Cluster centers in forsterite laser crystals Mg2SiO4 : Cr and Mg2SiO4 : Cr : Li

The structures of chromium-containing cluster centers in forsterite laser crystals Mg₂SiO₄ : Cr and Mg₂SiO₄ : Cr : Li have been simulated using the interatomic potential method. A system of position-dependent parameters of interatomic interaction potentials in forsterite has been developed. In the ionic approximation, this system adequately describes the structure, properties, and defects of the crystal with correct representation of the preferred positional arrangement of chromium ions. The preferred mechanisms of chromium dissolution in forsterite crystals have been evaluated from a comparison of the energies of formation of chromium-containing clusters with different configurations. It has been demonstrated that the results of the simulation of interatomic interaction potentials are consistent with the experimental data obtained from electron paramagnetic resonance and optical spectroscopy studies.     

Interaction of impurity and intrinsic defects in forsterite and its role in the formation of spectral and luminescence properties

This paper reports on the results of investigations of the coefficients of chromium distribution between a crystal and a melt of forsterite, the absorption and luminescence spectra, and the electron paramagnetic resonance spectra of chromium centers in Mg₂SiO₄: Cr, Mg₂SiO₄: Cr: Sc, and Mg₂SiO₄: Cr: Li crystals. It has been established that the concentration dependences of these properties vary upon changing over from the range of trace concentrations of chromium, scandium, or lithium impurities in the melt to the range of higher concentrations of these impurities. The observed phenomenon is explained by the interaction of impurities with intrinsic defects of the crystal, which is called as the microimpurity trapping effect. According to the performed estimations, the concentration of predominant intrinsic defects (magnesium Frenkel defects) in the forsterite crystals grown from the melt is equal to (7.5 ± 0.3) × 10⁻⁶ atomic fractions. The energy of the formation of magnesium Frenkel defects can be estimated as 4.2 ± 0.2 eV.     

Localized electronic excitations in crystalline phenacite Be2SiO4

The results of coordinated spectroscopic studies of the nature and properties of electronic excitations localized at regular and defect sites of the Be₂SiO₄ lattice are presented. The methods employed are electron-beam-excited pulsed absorption spectroscopy, pulsed cathodoluminescence, and low-temperature VUV spectroscopy with selective excitation by synchrotron radiation. The bands in luminescence spectra of Be₂SiO₄ at 2.70 and 3.15 eV are assigned to [AlO₄]^5? and [SiO₄]^4? centers formed both in direct relaxation of electronic excitations at defect levels and through the formation of exciton-defect complexes. Disruptions of beryllium-oxygen bonds (short-lived defects in the form of beryllium vacancies V _Be ^? ) are considered as initiating the formation of optically active centers with characteristic absorption bands in the range 1.5–4.0 eV. The intrinsic luminescence of the Be₂SiO₄ crystal at 3.6 and 4.1 eV is attributed to radiative decay of self-trapped excitons of two types. A mechanism of exciton self-trapping at the [SiO₄] and [BeO₄] tetrahedral groups is proposed, which involves excitation transfer from a threefold-coordinated oxygen atom to neighboring silicon or beryllium atoms.     

Effect of high-energy electron irradiation on forsterite laser crystals

The effect of 21-MeV electron irradiation on the optical absorption characteristics of Czochralski-grown forsterite (Mg₂SiO₄) single crystals (both undoped and chromium-doped) has been investigated. The irradiation is found to induce additional optical absorption (AOA) in the crystals in the range of 225–1200 nm due to the formation of color centers based on intrinsic host point defects and the change in the oxidation state of chromium ions. The AOA spectra have been decomposed into elementary bands. The influence of the chromium concentration in crystals, the oxygen content in the growth atmosphere, and additional doping with lithium on the behavior of these bands has been analyzed. A possible structure of the color centers responsible for the AOA is discussed. It is shown that the electron irradiation somewhat decreases the intensity of the characteristic absorption bands of tri- and tetravalent chromium ions and gives rise to a new absorption band in Mg₂SiO₄:Cr and Mg₂SiO₄:Cr,Li crystals heavily doped with chromium.     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Nuclear quadrupole coupling tensors of 17O in forsterite,Mg2SiO4

The nuclear quadrupole coupling tensors (eigenvalues and eigenvectors) of ¹⁷O were determined in a single crystal of Mg₂SiO₄ using pulsed nuclear magnetic resonance. The tensors are of the same order of magnitude as in Al₂O₃ and TiO₂.     

