Electronic structure of an oxygen vacancy in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> from the results of Ab Initio quantum-chemical calculations and photoluminescence experiments

The electronic structure of an oxygen vacancy in α-Al₂O₃ and γ-Al₂O₃ is calculated. The calculation predicts an absorption peak at an energy of 6.4 and 6.3 eV in α-Al₂O₃ and γ-Al₂O₃, respectively. The luminescence and luminescence excitation spectra of amorphous Al₂O₃ are measured using synchrotron radiation. The presence of a luminescence band at 2.9 eV and a peak at 6.2 eV in the luminescence excitation spectrum indicates the presence of oxygen vacancies in amorphous Al₂O₃.     

Luminescence of thulium-activated cubic boron nitride

Under high pressure and temperature conditions, we have obtained samples of thulium-activated cubic boron nitride in the form of micropowders, ceramics, and polycrystals activated by thulium in the presence of aluminum. We studied the cathodoluminescence (CL), photoluminescence (PL), and photoluminescence excitation spectra of the samples. In the luminescence spectra we observe structured bands with maxima at ∼370, ∼475, ∼660, and ∼ 800 nm, assigned to electronic transitions in the triply charged thulium ions. We have established that the most efficient method for excitation of “blue” luminescence at ∼475 nm for thulium ions in cBN is excitation by an electron beam. The cBN samples synthesized in the presence of Al have photoluminescence spectra with a more complex structure compared with samples not containing Al, with the band of dominant intensity at about 660 nm. Hypothetically, this is a consequence of incorporation of thulium ions into the crystalline phases cBN and AlN, which are equally likely to be formed during synthesis. The observed photoluminescence spectrum of the indicated samples is the superposition of the photoluminescence spectra of the Tm³⁺ ions located in the crystal fields of cBN and AlN of different symmetries. The presence in the photoluminescence excitation spectra (at 450, 490, and 660 nm) of structure, with features at wavelengths shorter than the excited photoluminescence, suggests a nonresonant mechanism for its excitation. We have established that luminescence of Tm³⁺ ions is less intense than for other rare earth elements incorporated into cubic boron nitride. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 547–555, July–August, 2008.     

Pressure induced amorphization of AlPO4

AlPO₄ has been compressed to pressures of 16 GPa in a diamond anvil cell and its X-ray diffraction pattern studied by the energy-dispersive technique. The compound is observed to become amorphous at ∼ 12 GPa. This explains the loss of Raman spectrum of AlPO₄ reported by Jayaraman and coworkers (1987).     

Luminescence of amorphous silicon nanoclusters

Films of amorphous silicon suboxide α-SiO _x containing amorphous silicon nanoclusters have been grown by direct current magnetron sputtering. It has been found that two radiation bands are observed in the photoluminescence spectra of relatively large amorphous nanoclusters (a size of ∼2 nm) unlike one photoluminescence band of silicon nanocrystals of the same size. The form of the spectra upon the change in the nanocluster sizes agrees with that predicted in theoretical works, in which the energy spectrum of amorphous nanoclusters has been calculated taking into account quantum confinement of delocalized, weakly localized, and strongly localized states.     

Magnetic structure and properties of a bulk Fe72Al5P10Ga2C6B4Si1 alloy in the amorphous and nanocrystalline states

The structure forming under controlled crystallization of a bulk Fe₇₂Al₅P₁₀Ga₂C₆B₄Si₁ amorphous alloy has been studied using differential scanning calorimetry, transmission electron microscopy, and x-ray diffraction. Crystallization of the alloy was established to result in the formation of a nanocrystalline structure consisting of three phases. The domain structure and magnetic properties of amorphous and nanocrystalline samples were investigated using the magnetooptic indicating film technique (MOIF) and a vibrating-sample magnetometer. The coercive force and the saturation magnetization of the amorphous samples were found to be 1 Oe and 130 emu/g, respectively. It was shown that the formation of the nanocrystalline structure entails a dramatic decrease in domain size (down to 1–4 μm) as compared to an amorphous sample (∼1 mm). Simultaneously, a decrease in the saturation magnetization and a strong increase in the coercive force of the samples were observed. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 5, 2004, pp. 858–863. Original Russian Text Copyright ? 2004 by Abrosimova, Aronin, Kabanov, Matveev, Molokanov.     

