Spectroscopic properties of a Tm3+:Bi2TeO5 single crystal

Single crystal of bismuth tellurite Bi₂TeO₅ (BTO) doped with trivalent thulium (Tm³⁺) was grown by the Czochralski method and investigated by spectroscopic techniques (absorption, emission). Absorption and emission of the Tm:BTO crystal collected in the VIS‐IR spectral range are presented. Spectroscopic features were investigated as a function of the excitation light polarisation (E//X, Y, and Z axis of optical indicatrix) and sample temperature. The oscillator strength of the ³H₆ → ³F₄ transition at 1.7 μm was determined by numerical integration of the X, Y and Z polarised absorption spectra. The obtained values are: P_X = 4.7 × 10⁻⁶, P_Y = 6.8 × 10⁻⁶ and P_Z = 5.9 × 10⁻⁶ that gives a mean value P_mean = 5.8 × 10⁻⁶. Emission was observed from the ¹G₄ and ³H₄ levels. The ³H₄ and ¹G₄ excited state dynamics was studied. Decay curves and time constants of luminescence were collected at 5 and 300 K and analysed. The ³F₄ → ³H₆ luminescence at around 1.8 μm was too weak to be acquired from the low concentrated sample. However, based on optical data it was possible to estimate the radiative probability A_rad of this transition and the ³F₄ radiative lifetime. The resultant values are: A_rad = 668 ± 0.4 s⁻¹ and τ_rad = 1.5 ms. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of temperature and isomorphic atom substitution on optical absorption edge of TlInS2xSe2(1‐x) mixed crystals (0.25 ≤ x ≤ 1)

The optical properties of the TlInS_2xSe_2(1‐x)mixed crystals (0.25 ≤ x ≤ 1) have been investigated through the transmission and reflection measurements in the wavelength range of 400–1100 nm. The optical indirect band gap energies were determined by means of the analysis of the absorption data. It was found that the energy band gaps decrease with the increase of selenium atoms content in the TlInS_2xSe_2(1‐x)mixed crystals. The transmission measurements carried out in the temperature range of 10–300 K revealed that the rates of change of the indirect band gaps with temperature are γ = –9.2×10^–4 eV/K, –6.1×10^–4 eV/K, –4.7×10^–4 eV/K and –5.6×10^–4 eV/K for TlInS₂, TlInS_1.5Se_0.5, TlInSSe and TlInS_0.5Se_1.5 crystals, respectively. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical Parameters of Nd‐Doped Gadolinium Aluminium Tetraborate Crystals

Nd‐doped gadolinium aluminium tetraborate, Nd_xGd_1‐xAl₃(BO₃)₄ (NGAB), crystallizes with x = 0.1 in the trigonal system with point group 32, conforming space group R32. They were grown using flux method, of large sizes and good optical quality. The unit cell constants were a = 0.93057 (6) and c = 0.72481 (3) nm, and z = 1. The measured absorption of the NGAB is compared to Judd‐Ofelt (JO) theory. When applied, the JO theory of parity‐forbidden electric‐dipole transitions of rare earth ions on noncentrosymmetric sites demonstrates good agreement. A measured band gap of the eigentransition was about 4.00 eV. The fitted intensity parameters Ot (t = 2, 4, and 6) were 2.446 × 10^‐20, 2.266 × 10^‐20 and 2.598 × 10^‐20 cm². Both the emission properties of the sub‐stable ⁴F_3/2 state with the level lifetime of 506.20 μs and a fluorescence spectrum corresponding to the transition ⁴F_3/2 → ⁴I_11/2 were studied. The results indicate the pass band of laser for potential applications in practice.     

Growth of large KDP single crystals for UV spectrum range

The influence of various technological parameters of crystallization (acidity of growth solutions, crystallization temperature, growth rate, degree of solution purification) on the optical absorption of large KDP single crystals has been studied in the UV range of the spectrum. It is shown that the method of solvent recirculation with the use of the starting material with the microimpurity content not exceeding 5 × 10^?5 wt % and solution ultrafiltration under the optimum crystallization conditions (t_cr = 80°C, V_cr ～ (0.8–1.6) × 10^?6 cm/s, pH 4) enables one to grow KDP single crystals with cross sections up to 300 × 300 mm² and the transmission in the vicinity of the fundamental absorption edge λ = 200 nm) equal to 86%.     