Radiation induced defects in SiO 2

The main luminescent centers in SiO 2 films are the red luminescence R (650 v nm; 1.85 v eV) of the non-bridging oxygen hole center (NBOHC) and the twofold-coordinated (divalent) silicon with a blue B (460 v nm; 2.7 v eV) and a UV band (285 v nm; 4.4 v eV). Especially the latter ones are produced under irradiation, but from existing precursors assumed as silicon related oxygen deficient centers (SiODC). Therefore, in order to prove these models we compare a direct oxygen implantation with a direct silicon implantation into SiO 2 layers. The main result is: implanting oxygen increases the red band R but does not affect the blue band B. Silicon surplus increases the amplitude of the blue (B) luminescence, but reduces the amplitude of the red (R) one. Studying the cathodoluminescence dose dependence of these blue and red bands we have established defect transformation kinetics in SiO 2 including six main defects and precursors as well as the mobile oxygen as the main transmitter between precursors and the radiation induced defects. The kinetics is described by eight rate equations which predict the dose dependence of the red (R) and blue (B) luminescence intensities and their temperature dependences very well.     

Concentration of Cr<Superscript>4+</Superscript> impurity ions and color centers as an indicator of saturation of forsterite crystals Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> with oxygen

The influence of the oxygen partial pressure P _{O 2} in the growth atmosphere on the coefficient of chromium distribution between the crystal and the melt of forsterite, the Cr³⁺ and Cr⁴⁺ ion contents in crystals, and the concentration of color centers induced by irradiation has been investigated. It has been established that the crystals grown at low oxygen partial pressures P _{O 2} (0.01–0.05 kPa) are characterized by low concentrations of Cr⁴⁺ ions and color centers. A change in the oxygen partial pressure to P _{O 2} ∼ 0.85 kPa leads to an increase in the Cr⁴⁺ center concentration by a factor of ∼10 and in the color center concentration by a factor of ∼5. A further increase in the oxygen partial pressure to P _{O 2} to 12 kPa remains the concentration of these centers almost unchanged. A model has been proposed according to which the intrinsic defects formed under conditions of a relative excess of oxygen leads to both the self-oxidation of chromium and the formation of color centers in the forsterite crystals under irradiation.     

EPR Study of the Vanadium Ions in Mg2SiO4 Crystal

Vanadium-doped forsterite crystal has been studied with X-band electron paramagnetic resonance (EPR) spectroscopy. The sample was grown by the Czochralski technique in an argon atmosphere with 2 vol% of hydrogen. The EPR spectrum of the sample at T = 15 K is predominantly represented by the V⁴⁺ ion signals that possess a characteristic eight-line hyperfine structure and are observed close to g = 2. The observation of the two magnetically nonequivalent centers in the angular dependence in the (ab) crystal plane and one center in the (ac) and (bc) planes, combined with the published optical spectroscopy data, unambiguously show that the V⁴⁺ ions are located at the silicon lattice site. Principal values of the hyperfine A and g-tensor and magnetic axes orientations of the V⁴⁺ centers have been determined. The orientation disorder of the V⁴⁺ centers has been found around the crystalline c axis but not in the (ab) crystal plane. The angular variation of the hyperfine component linewidth is described best with a disorder range of ±3.0°.     

Correlation between defect-related electroluminescence and charge trapping in Gd-implanted SiO<Subscript>2</Subscript> layers

When amorphous silica is bombarded with energetic ions, various types of defects are created as a consequence of ion-solid interaction (oxygen deficient centers (ODC), non-bridging oxygen hole centers (NBOHC), E^′-centers, etc.). Luminescent peaks from oxygen deficiency centers at 2.7 eV, non-bridging oxygen hole centers at 1.9 eV and defect centers with emission at 2.07 eV were observed by changing the concentration of implanted Gd³⁺ ions. Charge trapping in Gd-implanted SiO₂ layers was induced using constant current electron injection to study the electroluminescence intensity with dependence on the applied voltage change. The process of electron trap generation during high field carrier injection results in an increase of the electroluminescence from non-bridging oxygen hole centers. Direct correlation between electron trapping and the quenching of the electroluminescence at 2.07 eV and 2.7 eV was observed with variation of the implanted Gd concentration. PACS 78.60.i; 72.20.Jv; 78.20.-e     