Luminescence and Reversible Luminescence Thermochromism of Bulk and Microcrystals of Dibenzoylmethanatoboron Difluoride

Essential differences in the luminescence properties of dibenzoylmethanatoboron difluoride (1) bulk and microcrystals were detected. Analysis of the spectral data showed that in every case the fluorescence spectrum of 1 consisted of three components: monomer fluorescence, excimer fluorescence, and fluorescence related with interdimer interaction. Evolution of luminescence spectra observed with decrease of the crystal size are bound with decrease of monomer fluorescence intensity and considerable growth of intensity of fluorescence related to interdimer interaction. The presence of reversible luminescence thermochromism was discovered for 1: lowering the temperature from 300 to 77 K resulted in essential hypsochromic shift of the luminescence band maximum (∼60 nm) connected with considerable decrease of the distances between the planes of the neighboring molecules (∼0.1 Å) that lead to the weakening of interdimer interaction and intensification of monomer luminescence.     

Upconversion due to energy transfer involving Pr<Superscript>3+</Superscript> ions in pairs

Upconversion luminescence in triply ionized praseodymium-doped TeO₂–Li₂O glass using excitation at ∼590 nm into the ¹D₂ level from a dye laser pumped with the second harmonic of a pulsed Nd:YAG laser has been reported. The mechanism involved in the upconversion emission observed at ∼480 nm indicates that the most important contribution is energy transfer among praseodymium ions in pairs followed by the dipole–dipole interaction. The rate-equation model for the emission at ∼480 nm that provides direct information to determine the energy-transfer rates containing the pair of states involved in the upconversion process has been explored.     

Effect of vacancies and interstitials on the dynamic properties of the La2−x SrxCuO4 superconductor

The effect of vacancies and interstitials in the CuO₂ layer on the vibrational spectrum in the La_2−x Sr_xCuO₄ system has been calculated by molecular dynamics. It is shown that the excitation probability for local ∼0.4-eV high-frequency vibrations of nonphonon origin in the vicinity of Sr impurity atoms decreases if copper vacancies are introduced at a concentration x=0.17, which corresponds to the maximum superconducting transition temperature, this decrease being still more effective (by about ten times) if interstitial atoms are present. The appearance of interstitials makes a considerable region around them (five to six nearest neighbors) quasi-amorphous. A comparison with available experimental data is made. It is concluded that the behavior of the system under irradiation is accounted for primarily by interstitials, which bring about strong perturbation in the lattice (∼1 nm) up to making it completely amorphous. Fiz. Tverd. Tela (St. Petersburg) 40, 984–988 (June 1998)     

Composition and structure-property relationships of chromium-diboride/molybdenum-disulphide PVD nanocomposite hard coatings deposited by pulsed magnetron sputtering

The composition and structure-property relationships of physical vapour deposited coatings containing mixtures of CrB₂ and MoS₂ are reported. The coatings were produced by pulsed magnetron sputtering of loosely-packed powder targets formed from a blend of chromium and boron powders, alloyed with 12.8, 18.9 and 24.0 atom percent MoS₂. Results of coating characterisation (by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Auger electron spectroscopy and nanoindentation measurement of hardness and elastic modulus) revealed that increasing amounts of MoS₂ produced the following effects: frustration of crystallisation and phase separation; a decrease in average grain sizes (from ∼5.5 to ∼ 4.3 nm) and a decrease in coating hardness (from ∼15 to ∼ 10 GPa). Scratch testing also showed that the load-bearing capability of coatings was altered; coatings possessing an intermediate concentration of MoS₂ exhibited the best behaviour with no failure observed in mechanical testing, due to an optimal nanocomposite structure. The corrosion resistance (investigated by potentiodynamic polarisation tests) however tended to improve as more MoS₂ was introduced. An investigation of the effects of generating an amorphous structure by adding Ti and C into Cr-B-MoS₂ coatings revealed improved corrosion behaviour, which significantly exceeded that of uncoated stainless steel and CrB₂-coated samples. PACS 68.37.Lp; 68.55.A-; 68.55.Ln; 68.55.Nq; 68.60.Bs     