The molecular and crystal structure of 2-oxo-1-pyrrolidine-acetamide

C₆H₁₀N₂O₂, P1 , a = 6,607(2) Å, b = 8,538(2) Å, c = 6,392(2) Å, α = 102,43(2)°, β = 91,11(2)°, y = 79,82(2)°, V = 349,1 ų, Z = 2, D_m = 1,36 g × cm⁻³, D_x = 1,35 g × × cm⁻³, MoKα radiation, λ = 1.71069 Å, μ(MoKα) = 1.11 cm⁻¹. The structure was solved by direct methods. The parameters were refined by full matrix least squares technique to a final R = 0.088 for 834 reflections with ∥F₀∥ > 4σ(F₀). The dihedral angle between the least-squares plane through the pyrrolidine ring and that through the acetamide group is 90.4°. The N H … O hydrogen bonds connect molecules to form bands parallel to the z axis.     

An EPR Study of Scapolite

In single crystals of scapolite from two different localities, three paramagnetic centres are detected by electron paramagnetic resonance (EPR): 1. One isotropic singlet with g_iso = 2.005; 2. One triclinic singlet with g‖ = 2.005 ± 0.001 and g⟂= 2.009; 3. One triclinic sextet with g‖= 2.005 ± 0.001, g⟂ = 2.011; A‖ = 85.4 × 10⁻⁴ cm⁻⁴, A⟂ = 85.3 × 10⁻⁴ cm⁻¹. Centres 1 and 2 can be attributed to colour centres as they are bleached after annealing. Centre 3 can be due to Mn²⁺ (only the central M_s = ± 1/2 transition is observable) most likely substituting for Ca²⁺ The site symmetry must be triclinic but due to Al, Si disorder and mixed Na, Ca composition the different components from magnetically non-equivalent sites are averaged out for many orientations.     

Electron Spin Resonance of Mn2+ in Hemimorphite

The Electron Spin Resonance of Mn²⁺ in natural crystals of hemimorphite was studied at RT, X-band. No fine structure other than the central M = | + 1/2 〉 ⇆ | −1/2 > transition with allowed (Δm = 0) and forbidden (Δm = ±1) hyperfine transitions were observed. The spectrum was fitted with the spin Hamiltonian parameters g = 2.001, A = −84.6 × 10⁻⁴ cm⁻¹. The crystal field parameter D was estimated equal to (8 ± 2) × 10⁻³ cm⁻¹. The most striking result is the size of the hyperfine splitting constant favoring occupancy of sixfold coordinated sites.     

Thermoelectric properties of indium sesquiselenide single crystals

Single crystals of δ-In₂Se₃ were prepared in the solid state laboratory at Qena-Egypt, by means of Bridgman technique. The temperature dependence of the thermal e.m.f. α in the temperature range from 205 K up to 360 K of In₂Se₃ was studied. The δ-phase In₂Se₃ sample appeared to be n-type. The ratio of the electron and hole mobilities are found to be μ_n/μ_p = 1.378. The effective masses of charge carriers are m = 1.3 × 10⁻³⁰, m = 8.27 × 10⁻³¹ kg for holes and electrons, respectively. The diffusion coefficient was estimated to be D_n = 3.37 cm²/s and D_p = 2.45 cm²/s for both electrons and holes, respectively. The mean free time between collision can be deduced to be τ_n = 70 × 10⁻¹⁶ s and τ_p = 8 × 10⁻¹⁴ s for both electrons and holes. The diffusion length of the electrons and holes are found to be L_n = 1.5 × 10⁻⁷ cm and L_p = 4.4 × 10⁻⁷ cm.     