Electronic excitations in BeAl<Subscript>2</Subscript>O<Subscript>4</Subscript>, Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, and Be<Subscript>3</Subscript>Al<Subscript>2</Subscript>Si<Subscript>6</Subscript>O<Subscript>18</Subscript> crystals

Low-temperature (T = 7 K) time-resolved selectively photoexcited luminescence spectra (2–6 eV) and luminescence excitation spectra (8–35 eV) of wide-bandgap chrysoberyl BeAl₂O₄, phenacite Be₂SiO₄, and beryl Be₃Al₂Si₆O₁₈ crystals have been studied using time-resolved VUV spectroscopy. Both the intrinsic luminescence of the crystals and the luminescence associated with structural defects were assigned. Energy transfer to impurity luminescence centers in alexandrite and emerald was investigated. Luminescence characteristics of stable crystal lattice defects were probed by 3.6-MeV accelerated helium ion beams.     

The electronic structures of the core and valence ion states of metal oxides

SCF-Xα SW MO calculations on metal core ion hole states and X-ray emission (XES) and X-ray photoelectron (XPS) transition states of the non- transition metal oxidic clusters MgO₆^10?, AlO₄^5? and SiO₄^4? show relative valence orbital energies to be virtually unaffected by the creation of valence orbital or metal core orbital holes. Accordingly, valence orbital energies derived from XPS and XES are directly comparable and may be correlated to generate empirical MO diagrams. In addition, charge relaxation about the metal core hole is small and valence orbital compositions are little changed in the core hole state. On the other hand, for the transition metal oxidic clusters FeO₆^10?, CrO₆^9? and TiO₆^8? relative valence orbital energies are sharply changed by a metal core orbital or crystal field orbital hole, the energy lowering of an orbital increasing with its degree of metal character. Consequently O 2p nonbonding → M 3d-O 2p antibonding (crystal field) energies are reduced, while M 3d bonding → O 2p nonbonding and M 3d-O 2p antibonding → M 4s,p-O 2p antibonding (conduction band) energies increase. Charge relaxation about the core hole is virtually complete in the transition metal oxides and substantial changes are observed in the composition of those valence orbitals with appreciable M 3d character. This change in composition is greater for e _g than for t_2g orbitals and increases as the separation of the e_g crystal field (CF) orbitals and the O 2p nonbonding orbital set decreases. Based on the hole state MO diagrams the higher energy XPS satellite in TiO₂ (at about 13 eV) is assigned to a valence → conduction band transition. The UV PES satellites at 8.2 eV in Cr₂O₃ and 9.3 eV in FeO are tentatively assigned to similar transitions to conduction band orbitals, although the closeness in energy of the crystal field and O 2p nonbonding orbitals in the valence orbital hole state prevents a definite assignment on energy criteria alone. However the calculations do clearly show that charge transfer transitions of the e_g bonding → e_g crystal field orbital type would generally occur at lower energy than is consistent with observed satellite structure.A core electron hole has little effect upon relative orbital energies and is only slightly neutralized by valence electron redistribution for MgO and SiO₂. For the transition metal oxides a core hole lowers the relative energies of M3d containing orbitals by large amounts, reducing O → M charge transfer and increasing M 3d crystal field → conduction band energies. Large and sometimes overcomplete neutralization of the core hole is observed, increasing from CrO₆^9? to FeO₆^10? to TiO₆^8?. as the O → M charge transfer energy declines.High energy XPS satellites in TiO₂ may be assigned to O 2p nonbonding → conduction band transitions while lower energy UV PES satellites in FeO and Cr₂O₃ arise from crystal field or O 2p nonbonding → conduction band excitations. Our “shake-up” assignment for FeO₆^10?, CrO₆^9? and TiO₆^8? are less than definitive because no procedure has yet been developed to calculate “shake-up” intensities resulting from transitions of the type described. However the results do allow a critical evaluation of earlier qualitative predictions of core and valence hole effects. First, we find that the comparison of hole or valence state ionic systems with equilibrium distance systems of higher nuclear and/or cation charge (e.g. the comparison of the FeO₆^10? Fe 2p core hole state to Co₃O₄) is dangerous. For example, larger MO distances in the ion states substantially reduce crystal field splittings. Second, core and CF orbital holes sharply reduce O → M charge transfer energies, giving 2e_g → 3e_g energy separations which are generally too small to match observed satellite energies. Third, highest occupied CF-conduction band energies are only about 4–5 eV in the ground states, but increase to about 7–11 eV in the core and valence hole states of the transition metal oxides studied. The energetic arguments presented thus support the idea of CF and/or O 2p nonbonding → conduction band excitations as assignments for “shake-up” satellites, at least in oxides of metals near the beginning of the transition series.     