Luminescence and lasing properties of neodymium- and uranium-activated inorganic laser liquids

An attempt was made to describe and show the possibilities of new inorganic neodynium- and uranium-activated laser liquids: SO₂-GaCl₃-NdCl₄; SO₂Cl₂-GaCl₃-NdCl₃-UO₂Cl₂; POCl₂-MCl_n-NdCl₃-UO₂Cl₂ for development and synthesis of direct nuclear reaction-excited lasers. Luminescence data presented in the work were used to calculate the luminescence parameters of the laser liquids such as oscillator strengths f, probability of spontaneous radiation A, intermultiplet luminescence branching coefficient β, cross-section for induced radiation σ, luminescence decay time τ, quantum yield η, and others. It is shown that the oscillator strengths of the normal absorption bands of Na³⁺, which play the main part in the pumping processes, exceed the oscillator strengths of Na³⁺ for aqueous and many other nonaqueous systems. In the luminescence excitation spectra of the Na³⁺ ion, bands are isolated in the range 400–1000 nm atλ _rec =1.06 μm. With excitation, luminescence occurs through the⁴F_3/2→⁴I_{9/2,11/2.13/2} channels. Luminescence spectral data are related to the lasing parameters. The threshold lasing energy is∼18 J/cm³. For a resonator with mirros h₁=100% and h₂=20, 40, 56, and 80%, the lasing energy is∼20–120 MJ/cm³ in the pumping energy range 18–180 J/cm³. The differential efficiency is ∼0.2% The substantial angular radiation divergence (θ∼4·10⁻² rad) and strong thermostatic distortions that occur in the active element (dn/dT≈−1.9·10⁻⁴K⁻¹) are a disadvantage of laser liquids. It is shown that operation of neodymium- and uranium-activated inorganic liquid lasers is stable under the present conditions. A. I. Gertsen Russian State Pedagogical University, Moika Embankment, 48, St. Petersburg, 191186, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 607–619, September–October, 1997.     

Luminescence of short-lived color centers induced in LiF crystals by a pulsed microwave discharge

A new phenomenon — intense luminescence of noncolored lithium fluoride (LiF) crystals excited by an electrodeless pulsed microwave discharge at the prebreakdown stage of development — is observed. This luminescence consists of the luminescence of short-lived aggregate F₂ and F ₃ ⁺ color centers at room temperature. It is shown that the density of short-lived color centers induced in the surface layer of LiF crystals by a microsecond microwave discharge reaches values of ∼10¹⁹−10²⁰ cm⁻³. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 163–167 (10 August 1997)     

The special features of the luminescence and light resistance of europium complexes and their mixtures with lanthanum complexes in polymethyl methacrylate

The kinetics of luminescence and transformation of short-lived products of the photolysis of europium and lanthanum complexes with thenoyltrifluoroacetone and 1,10-phenanthroline and their mixtures in polymethyl methacrylate films was studied by the nanosecond laser photolysis method with recording both light emission and absorption. Fast (535 and 585 nm, ⁵ D ₁ → ⁷ F ₀, ⁷ F ₃, decay time 0.7 μs) and slow (613 nm, ⁵ D ₀ → ⁷ F ₂, luminescence rise and decay times 0.7 μs and 0.5 ms, respectively) luminescence was studied. Induced absorption with a maximum at 600 nm and decay time ∼3 ms was observed; this absorption was assigned to triplet states of the deprotonated form of thenoyltrifluoroacetone. The dependences of luminescence intensity on the concentration of the components in a mixture of complexes were analyzed, and synergistic effects of luminescence strengthening were estimated. The kinetics of a decrease in luminescence intensity during photolysis was studied. Possible mechanisms of a decrease in the relative initial process rate and an increase in the quasi-stationary value of relative luminescence intensity as the concentration of complexes in the polymer increased were discussed.     

