Crystal growth and scintillating properties of (Pr,Si)‐doped YAlO3

This paper deals with Pr‐doped and Pr, Si‐codoped YAlO₃ single crystal growth by the micro‐pulling‐down method and investigation of their spectroscopic and scintillating properties. The Pr³⁺ 5d ‐4f radioluminescence intensity is more than 10 times higher than that of Bi₄Ge₃O₁₂ standard sample, but the Si‐codoping decreases it. Absorption spectra of as‐grown and air‐annealed Si,Pr‐codoped YAlO₃ samples show along with an onset of 4f ‐5d transition round 230 nm the induced absorption band at 400 nm which possibly related to a hole center absorption (Pr⁴⁺ or O^‐). Thermoluminescence measurements above the room temperature were performed in order to monitor deep electron traps. Strong concentration dependence of thermoluminescence was observed for Pr:YAlO₃ glow curves. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrical,optical and photoconductive properties of Poly(dibenzo‐18‐crown‐6)

To investigate the energy levels, absorption bands, band gap, dominant transport mechanisms, recombination mechanisms and the free carrier life time behavior of poly‐dibenzo‐18‐crown‐6, poly‐DB18C6, films, the dark electrical conductivity in the temperature range of 200‐550 K, the absorbance and photocurrent spectra, the photocurrent –illumination intensity and time dependence at 300 K were studied. The dark electrical conductivity measurements revealed the existence of three energy levels located at 0.93, 0.32 and 0.76 eV below the tails of the conduction band. The main transport mechanism in the dark was found to be due to the thermal excitation of charge carriers and the variable range hopping above and below 260 K, respectively. The photocurrent and absorbance spectra reflect a band gap of 3.9 eV. The photocurrent ‐illumination intensity dependence reflects the sublinear, linear and supralinear characters indicating the decrease, remaining constant and increase in the free electron life time that in turn show the bimolecular, strong and very strong recombination characters at the surface under the application of low, moderate and high illumination intensity, respectively. A response time of 25.6 s was calculated from the decay of I_ph‐time dependence. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Infrared Spectra and Photoinduced Absorption of C60 Doped Polyhexylthiophene

Abstract

We report the IR spectra and the photoinduced absorption of polyhexylthiophene(PHT) doped with C₆₀. The presence of C₆₀ ^?n anions is observed in the IR spectra by a mode at 1383 cm^?1 and a broad electronic transition at 1.2 eV, while most of the C₆₀ molecules stay neutral. This is indicative that for a small fraction of C₆₀ molecules, charge transfer occurs in the ground state.

The photoinduced absorption spectra display a sharp transition at 1.15 eV peculiar to C₆₀ monoanion, the spectral features change with fullerene concentration. The intensity of the polymer photoinduced bands increases 5-10 times due to photoinduced charge transfer to C₆₀.     

Luminescence and defects of Yb3+-doped sol–gel silica glasses

The optical properties of Yb-doped sol–gel silica glasses were studied by optical absorption and radio-luminescence (RL) measurements, that revealed the typical absorption and emission pattern of Yb³⁺ ions. Moreover, RL bands in the 1.5–3.5 eV interval were also observed, and related to defects of the silica matrix. The RL intensity temperature dependence, investigated in the 10–320 K interval, evidenced the presence of the SiO₂ self-trapped exciton emission at 2.2 eV, whose intensity was rapidly quenched by temperature increasing. At variance, the Yb³⁺ emission intensity increased markedly by temperature increasing. This phenomenon is interpreted by considering a competitive role of point defects in free carrier trapping, evidenced by parallel wavelength resolved thermally stimulated luminescence measurements.     

Optical Absorption Edge of Mg + Zn: LiNbO3

The optical transmittance of LiNbO₃ single crystal double doped with MgO and ZnO was measured from the ultraviolet to the visible range. The wavelength dependence of the absorption coefficient α and its root α^1/2 (α versus hv and α^1/2 versus hv, respectively) were calculated and the characteristics of the absorption edge were discussed. The energy gaps E_g and E_g of the crystals which correspond to the direct transition and the indirect transition, respectively, and the energy of phonons taking part in the indirect transition were calculated. The effects of dopants Mg and Zn on the optical absorption properties are discussed. It was found that the energy E_g of our sample which was double doped with MgO and ZnO was smaller than that of congruent LN, causing the indirect transition absorption edge to move towards the infrared.     

