Some defects appearing in chromium doped Al2O3 monocrystals as a result of thermal treatment

Results of experiments related to thermal treatment of Al₂O₃ crystals doped by chromium (ruby) in various gaseous media: CO, H₂, vacuum and O₂ are given. The kinetics of the formation and destruction of dye centres during this process is discussed. Special attention is given to revealing the causes of the appearance of an absorption band in the region of 315 nm which is related to the internal stability of the crystal with respect to intensive light radiation. – An assumption is made on the nature of the absorption band. – A computation is made of the diffusion coefficient of dye centres related to 315 nm absorption band. This is derived as a function of chromium concentration.     

UV‐visible emission of (O2‐ ‐ F+) centres in KBr

Single crystals of KBr containing the (O^2‐ ‐ F⁺) color centres and elaborated in atmospheric air by the Czochralski method are studied. The measure of the UV‐visible emission spectra at 78 K present several emission bands situated between 340 and 800 nm. The photoluminescence excitation shows that these emissions are attributed to O^‐₂ and (O^2‐ ‐ F⁺) centres. This study show the new emission bands of (O^2‐ ‐ F⁺) centres which are situated in the UV‐visible spectral domain. The comparison between the emission spectra before and after the thermal treatment of samples shows clearly the transformation of O^‐₂ centers at high temperature to (O^2‐ ‐ F⁺) centres. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

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.     

Colour centre studies in MoO3 films

The growth of defects in vacuum-evaporated MoO₃ films has been studied by optical absorption in the present work. The as-grown films were subjected to different kinds of treatment such as thermal annealing, UV and X-ray irradiation, and their optical absorption spectra were recorded between 300 and 1500 nm at room temperature as well as at liquid N₂ temperature The films were found to be amorphous from X-ray and electron-microscopic studies. From these studies it is observed that in addition to point defects, defect aggregates similar to the colloidal centres in silver and alkali halides, are present in these films.     

Vacuum-ultraviolet absorption of interstitial O2 and H2O molecules in SiO2 glass

Vacuum-ultraviolet (VUV) absorption of O₂ and H₂O molecules incorporated in interstitial voids in SiO₂ glass by thermal annealings was examined. Interactions of the interstitial molecules with the surrounding SiO₂ glass network lead to a redshift of the VUV absorption band of interstitial O₂, while a blueshift of that of interstitial H₂O, both accompanied by an increase in the intensity of the absorption bands. The Coulomb repulsion, London dispersion, and hydrogen bonding are the main interactions responsible for the modification of the VUV absorption bands.     

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.     

Excited state absorption and up-conversion luminescence of Ho3+ centres in 3CaO–Ga2O3–3GeO2 glass

3CaO–Ga₂O₃–3GeO₂ glass excited state absorption spectra-activated with Ho³⁺ (Ho₂O₃ – 0.7 wt% content) have been measured and analysed. Up-converted emission channels have been identified and the predicted up-converted emission bands have been registered under Ar ion laser (λ = 488 nm) excitation according to the excited state absorption data. A mechanism of up-converted transitions for Ho³⁺ centres in this prototype glass network is proposed on the basis of the obtained results.     

Study of sodium silicate melt and glass by infrared reflectance spectroscopy

Infrared reflectance spectra and the derived absorption spectra of a Na₂O-1.41 SiO₂ glass and of the parent melt are reported. Polymers with 2 bridging oxygens per silicon (chains) and 3 bridging oxygens (sheets) are identified. Spectra of glass and melt are qualitatively similar. Melt absorption bands show a 10–30 cm^?1 shift to lower frequencies. They are broader and less intense than those of the glass which does not agree with Sweet and White's reflectance measurements on similar glass and melt. The small differences between glass and melt can be attributed to the thermal expansion of the medium.     

Photoluminescence and radiation damage in W,Mg, Ca doped Bi4Ge3O12 crystals

Spectral properties and radiation damage in W, Mg and Ca doped Bi₄Ge₃O₁₂ (W:BGO, Mg:BGO, Ca:BGO) crystals before and after thermal treatment and gamma‐ray (γ‐) or ultraviolet (UV) radiation were studied. The absorption and the photoluminescence (PL) spectra of doped BGO crystals in visible region were measured. Before γ or UV radiation, the emission intensity of W:BGO crystal is stronger than that of pure BGO at about 500 nm. After γ radiation (10k Gy), the emission intensities of doped BGO are all weaker than pure BGO under identically condition. However, the emission intensity of W:BGO is stronger than that of pure BGO after UV exposure (10k Gy). Thermal treated (annealed in N₂ at 550 °C for 6 h) W:BGO has shown a much stronger emission intensity than others. (© 2011 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.     

Recharging processes of Cr ions in Mg2SiO4 and Y3Al5O12 crystals under influence of annealing and γ ‐ irradiation

Recharging processes of chromium ions were investigated for Mg₂SiO₄:Mg, Cr single crystals using annealing in O₂ and in air and γ‐irradiation, as compare to YAG :Ca, Cr single crystals. The formation of tetravalent Cr ions in the Mg₂SiO₄ :Mg, Cr is related not only to the initial Cr content in the melt, oxygen partial pressure and O₂‐ vacancy existing in the crystal, but also to the external field such as γ‐irradiation. The additional absorption after γ‐irradiation shows the decrease in intensity of the absorption of Cr³⁺ and Cr⁴⁺ ions in some part of the spectrum and increase in the other giving evidence on recharging effects between Cr³⁺ and Cr⁴⁺. There arises also color centers observed between 380 nm and 570 nm that may participate in energy transfer of any excitation to Cr⁴⁺ giving rise to Cr⁴⁺ emission. Opposite to forsterite crystal, absorption spectrum of YAG:Ca, Cr crystal after γ‐irradiation reveals only increase in the absorption of the Cr bands. The observed behavior of the absorption spectrum of YAG:Ca, Cr crystal under influence of γ‐irradiation suggests that γ‐irradiation ionizes only Cr ions. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Effect of fictive temperature on the optical absorption of cobalt (II) and nickel (II) in some phosphate glasses