Spodumene and garnet luminescence excited by subnanosecond electron beams

Pulsed cathodoluminescence of spodumene and yttrium-aluminum garnet crystals activated by Mn²⁺ and Nd³⁺ ions, respectively, is investigated. The luminescence was excited upon crystal irradiation by electron beams with current densities of 35 and 100 A/cm² and average electron energy of ∼ 50 keV for 0.1, 0.25, and 0.65 ns. It is demonstrated that the electron beam duration decreased to several tenth of a nanosecond does not lead to essential changes of the mechanisms of pulsed cathodoluminescence excitation and character of its spectrum, but in this case, the intensity of luminescence of the hole centers increases compared with the intracenter luminescence.     

Analysis of the latent structure of luminescence and absorption spectra of thallium complexes

Comprehensive investigations of luminescence, excitation, and absorption spectra as well as of the luminescence kinetics of a frozen LiCl-Tl⁺ solution are carried out. It is established that the luminescence spectrum consists of four components. One component is caused by luminescence of the matrix and the remainder by luminescence of one luminescence center, namely, by the saturated complex of thallium TlCl₂(H₂O)Cl₄. The absorption spectrum consists of three components. Their parameters have been evaluated. Each component of the luminescence spectrum is excited in several components of the absorption spectrum. It is found that the luminescence spectrum components and their intrinsic absorption bands are located differently on the frequency axis. These data are similar to those obtained for other activated solutions of electrolytes. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 75–78, January–February, 2000.     

Thermal stability and electronic structures of N-doped SiSb films for high temperature applications of phase-change memory

Undoped and N-doped Si_10.5Sb_89.5 films were deposited by magnetron sputtering. The X-ray diffraction spectra indicated that all of the films crystallized into crystalline Sb with a rhombohedral structure after annealing at 280°C for 3 min. X-ray photoelectron spectroscopy analysis indicated that the incorporated nitrogen combined with Si to form silicon nitride in the SiSb films. The changes in electrical resistance and thermal stability of the undoped and N-doped Si_10.5Sb_89.5 films were investigated. The crystallization temperature increased from ∼225°C to ∼250°C when 13 at.% nitrogen was added into the Si_10.5Sb_89.5 film and increased further with increasing nitrogen content. The thermal stability of the amorphous film was enhanced by nitrogen doping. The maximum temperature for 10-year retention of amorphous state of a pure Si_10.5Sb_89.5 film is ∼140°C and the temperature of N-doped Si_10.5Sb_89.5 films is even higher, which may be helpful to improve the data retention and performance of phase-change memory in high temperature applications.     

Spectral and kinetic characteristics of CdI<Subscript>2</Subscript> and CdI<Subscript>2</Subscript>:Pb scintillators

