base. Photoluminescent spectra showed that ZnO in glass matrices behaved somewhat differently from ZnO crystals. Especially, the introduction of fluorine ions led to dramatic shift of UV emission band of glasses closer to that of ZnO crystals. Raman spectral analysis provided consistent results. In particular, Raman bands in the high frequency region are sensitive to effects of different ZnO/BaO or BaF₂/BaO ratio on structure of glasses.     

Structural and mechanical properties of KН2PО4 single crystals with embedded nanoparticles and organic molecules

Single crystals of KDP crystals with embedded Urea molecules and TiO₂ nanoparticles have been grown from aqueous solution by the temperature lowering method. The effect of the organic molecules and nanoparticles on the structural and mechanical properties has been studied. It has been observed that addition of Urea molecules improves laser induced damage threshold and mechanical strength of the crystal, while TiO₂ nanoparticles have the opposite effect. The structure and composition of KDP:Urea crystal are studied by three‐crystal X‐ray diffraction analysis, which reveals the existence of a correlation between the increase of the microhardness value and the change of the crystal lattice parameter. The surface features of KDP:TiO₂ crystals are analyzed by scanning electron microscopy that reveals the presence of quasi‐equidistant growth bands caused by capture of the nanoparticles. It is shown that the rise of TiO₂ nanoparticles concentration up to 10⁻⁴ wt.% and higher resulted in 3‐fold reduction of the laser damage threshold of KDP:TiO₂ relative to pure KDP in [001] and [100] crystallographic directions. It is found that microhardness and fracture toughness decrease at the nanoparticles concentration of 10⁻³ wt.% due to crack formation at crystal lattice discontinuities. The grown crystals also have been subjected to dielectric studies.     

Photoluminescence Spectra of GaS0.75Se0.25 Layered Single Crystals

Photoluminescence (PL) spectra of GaS_0.75Se_0.25 layered single crystals have been studied in the wavelength region of 500‐850 nm and in the temperature range of 10‐200 K. Two PL bands centered at 527 ( 2.353 eV, A‐band) and 658 nm (1.884 eV, B‐band) were observed at T = 10 K. Variations of both bands have been studied as a function of excitation laser intensity in the range from 8 × 10^‐3 to 10.7 W cm^‐2. These bands are attributed to recombination of charge carriers through donor‐acceptor pairs located in the band gap. Radiative transitions from shallow donor levels located 0.043 and 0.064 eV below the bottom of conduction band to acceptor levels located 0.088 and 0.536 eV above the top of the valence band are suggested to be responsible for the observed A‐ and B‐bands in the PL spectra, respectively.     

Growth and etching of calcite crystals

Single crystals of calcite (CaCO₃) have been grown by the method employed by GRUZENSKY , using an aquoeus solution of CaCl₂ and a solid (NH₄)₂SO₃, The chemical reaction takes place according to the following equation: CaCl₂ + (NH₄)₂SO₃ CaCO₃ + 2 NH₄Cl The crystals grown by this method are about 0.2 to 0.8 mm in edge dimensions. Synthetic calcite crystals have been cleaved along (100) planes and the cleavage surfaces have been studied by multiple beam interferometry. The interferograms have revealed that the cleavages are quite flat. The cleavage faces have also been chemically etched and the etch patterns studied optically. By etching a cleavage successively for three different periods it was found that the bottoms of the point-bottomed pits follow a linear etch path. By etching a cleavage pair, one face in one etchant and the other face in a different etchant and by comparing the etch patterns produced, before and after polishing a cleavage face it has been shown that the etch pits nucleate at the sites of dislocations in the crystal. The etch patterns have also been compared with those produced on the cleavage faces of natural crystals. The density of dislocations in the syntheitc calctie crystals was generally less than the density of dislocations in the natural calcite crystals. The implications have been discussed.     

Influence of doping on OH absorption in LiNbO3 crystals

Undoped, Cr doped and Mg, Cr codoped LiNbO₃ crystals were grown by conventional Czochralski technique. Comparative study was carried out using Fourier transform infrared (FTIR) and UV‐Visible spectroscopy. Infrared optical absorption for OH^– ion has been used to study the effect of dopants on the crystals. The peak position of OH^– shift to 3535 cm^‐1 for Mg, Cr codoped crystals compared to 3484 cm^‐1 for undoped and Cr doped crystals. Prominent absorption bands are found in the visible region centered at 480 nm (20833 cm^‐1) and 653 nm (15313 cm^‐1) in Cr doped crystals. Whereas in Mg, Cr codoped crystals these broad absorption bands are red shifted to 517 nm (19342 cm^‐1) and 678 nm (14749 cm^‐1). UV cutoff in Cr doped crystals shift towards higher wavelength compared to undoped LiNbO₃ crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

EPR and Optical Absorption Studies of γ-irradiated Pyrene Single Crystals

Pyrene single crystals irradiated with γ rays at room temperature have been investigated by electron paramagnetic resonance and optical absorption experiments. EPR spectra exhibit a triplet characteristic and each line of the triplet shows characteristic features with rotations of the crystals in a magnetic field. From analyses of these spectra the presence of two kinds of hydrogen added pyrene radicals, 3-H₂-pyrene and 2-H₂-pyrene radicals, is concluded. In the optical absorption spectrum nine main absorption bands have been detected. These absorption bands are compared with the theoretically calculated transition energies with SCF-CI molecular orbital calculations for 3-H₂-pyrene and 2-H₂-pyrene radicals. Reasonable correspondences are obtained between theoretical values and the experimental spectrum.     