Optical properties of Er3+-singly doped and Er3+/Yb3+-codoped novel oxyfluoride glasses

Novel oxyfluoride glasses SiO₂–Al₂O₃–Na₂O–ZnF₂ doped with Er³⁺ and Er³⁺/Yb³⁺ were fabricated. The optical properties of the synthesized glasses were experimentally and theoretically investigated in detail. The experimental and calculated oscillator strengths of Er³⁺ were determined by measurement of the absorption spectrum of Er³⁺-singly doped glass. According to the Judd–Ofelt theory, the experimental intensity parameters were calculated, from which the radiative transition probabilities, fluorescence branching ratios and radiative lifetimes were obtained. The fluorescence lifetime and quantum efficiency for the near-infrared emission of Er³⁺-singly doped glass were determined to be 3.0 ms, and 42%, respectively. Visible upconversion luminescence was observed under 980 nm diode laser excitation. The dependence of the upconversion emission intensity upon the excitation power was examined, and the upconversion mechanisms are discussed.     

EDA complex stability constants and formation enthalpies in a binary liquid crystalline system with induced smectic phase

In the binary system 4,4′-bis-[n-butylamino]-biphenyl/-(2,2-dicyano-ethenyl)-phenyl 4-n-nonyloxybenzoate which due to EDA complex formation exhibits an induced S_A phase, measurements of the charge transfer band, the molar volumina and transition enthalpies were done. By the concentration and temperature dependence, resp., of the charge transfer absorption and the strongly negative excess volumina we estimated the stability constant and the formation enthalpy of the complex. The data obtained by the two independent methods agree sufficiently.     

Effect of cationic impurities on solubility and crystal growth processes of ammonium oxalate monohydrate: Role of formation of metal‐oxalate complexes

The effect of different bi‐ and trivalent cationic impurities on the solubility of ammonium oxalate and the composition and distribution of chemical complexes formed in saturated ammonium oxalate aqueous solutions as a function of impurity concentration are investigated. The knowledge of the composition and stability of complexes formed in saturated aqueous solutions is then employed to explain the appearance of dead zones of supersaturation for growth and the difference in the effective segregation coefficient of the impurities. Analysis of the experimental results revealed that: (1) at a constant temperature, the dependence of concentration of complex species formed in saturated solutions on the concentration of different impurities can be described by an equation similar to that of the concentration dependence of density of solutions, (2) the dominant metal‐containing species present in saturated solutions are negatively‐charged, most stable oxalato complexes like Cu(C₂O₄)₂²⁻, Mn(C₂O₄)₃⁴⁻, Zn(C₂O₄)₃⁴⁻, Cr(C₂O₄)₃³⁻ and Fe(C₂O₄)₃³⁻, (3) in the investigated range of impurity concentration, the solubility of ammonium oxalates increases linearly with the concentration of all impurities and the increase is associated with the stability of dominant complexes, (4) appearance of dead supersaturation zones in the presence of impurities is associated with instantaneous adsorption of all growth sites by dominant oxalato complexes in relatively short adsorption time, and (5) the segregation coefficient of an impurity cation M of charge z + increases with a decrease in the solubility product constant K_sp for the hydrolysis products of reactions of the type: M^{z +} ↔ M₁^{(z −1)+} + H⁺ (where the cation M has z + charge, and H⁺ is hydrogen ion). (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterisation of Bi2Se3 Crystals Highly Doped with Pb

Pb-doped Bi₂Se₃ crystals were prepared from starting elements Bi, Se and Pb of 5N purity in the concentration interval c_pb = 0 – 4 × 10²⁵ Pb atoms m⁻³ by a modified Bridgman method. The measured values of the transmittance and reflectance were used to determine the dependence of the absorption coefficient K on the photon energy for crystals with various values of cpb and to prove the shift of the short-wavelength absorption edge with cpb. On the basis of the assumption of the validity of the “single valley” model, which can describe the lowest conductivity band of Bi₂Se₃, and using the values of the freecarrier effective mass in the directions perpendicular and parallel to the trigonal axis c we determined the value of the reduced Fermi energy η 300 K for crystals with various values of cpb. Using the value of η, we calculated the dependence of the Seebeck coefficient on cpb and compared it with the experimentally determined values. The comparison has shown that the increasing content of Pb atoms in the Bi₂Se₃ lattice leads to a suppression of the role of the mechanism of scattering by ionised impurities; at higher concentrations of Pb in the crystal the mechanism of scattering of free carriers by acoustic phonons becomes dominant. Further, the ideas on the nature of the point defects in the Bi₂Se₃(Pb) crystals are presented and the “anomalous” dependence of the free-electron concentration on cpb is qualitatively accounted for.     