We have studied the effect of lead dopant on the optical absorption, photoluminescence, and x-ray luminescence spectra, and the scintillation characteristics of CdI₂ at room temperature. The crystals for the study were grown by the Stockbarger-Bridgman method. Activation of CdI₂ from the melt by the compound PbI₂ leads to the appearance in the absorption spectra in the near-edge region of an activator band at 395–405 nm, which is interpreted as an A band connected with electronic transitions from the ¹S₀ state to the ³P₁ levels in the Pb²⁺ ion. For x-ray excitation, CdI₂:Pb²⁺ crystals with optimal dopant concentration (∼1.0 mol%) are characterized by a light yield with maximum in the 570–580 nm region that is an order of magnitude higher than for CdI₂ crystals in the 490–500 nm band. For α excitation, the radioluminescence kinetics for cadmium iodide is characterized by a very short (∼0.3 nsec) rise time and fast decay of luminescence, with τ₁ ≈ 4 nsec and τ₂ = 10–76 nsec. Depending on the conditions under which the crystals were obtained, the fast component fraction is 95%–99%. The crystal is characterized by a similar scintillation pulse in the case of excitation by x-ray pulses. The radioluminescence pulse shape for CdI₂:Pb in the decay stage is predominantly exponential, with luminescence decay time constants τ₁ ≈ 10 nsec and τ₂ = 200–250 nsec. This system is characterized by low afterglow, at the level for the Bi₄G₃O₁₂ scintillator. We have demonstrated the feasibility of using CdI₂:Pb as a scintillator for detecting α particles. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 825–830, November–December, 2008.     

Luminescence of fluctuation tails of disordered solid solutions

The form of the stationary luminescence spectra of excitons, localized by composition fluctuations, in disordered solid solutions under weak excitation is calculated. The tail states for which there are no nonradiative transition channels are distinguished by means of continuum percolation theory. Such states are responsible for the “zero-phonon” luminescence band. The shape of the short-wavelength luminescence band edge is determined mainly by the number of isolated localizing clusters and their smallest complexes, which decreases rapidly near the mobility threshold. The real luminescence spectrum is due to the simultaneous emission of phonons. The phonon emission determines the form of the long-wavelength wing of the emission band. The computed shape of the emission spectrum is compared with the experimental luminescence spectra of the solid solution CdS_(1−c)Se_c. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 3, 274–279 (10 February 1997)     

Photoluminescence and optical absorption properties of polymer modified carbon nanotubes

Polymethyl methacrylate modified carbon nanotubes were prepared using γ radiation, and the modified carbon nanotubes exhibited strong luminescence (∼ ∼568 nm) at room temperature and an absorption peak at ∼ ∼247 nm can be observed in the polymer modified samples.     

Atomic frequency offset locking in a Λ type three-level Doppler broadened Cs system

We here present a comparative study of frequency stabilities of pump and probe lasers coupled at a frequency offset generated by coherent photon-atom interaction. Pump-probe spectroscopy of the Λ configuration in D₂ transition of cesium is carried out to obtain sub-natural (∼2 MHz) electromagnetically induced transparency (EIT) and sub-Doppler (∼10 MHz) Autler-Townes (AT) resonance. The pump laser is locked on the saturated absorption spectrum (SAS, ∼13 MHz) and the probe laser is successively stabilized on EIT and AT signals. Frequency stabilities of pump and probe lasers are calculated in terms of Allan variance σ(2,τ) by using the frequency noise power spectrum. It is found that the frequency stability of the probe stabilized on EIT is superior (σ∼2×10⁻¹³) to that of SAS locked pump laser (σ∼10⁻¹²), whereas the performance of the AT stabilized laser is inferior (σ∼6×10⁻¹²). This contrasting behavior is discussed in terms of the theme of conventional master-slave offset locking scheme and the mechanisms underlying the EIT and sub-Doppler AT resonances in a Doppler broadened atomic medium.     

Low-temperature specific heat of crystalline and amorphous Eu2(MoO4)3

The specific heat C _total of crystalline and amorphous Eu₂(MoO₄)₃ is measured in the temperature interval 4.5–30 K. The amorphous state is obtained by applying pressure ∼7 GPa at room temperature. It is found that the specific heat of the crystal at T⩽7.5 K is described by a cubic function of temperature, while the specific heat of the amorphous sample has a strongly non-Debye character in the entire experimental temperature interval. The curve of C _total for amorphous europium molybdate is analyzed in a model of soft atomic potentials, and it is shown that it agrees well with universal low-temperature anomalies of the specific heat of classical glasses obtained by quenching from the liquid. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 8, 623–627 (25 October 1998)