Absorption and electrical conductivity of CaMoO4 crystals

The electrical conductivity σ of CaMoO₄ crystals was investigated between room temperature and 850°C. The mobility v_v and the diffusion coefficient D_v of the O⁻ ion vacancies have been derived from σ: v_vT = 3300 exp (−1.52 eV/kT) cm² K/Vs, D_v = (0.1…1) × exp (−1.52 eV/kT) cm²/s. An absorption occuring in crystals which are reduced or X-irradiated at low temperatures is dichroitic and caused by Mo⁵⁺ ions. For measurement in c direction the oscillator strength of the 680 nm absorption band is found to be about 0.1.     

Temperature‐tuned band gap energy and oscillator parameters of Tl2InGaSe4 semiconducting layered single crystals

The optical properties of Tl₂InGaSe₄ layered single crystals have been studied through the transmission and reflection measurements in the wavelength range of 500‐1100 nm. The analysis of room temperature absorption data revealed the presence of both optical indirect and direct transitions with band gap energies of 1.86 and 2.05 eV, respectively. Transmission measurements carried out in the temperature range of 10‐300 K revealed that the rate of change of the indirect band gap with temperature is γ = – 4.4 × 10^‐4 eV/K. The absolute zero value of the band gap energy was obtained as E_gi(0) = 1.95 eV. The dispersion of the refractive index is discussed in terms of the single oscillator model. The refractive index dispersion parameters: oscillator wavelength and strength were found to be 2.53 × 10^–7 m and 9.64 × 10¹³ m^–2, respectively. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth,thermophysical and electrical properties of the nonlinear optical crystal BPO4

Bulk BPO₄ crystals have been successfully grown from high temperature solution of BPO₄, Li₂O, and MoO₃ in the molar ratio of 2.3:1:1.3 by the top‐seeded solution growth (TSSG) method using [101]^c orientation seeds. There are no visible scattering centers and impurity of Mo in the as‐grown BPO₄ crystals, whose optical homogeneity reaches up to 1.6×10^–5/cm. BPO₄ possesses a specific heat of 0.50–1.00 J·g^–1·K^–1 in the temperature range from 298 to 698 K and exhibits strong anisotropic thermal expansion behavior with α_a = 14.2 × 10^–6 K^–1 and α_c = ‐4.0 × 10^–7 K^–1. Moreover, the thermal conductivity coefficients are calculated to be κ_a = 62.4 W·m^–1·K^–1 and κ_c = 51.5 W·m^–1·K^–1, which are remarkably larger than those of some commonly used borates. The measured dielectric constants, ε_a and ε_c, are 4.8 and 6.1, respectively, and the ionic conductivity coefficients, σ_a = 4.3 × 10^–8 S/cm and σ_c = 9.5 × 10^–8 S/cm, are several orders of magnitude lower than that of LiB₃O₅ (LBO). (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electric Characterization of Indium Sesquiselenide Single Crystals

Conductivity, Hall-effect measurements were performed on δ-phase In₂Se₃ single crystals, grown by the Bridgman method over the temperature range 150–428 K, in the directions perpendicular and parallel to the c-axis. The anisotropy of the electrical conductivity and of the Hall coefficient of n-type In₂Se₃ had been investigated. The values of the Hall coefficient and electrical conductivity at room temperature spreads from an order of R_H11 = 1.36 × 10⁴ cm³/coul, σ₁₁ = 4.138 × 10⁻³ Ω⁻¹ cm⁻¹ and R_H = 66.55 × 10⁴ cm³/coul, σ = 0.799 × 10⁻³ Ω⁻¹ cm⁻¹ for parallel and perpendicular to c-axis, respectively. The temperature dependence of Hall mobility and carrier concentration are also studied.     

The emission and structure of a new laser crystal Nd3+: NaY(WO4)2

A new laser Nd³⁺ : NaY(WO₄)₂ crystal rod of Φ 2.5 × 5 mm was pumped by a xenon flash lamp, and a 1.06 μm laser output was for the first time obtained in our laboratory, which has a threshold lower than 1 J. The crystal structure of NaY(WO₄)₂ was determined. The crystal is tetragonal, with the space group 14₁/a, a = 5.205(2) Å, c = 11.251(3) Å, V = 304.8(2) ų, Z = 2, D_calc = 6.62 g/cm³, D_obs = 6.51 g/cm³.     