Temperature dependence of electrical conductivity and hall effect of Ga2Se3 single crystal

Electrical conductivity (σ) and Hall coefficient (R_H) of single crystal grown from the melt have been investigated over the temperature range from 398 K to 673 K. Our investigation showed that our samples are p-type conducting. The dependence of Hall mobility an charge carrier concentration on temperature were presented graphically. The forbidden energy gap was calculated and found to be 1.79 eV. The ionization energy of impurity level equals 0.32 eV approximately. At 398 K the mobility equals to 8670 cm² V⁻¹ s⁻¹ and could described by the law μ = aTⁿ (n = 1.6) in the low temperature range. In the high temperature range, adopting the law μ = bT^–m (as m = 1.67), the mobility decreases. This result indicates that in the low temperature range the dominant effect is scattering by ionized impurity atoms, whereas in the high temperature range the major role is played by electron scattering on lattice vibrations (phonons). At 398 K the concentration of free carriers showed a value of about 1.98 × 10⁷ cm⁻³.     

Investigation of Optical Properties of YAlO3Pr3+ Single Crystals

Colour centers in YAlO₃:Pr³⁺ crystals originating under xenon lamp or y–radiation and oxidizing annealing are considered. The nature of colour centers under these treatments is similar in nominally pure and Pr³⁺ containing crystals but the intensity of induced absorption lines is higher in activated crystals which assumably is associated with valent transitions of Pr ions.     

Optical properties of pure and metal ions doped ammonium sulfate single crystals

A study of the optical properties of pure‐and some metal ions doped ammonium sulfate crystals (AS) were made. Optical constants of AS crystals were calculated at room temperature. The optical absorption coefficient (α ) was analyzed and interpreted to be in the allowed direct transition. The introduction of Rb⁺ or Cs⁺ ions gives rise to an intense charge transfer band with a maximum at λ= 310 nm in the optical spectrum. In case of Cr³⁺ ‐doping, the absorption shows a shoulder just before the onset band to band transition. The values of the allowed direct energy gap E_g for undoped and doped crystals were calculated. It was found that E_g values were decreased with metal ions doping. The refractive index, the extinction coefficient and both the real and imaginary parts of the dielectric permittivity were calculated as a function of photon energy. The validity of Cauchy‐Sellimeier equation was checked in the wavelength range 4.9 ‐ 5.6 eV and its parameters were calculated. Applying the Single‐Effective‐Oscillator model, the moments of ε (E ) could be estimated. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Absorption,Fluorescence and Phosphorescence and Phosphorescence of Single Crystals of 1,2,4,5-Tetrachlorobenzene and 1,4-Dichlorobenzene at Low Temperatures

Abstract

The emission spectra of ultra pure single crystals of 1, 2, 4, 5. tetrachlorobenzene (TCB) and 1, 4-dichlorobenzene (DCB) at temperatures from 4.2°K upwards are reported. In addition, by use of the phosphorescence excitation technique the singlet-triplet absorption spectrum at 4.2°K has been obtained.

The phosphorescence emission of TCB at 4.2°K occurs predominantly from a defect origin “X” situated 48 cm^?1 below the triplet exciton band. The triplet exciton energy level is at 26676 cm^?1 from both emission and absorption studies. This is the triplet emission origin when the crystal is above 12°K. The temperature dependence of the emission intensity from the defect has an activation energy of 40±8 cm^?1. This value is consistent with our suggestion of thermal depopulation of the traps.

Single crystals of DCB show strong excimer emission and weak triplet exciton emission. There is no evidence for trapping levels. The triplet exciton emission. There is no evidence for trapping levels. The triplet exciton origin is 27890 cm^?1 from both emission and absorption studies.

Weak fluorescence (φ < 10⁰²) is detected from both TCB and DCB.

Vibrational analyses are reported for the absorption, fluorescence and phosphorescence spectra.     

Metastable photoexpansion of hydrogenated amorphous silicon produced by exposure to short laser pulses

The study of the metastable expansion of hydrogenated amorphous silicon after exposure to nanosecond laser pulses as well as to cw light of similar average intensity has revealed a decrease from 1 to 0.5 in the short-time power-law exponent of photon flux dependence of the effect. This transition appears at a carrier generation rate of approximately G = 10²³ cm⁻³ s⁻¹ and is compatible with the assumption that the underlying structural change is produced by band-to-band/tail recombination of photo-excited carriers. This view is further supported by our observation that the quantum efficiency of photoexpansion does not depend on photon energy.     

Cleavage Mechanoluminescence in Crystals

When a crystal is cleaved, initially the mechanoluminescence (ML) intensity increases linearly with time, attains an optimum-value I_m at a particular value of timet_m, and then decays exponentially with time. Cleavage ML provides a new tool to determine the velocity, v of cracks in crystals, and it may be given by v = H/t_m, where H is the thickness of the crystal. Both, the peak ML intensity I_m and total ML intensity I_T increase linearly with the area of newly created surfaces A as well as with the surface charge density γ. The ML intensity decreases with temperature primarily due to the decrease in the surface charge density. Beyond a particular temperature, the surface charge density may decrease to such a value where the breakdown of gases and solids may not be possible and thereby the ML may not appear. Depending on the prevailing conditions either the ML emission resembling gas discharge or other types of the luminescence of solids, or that having these two characters may be obtained. There exists a good correlation between the theoretical and experimental results obtained for cleavage ML in crystals.     