The optical absorption of cobalt (II) in Na₂O, 4P₂O₅ melts and in H₂ONaCl mixtures has been studied at different temperatures; the equilibrium: octahedral ? tetrahedral shifted towards the right with increasing temperature in both solvents. The optical absorption of cobalt (II) and nickel (II) has been studied in a series of metaphosphate glasses: Na₂OCaOP₂O₅, and it has been shown that the equilibrium octahedral/tetrahedral ratio of these ions measured at room temperature can be correlated with the transformation temperature of these glasses. The colour of cobalt (II) or nickel (II) containing CaO·P₂O₅ glasses has been found to be significantly dependent on thermal history; the intensity of optical absorption changed reversibly on heat treatment at the transformation range of the glass.     

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.     

Intrinsic and impurity infrared absorption in As2Se3 glass

A quantitative study of infrared absorption in the 250–4000 cm^?1 region of As₂Se₃ glasses doped with small amounts of As₂O₃ or purified by various procedures has been carried out with particular attention to absorption in the wavelength regions of the CO₂ and CO lasers. The dependence of the relative intensities of the oxide impurity bands in the 650–1340 cm^?1 region on the total amount of As₂O₃ added to the glass indicates the existence of three distinct oxide-impurity species. A number of higher-frequency impurity bands which are due to the presence of hydrogen in the glass and whose intensities are highly dependent on the glass-melting conditions have been observed and classified. Intrinsic multiphonon absorption in the 400–1100 cm^?1 region has been interpreted in terms of combination and overtone bands of the two highest-frequency fundamental vibrational modes. Absorption coefficients of As₂Se₃ glass in the 920–1090 cm^?1 CO₂ laser region are limited by intrinsic multiphonon absorption to values of around 10^?2 cm^?1. The lowest absorption coefficients measured in the 1700–2000 cm^?1 CO laser region were around 2 × 10^?3 cm^?1 and may contain contributions from hydrogen-impurity bands.     

Bulk and impurity infrared absorption in 0.5 As2Se30.5 GeSe2 glass

A study of infrared absorption in the 250–4000 cm^?1 region has been carried out for 0.5 As₂Se₃0.5 GeSe₂ glasses quantitatively doped with oxide impurity. The frequencies of the intrinsic 2- and 3-phonon absorption bands at 490 and 690 cm^?1 correspond well to those predicted from combinations of the high frequency bands in the first order IR and Raman spectra of As₂Se₃ and GeSe₂ glasses.Glasses doped with As₂O₃ exhibit the same oxide impurity absorptionbands as those doped with GeO₂. Unlike As₂Se₃ glass, at impurity concentrations up to 1000 ppm As₂O₃, 0.5 As₂Se₃0.5 GeSe₂ glass exhibits only one major oxide impurity species, characterized by absorption bands at 780 and 1260 cm^?1 and due to oxygen bonded to network Ge. The observation of a much weaker network AsO vibration band at 670 cm^?1 confirms that oxygen bonds preferentially to Ge in this glass. The same minor oxide species appears to determine excess IR absorption at the CO₂ laser wavelength of 10.6 μm in both As₂Se₃ and 0.5 As₂Se₃ 0.5 GeSe₂ glasses. The frequencies and intensities of absorption bands due to hydrogen impurities are also quite comparable for these two materials.     

IR study of ultrathin plasma SiO2 and plasma treated thermal SiO2 films

The infrared absorption spectra both of ultrathin plasma SiO₂ and of thermal oxide (15–100 nm) treated in RF O₂ plasma are investigated in the wave number range from 400 to 4000 cm⁻¹. A conclusion is made that the plasma oxide consists of amorphous and different kinds of crystalline phases. The IR spectra of plasma oxide depend slightly on the discharge parameters. The structure of the as-grown thermal oxide, thinner than 40 nm, is shown to have defects and the presence of crystalline phases is observed too. The IR spectra of these oxides are changed significantly after plasma exposure. The influence of RF O₂ plasma on the thermal oxide, thicker than 40 nm, is negligible with respect to structural changes.     

Excitons in α-Oxygen Crystals

The investigation results of exciton, exciton-magnon and biexciton absorption by α-oxygen at T = 1.5 K are reported.

It is shown that the doublet structure of exciton-magnon bands is due to anisotropy of the exciton and rnagnon bands; the doublet structure of the bands in the two-particle absorption results from the bound two-exciton states, the biexcitons, present in α-O₂.     

Optical spectra of borate glasses containing Ti and Co in relation to their structure

The optical absorption spectra of borate glasses of the base composition (mol%) 35 (Na₂O+BaO)·65 B₂O₃, to which Ti and Co ions were introduced, have been measured in the range 190–900 nm. The addition of increasing amounts of TiO₂ up to 16 g/100 g glass, introduces an intense charge transfer band in the UV region that shifts towards longer wavelengths without imparting any coloration to the glass samples.Titanium ions are present as the Ti⁴ state and its addition produces glass of more coherent structure. The cobalt ions are found to be present in two symmetries; as CoO₆ units with absorption bands (denoted here as bands a and b) around 525–530 nm and 580–595 nm (respectively), and as CoO₄ units with absorption bands (denoted here as band-c) around 620–635 nm. Replacing Na ions by Ba ions or increasing the TiO₂ content favours the conversion of CoO₄ units into the CoO₆ ones.