Structures of azomethine imines of the pyrazolid-3-one-type (V). The structure of 1-[pyrenyl-(1)-methylene]-5,5-dimethyl-pyrazolid-3-one-betaine.

C₂₂H₁₈N₂O, P2₁, a = 7.473(2), b = 13.563(3), c = 18.264(3) Å, β = 115.49(4)°, Z = 4, U = 1670.9(6) ų, D_x = 1.295 Mg m⁻³, μ(MoKα) = 0.855 cm⁻¹, crystal size: 0.3 × 0.2 × 0.2 mm, colour: yellow. Final R = 0.086 for 1973 independent reflections excluding those with |F₀ < 3σ(F₀). The intensities were measured with an automatic diffractometer. There are two symmetrically independent molecules in the unit cell. The azomethine imine parts of the molecules are similar to those of four other relevant structures determined by X-ray analysis. A polymethinic part of a molecule is linked with an aromatic part via the bond C(4)–C(5). The mean pyrenyl plains and the mean plains of the five membered rings include dihedral angles of 29.6° for molecule A and 23.7° for molecule B.     

Small-angle neutron scattering study of radiation-induced defects in synthetic quartz

The supraatomic structure of single crystals of synthetic quartz was studied by thermal neutron small-angle scattering in the initial state (dislocation densities 54 and 570 cm⁻²) and after irradiation in the WWR-M reactor (Petersburg Nuclear Physics Institute) by fast neutrons with energies E _n > 0.1 MeV at fluences F _n = 0.2 × 10¹⁷ −5 × 10¹⁸ neutrons/cm². It is established that fast neutrons form point, linear, and volume defects in the lattice throughout the entire volume of a sample. Large-volume structures—amorphous-phase nuclei—reach sizes of ∼100 nm in quartz, while occupying a small total volume of ∼0.3% even at the maximum fluence 5 × 10¹⁸ neutrons/cm². The main fraction of the damaged volume (up to 5%) corresponds to point (with a radius of gyration of 1–2 nm) and linear defects, giving a comparable contribution (∼1–4%). The extended linear structures with a radius of 2 nm, even at a moderate fluence of 7.7 × 10¹⁷ neutrons/cm², have a significant total length per volume unit (∼10¹¹ cm/cm³) and can form a connected network with a cell ∼30 nm in size in the sample. Foreign atoms and molecules can migrate through channels of this network.

     

Ultrafast Optical Response in Quasi-One Dimensional Halogen-Bridged Mixed-Valence Complexes [Pt(en)2][PtBr2(en)2](ClO4)4 and [Pd(en)2][PdCl2(en)2](ClO4)4

Abstract

Ultrafast optical response in two quasi-one-dimensional halogen-bridged mixed-valence complexs [Pt(en)₂][PtBr₂(en)₂](ClO₄)₄ (en=ethylenediamine) (abbreviated as PtBr) and [Pt(en)₂][PtBr₂(en)₂](ClO₄)₄ (as PdCl) has been investigated by femtosecond absorption spectroscopy at room temperature by pump-probe spectroscopy. The photo-induced absorption around 1.3 eV and the bleaching from 1.5 eV to 2.7 eV were observed in PtBr. Both consist of a fast-decay component due to STEs and a slow-decay component due probably to polaron pairs. The former decays exponentially with the time constant of 1.4 ± 0.2 ps. The latter decays as erf(t ^β) with β = -0.22 ± 0.02, indicating the geminate recombination of an electron polaron and a hole polaron after moving freely along the chain. The deviation of β from the ideal random-walk model (β = -0.5) is explained by introducing the effect of potential barrier between the polarons hindering the recombination. A pump-probe absorption spectrum of PdCl is obtained from the reflection spectrum by the Kramers-Kronig relations. The time dependence of the transient photoinduced absorption around 1.7 eV and the bleaching from 1.9 eV to 2.5 eV were calculated to be described with three components. They correspond to free excitons with lifetime of about 800 fs, self-trapped excitons with lifetime of about 3 ps, and polaron pairs which hardly relax within 100 ps.     