Intensities of circular dichroism and absorption bands and the states of <Emphasis Type="Italic">d</Emphasis> ions in absorbing media: II. Tetrahedrally coordinated positions of <Emphasis Type="Italic">d</Emphasis> ions

The factors affecting the band intensity in the circular dichroism (CD) and absorption spectra of tetrahedrally coordinated d ions in an absorbing medium (symmetry selection rules, structural position, and bond covalence) are analyzed. It is shown by the examples of the Cr⁴⁺ ion in Ca₃Ga₂Ge₄O₁₄ crystal and the Fe²⁺ and Fe³⁺ ions in SiO₄ crystal that the symmetry forbiddenness of the transitions from orbitally degenerate states and the covalence of the d-ion-ligand bond lead to changes in the intensity of the corresponding CD bands in a wide range, beginning from zero. It is shown by the example of Ca₃Ga₂Ge₄O₁₄, LiAlGeO₄, LiGaGeO₄, and LiGaSiO₄ crystals activated with Cr⁴⁺ ions that the preferred ion localization position corresponds to a higher effective symmetry.     

Properties of heavily doped GDSi with low resistivity

Significant decrease in resistivity has been observed in glow-discharge-produced silicon (GDSi) containing 10¹⁹?10²¹ cm^?3 phosphorous atoms. At the highest doping level a resistivity of 0.01 ω cm at room temperature was obtained. The temperature dependence of the resistivity follows the form, $\text{? = ?}{}_0\text{exp}\text{(T}{}_0\text{/T)}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}$, over a temperature range from 80–400 K. Optical absorption, which increased with wavelength and was roughly proportional to the conductivity, was observed in the longer wavelength side of the intrinsic absorption edge and it was ascribed to mobile charge carriers. Hall effect measurements have shown that μ_H of phosphorus doped GDSi is about 1 cm² V^?1s^?1 and has a normal (negative) sign.     

Study of optical and transport properties of K2CuCl4 · 2H2O single crystal

Optical absorption, transport properties and EPR of K₂CuCl₄ · 2H₂O single crystals have been studied. The optical absorption in UV, and visible region are characterized by a charge transfer band, and in the near infrared region at 3998, 4336, and 4480 cm⁻¹ are attributed to transitions between the stark levels of copper(II) ion in an extended octahedral crystal field. An anisotrophic ‘g’ value was observed with g_∥ = 2.12 and g_∥ = 2.24 by EPR method. The spin orbit coupling constant is found to be 500 cm₋₁. D.C. electrical conductivity measurements with temperature reveal an anisotropy characteristic of a two-dimensional layered structure and exhibit a first order irreversible structural phase-transition at 377 K, i.e. from tetragonal to monoclinic crystal system. X-ray diffraction studies and density calculations from the crystal structure data in both the phases suggest that the first order irreversible transition occurs following the loss of the two water molecules of hydration.     

Annealing effect on electrical and photoconductive properties of Si implanted GaSe single crystal

GaSe single crystals grown by Bridgman method have been doped by ion implantation technique. The samples were bombarded in the direction parallel to c‐axis by Si ion beam of about 100 keV to doses of 1 × 10¹⁶ ions/cm² at room temperature. The effects of Si implantation with annealing at 500 and 600 °C on the electrical properties have been studied by measuring the temperature dependent conductivity and photoconductivity under different illumination intensities in the temperature range of 100–320 K. It is observed that Si implantation increases the room temperature conductivity 10⁻⁷ to 10⁻³ (Ω‐cm)⁻¹ depending on the post annealing temperature. The analysis of temperature dependent conductivity shows that at high temperature region above 200 K, the transport mechanism is dominated by thermal excitation in the doped and undoped GaSe samples. At lower temperatures, the conduction of carriers is dominated by variable range hopping mechanism in the implanted samples. Annealing of the samples at and above 600 °C weakens the temperature dependence of the conductivity and photoconductivity. This indicates that annealing of the implanted samples activates Si‐atoms and increases structural deformations and stacking faults. The same behavior was observed from photoconductivity measurements. Hence, photocurrent‐illumination intensity dependence in the implanted samples obeys the power low I_pc ∝ Φⁿ with n between 1 and 2 which is an indication of continuous distribution of localized states in the band gap. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)