Absorption and circular-dichroism spectra of iron-doped berlinite crystals

Absorption and circular-dichroism spectra of iron-doped AlPO₄ crystals have been studied. For the first time, the experimental data on the electronic states of the [FeO₄]^5? complex are obtained in the range from 190 to 350 nm with due regard for the interactions that cannot be described within the one-electron approximation. The bands observed in the absorption and circular-dichroism spectra are attributed to corresponding electronic transitions. The advantages of the use of crystal-field-induced circular dichroism in comparison with other spectroscopic methods in the analysis of the electronic states of impurity ions in gyrotropic crystalline matrices are considered on the [FeO₄]^5? complex.     

Determination of Elastic Constant K 33 for Some Nematic Liquid Crystals with Strong Positive Dielectric Anisotropy by Means of IR Absorption Spectroscopy

The influence of a.c. electric field (2000 Hz) on the half-width of some bands from IR spectrum of three liquid crystals with strong positive dielectric anisotropy is investigated and U _c and K ₃₃ values are calculated.     

Ultraviolet Absorption of Hg2Cl2-and Hg2Br2 Single Crystals

The optical unpolarized absorption spectra of Hg₂Cl₂ and Hg₂Br₂ single crystals were measured in the spectral range 230–400 nm. A sharp exciton peak and other absorption bands of both halides were observed near the fundamental absorption edge. The absorption peaks due to the splitting of the halogen doublet were also observed. Positions of the exciton peaks are characteristic for the Frenkel (localized) type of excitons. Possible interpretations of the other observed bands are discussed.     

Solution growth and comparative characterization of L‐HFB single crystals

Single crystals of L‐histidine tetrafluoroborate (C₆H₁₀N₃O₂BF_{4 ,} L‐HFB) were grown by solution growth method using two different temperature profiles: conventional, in which the growth temperature was kept constant at 30°C and rapid, in which it was increased in steps of 1 K per day while keeping the other growth conditions same. Crystals grew in nearly 30 and 10 days in the two methods, respectively. The crystals were transparent and showing its characteristic morphology. Both types of crystals were characterized by XRD for their structural comparison. Surface morphology and growth features of the crystals were studied by SEM. Features of two dimensional layer growth steps, rectangular etch pits, slip lines and bands, etc. were observed. The presence of various functional groups and their bonding were studied by FTIR in the range 4000‐400 cm^‐1. Thermal stability of the crystals was determined by thermo‐gravimetric and differential thermal analysis. The generation of green light due to second harmonic generation for fundamental λ =1064 nm has been confirmed in both cases. Dielectric constant measurement was carried out in the range 20Hz‐2MHz. In the UV‐Vis studies, high transmittance and a shorter ‘lower cut off' value (232 nm) were observed. The effect of rapid growth on the structural, morphological and optical properties of the crystals were studied and compared to those of crystals grown in conventional way. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temperature and excitation intensity tuned photoluminescence in Tl4GaIn3S8 layered single crystals

Photoluminescence spectra of Tl₄GaIn₃S₈ layered crystals grown by Bridgman method have been studied in the wavelength region of 500–780 nm and in the temperature range of 26–130 K with extrinsic excitation source (λ_exc = 532 nm), and at T = 26 K with intrinsic excitation source (λ_exc = 406 nm). Three emission bands A, B and C centered at 514 nm (2.41 eV), 588 nm (2.11 eV) and 686 nm (1.81 eV), respectively, were observed for extrinsic excitation process. Variations in emission spectra have been studied as a function of excitation laser intensity in the 0.9‐183.0 mW cm^–2 range for extrinsic excitation at T = 26 and 50 K. Radiative transitions from the donor levels located at 0.03 and 0.01 eV below the bottom of the conduction band to the acceptor levels located at 0.81 and 0.19 eV above the top of the valence band were proposed to be responsible for the observed A‐ and C‐bands. The anomalous temperature dependence of the B‐band peak energy was explained by configurational coordinate model. From X‐ray powder diffraction and energy dispersive spectroscopic analysis, the monoclinic unit cell parameters and compositional parameters of Tl₄GaIn₃S₈ crystals were determined, respectively. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on the growth and optical characterization of Tm3+‐doped BaY2F8 single crystals