Optical absorption of Fe3+ Ion in LiF crystals

The absorption spectrum of LiF—Fe³⁺ single crystals was investigated at liquid nitrogen temperature. Six new absorption bands, unobserved earlier in other works, were found, which were located at 11 200, 16 000, 22 700, 27300, 30 500, and 41 900 cm⁻¹. The spectrum was interpreted in the cubic cristalline field approximation with D_q = 1397 cm⁻¹, B = 657 cm⁻¹, C = 3226 cm⁻¹. Above mentioned bands were assigned to the transitions from a ground state ⁶A_1g to the levels ⁴T_1g(G), ⁴T_2g(G), ⁴A_1g(G) (⁴E_g), ⁴E_g(D), ²T_1g(F), and ⁴T_1g(F), respectively.     

Structures of Azomethine Imines of the Pyrazolidone-(3)-type, (III) The Structure of 1-[Anthryl-(9)-methylene]-pyrazolidone-(3)-betaine

C₁₈H₁₄N₂O, Pbca, a = 19.541(4) Å, b = 14.800(2) Å, c = 9.572(3) Å, Z = 8, U = 2768.3 ų, D_x = 1.32 g cm⁻³, μ(MoKα) = 0.93 cm⁻⁻¹, crystal size 0.5 × 0.2 × 0.1 mm, colourless. Final R = 0.077 for 1177 independent reflections excluded those with |F₀| < 8 σ(F₀). The intensities were measured with an automatic diffractometer. The azomethine imine unit of the molecule has a geometry in approximate agreement with a polymethinic electron structure. The conjugation of the azomethine imine unit with the anthryl unit is only small. The anthryl ring and the five membered pyrazolidone ring include a dihedral angle of 65.4°. The main intermolecular forces are C–H … N hydrogen bridges.     

Growth and characterisation of potassium cobalt nickel sulfate hexahydrate for UV light filters

A new single crystal for ultraviolet light filter, KCNSH (Potassium Cobalt Nickel Sulfate Hexahydrate) was designed and its crystal structure was studied using X‐ray diffraction in this paper. The empirical of the title compound is K₂Co_0.1Ni_0.9(SO₄)₂.6H₂O with formula weight 437.15. KCNSH crystal belongs to the monoclinic space group P2(1)/c, a=6.1390(3)Å, b=12.1839(6)Å, c=9.0095(4)Å, α=γ=90°, β=105.060(2)°, V=650.74(5)ų, Z=2, Dc=2.231g/cm³. Using the cooling solution method, we have grown a deep green KCNSH crystal with dimension of 12×12×40mm³. The transmission spectrum of KCNSH in the range from UV to near IR wavelengths, its thermal properties, and the relationship between the structure and optical transmission properties are also studied and further discussed in this paper. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of AgGa1‐xInxSe2 single crystals grown by Bridgman method

High‐pure and single‐phase AgGa_1‐xIn_xSe₂ (x=0.2) polycrystalline was synthesized by the mechanical and temperature oscillation method. Adopting the modified Bridgman method an integral AgGa_1‐xIn_xSe₂ single crystal with diameter of 14 mm and length of 35 mm has been obtained at the rate of 6 mm/day. It was found that there is a new cleavage face which was (101), and observed the four order X‐ray spectrum of the {101} faces. By the method of DSC analysis the melting and freezing points of the AgGa_1‐xIn_xSe₂ (x=0.2) single crystal were about 828°C and 790°C. The transmission spectra of the AgGa_1‐xIn_xSe₂ (x=0.2) sample of 5×6×2 mm³ were obtained by means of UV and IR spectrophotometer. The limiting frequency was 774.316nm and the band gap was 1.6eV. It can be found in the infrared spectrum that the infrared transmission was above 60% from 4000cm^‐1 to 600cm^‐1. The value of α in 5.3µm and 10.6µm were 0.022cm^‐1 and 0.1cm^‐1 respectively. All results showed that the crystal was of good quality. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)