The BaY₂F₈ crystals doped with different concentrations of Tm³⁺ ions were prepared by the temperature gradient technique (TGT). X‐ray powder diffraction was applied to analyze the phase. The cracking phenomenon along (010) and (100) planes of the crystals grown by temperature gradient technique was studied on the basis of the structure of BaY₂F₈ crystals. The absorption spectra were measured and investigated in the ultraviolet‐visible and near‐infrared ranges at room temperature. Several characteristic absorption bands of Tm³⁺‐doped BaY₂F₈ crystal were observed. The emission and excitation spectra were obtained and investigated at room temperature and 12 K, showing the characteristic emission peaks of Tm³⁺ ions. The temperature dependence of Photoluminescence curve was also investigated in the range of 12–296 K. The luminescence intensity of emission bands decreased with increasing temperature, while the effective bandwidth increased. The up‐conversion spectrum excited at 650 nm was recorded and up‐conversion mechanism was analyzed in detail. The result showed the purple, green and yellow emissions corresponding to ³P₁→³F₃, ¹D₂→³H₅ and ³P₀→¹G₄ transitions, respectively.     

The study of bis-chloromethyl-phosphinic acid crystal by ATR and Raman spectroscopy and X-ray diffraction

Crystals of bis-chloromethyl-phosphinic acid ((CH₂Cl)₂POOH) are studied by attenuated total reflection (ATR) and Raman spectroscopy supported by X-Ray diffraction. The bands recorded in the ATR and in Raman spectra have the same wavenumbers within experimental uncertainty. It is in agreement with the X-Ray diffraction results which show that the molecules in crystals form infinite chains through hydrogen bonds and there is no center of inversion. The parameters of the unit cell, the bond lengths and angles, and the distance between two oxygen atoms in hydrogen bond bridges are determined. The spectral features and the intermolecular distance between oxygen atoms are characteristic for a strong hydrogen bonded system.     

Absorption and Circular Dichroism Spectra of La<Subscript>3</Subscript>Ga<Subscript>5</Subscript>SiO<Subscript>14</Subscript> Crystals Doped with Pr<Superscript>3+</Superscript>, Ho<Superscript>3+</Superscript>, and Er<Superscript>3+</Superscript> Ions

The absorption and circular dichroism (CD) spectra of La₃Ga₅SiO₁₄ langasite crystals doped with Pr³⁺, Ho³⁺, and Er³⁺ ions have been studied in the wavelength range of 350–700 nm. The electronic transitions of these ions, which replace La3+ ions in the 3e position with the symmetry 2, are observed in the spectra. All transitions are active in both the absorption and CD spectra. The dipole strengths D _om, rotational strengths R _om, and anisotropy factors g have been calculated for well-resolved bands. Some features are noted for the spectra that were obtained, and their relationship with the structure disorder is considered     

Crystal structure of Rb2[GeO2(OH)2]·2H2O

Single crystals of Rb₂[GeO₂(OH)₂] · 2H₂O are studied by X-ray diffraction. The crystals belong to the orthorhombic system, sp. gr. Pna2₁, a = 13.523(6) Å, b = 8.143(4) Å, c = 13.407(6) Å, Z = 8, R ₁ = 0.0506. In [GeO₂(OH)₂]^2? anions, the Ge-O distances (1.71–1.73(1) Å) are shorter than the Ge-OH distances (1.76–1.80(1) Å). Anions are linked to each other by pairs of hydrogen bonds to form infinite chains. The chains are linked by hydrogen bonds involving water molecules to form a 3D structure. The assignment of the bands in the IR spectrum of the compound under study is performed.     

Growth of R 1 − y Sr y F3 − y crystals with rare earth elements of the cerium subgroup (R = La, Ce, Pr, or Nd; 0 ≤ y ≤ 0.16) and the dependence of their density and optical characteristics on composition

Crystals of the R _{1 ? y} Sr _y F_{3 ? y} phases (R = La, Ce, Pr, or Nd; 0 ≤ y ≤ 0.16) with tysonite (LaF₃) structure are grown by the Bridgman method. A linear dependence of the crystal density on the SrF₂ concentration has been revealed for each series of solid solutions. A scheme of heterovalent isomorphous substitution in the tysonite structure, R ³⁺ + F^1? → M ²⁺ + V _F, with compensation of the difference in the cation charges due to the formation of anion vacancies, is confirmed experimentally. The optical transmission spectra are measured in the wavelength range λ = 2.18–22.22 μm. It is shown that the 50%-transmission edge in the IR range is 10.5 μm for all crystals. The refractive index and the polarizability of crystals decrease with decreasing SrF₂ content according to a linear law. The melting curves of the R _{1 ? y} Sr _y F_{3 ? y} phases studied have a maximum; therefore, these phases can be recommended for use as crystals with a high homogeneity and different optical properties in comparison with the corresponding RF₃ crystals.