Silicon negative ion implantation induced vacancy defects in thermally grown SiO2 thin films

ABSTRACT

Thermally grown SiO₂ thin films on a silicon substrate implanted with 100?keV silicon negative ions with fluences varying from 1?×?10¹⁵ to 2?×?10¹⁷ ions cm^?2 have been investigated using Electron spin resonance, Fourier transforms infrared and Photoluminescence techniques. ESR studies revealed the presence of non-bridging oxygen hole centers, E′-centers and P_b-centers at g-values 2.0087, 2.0052 and 2.0010, respectively. These vacancy defects were found to increase with respect to ion fluence. FTIR spectra showed rocking vibration mode, stretching mode, bending vibration mode, and asymmetrical stretching absorption bands at 460, 614, 800 and 1080?cm^?1, respectively. The concentrations of Si–O and Si–Si bonds estimated from the absorption spectra were found to vary between 11.95?×?10²¹ cm^?3 and 5.20?×?10²¹ cm^?3 and between 5.90?×?10²¹ cm^?3 and 3.90?×?10²¹ cm^?3, respectively with an increase in the ion fluence. PL studies revealed the presence of vacancies related to non-bridging oxygen hole centers, which caused the light emission at a wavelength of 720?nm.     

Evidence from numerical modelling for 3D spreading of [001] screw dislocations in Mg2SiO4 forsterite

Computer simulations have previously been used to derive the atomic scale properties of the cores of screw dislocations in Mg₂SiO₄ forsterite by direct calculation using parameterized potentials and via the Peierls–Nabarro model using density functional theory. We show that, for the [001] screw dislocation, the parameterized potentials reproduce key features of generalized stacking fault energies when compared to the density functional theory results, but that the predicted structure of the dislocation core differs between direct simulation and the Peierls–Nabarro model. The [001] screw dislocation is shown to exhibit a low-energy non-planar core. It is suggested that for this dislocation to move its core may need to change structure and form a high-energy planar structure similar to that derived from the Peierls–Nabarro model. This could lead to dislocation motion via an unlocking–locking mechanism and explain the common experimental observation of long straight screw dislocation segments in deformed olivine.     

On the theory of lasing at vibronic transitions in impurity crystals

Some aspects of lasing at vibronic transitions in impurity crystals are theoretically studied. The threshold conditions for a vibronic laser are shown to be dependent on the strength of the interaction of optical centers with a local vibration, which forms the vibronic spectrum, and the crystal lattice temperature. The theory can easily be generalized to the spectrum containing a structureless phonon sideband and well agrees with the experimental temperature dependence of the output power of a Mg₂SiO₄:Cr⁴⁺ forsterite laser.     

Luminescence of LaBr3: Ce,Hf crystals under photon excitation in the ultraviolet,vacuum ultraviolet,and X-ray ranges

This study has been carried out using synchrotron radiation, time-resolved luminescence ultraviolet and vacuum ultraviolet spectroscopy, optical absorption spectroscopy, and thermal activation spectroscopy. It has been found that, in scintillation spectrometric crystals LaBr₃: Ce,Hf characterized by a low hygroscopicity, along with Ce³⁺ centers in regular lattice sites, there are Ce³⁺ centers located in the vicinity of the defects of the crystal structure. It has also been found that the studied crystals exhibit photoluminescence (PL) of new point defects responsible for a broad band at wavelengths of 500–600 nm in the PL spectra. The minimum energy of interband transitions in LaBr₃ is estimated as E _g ～ 6.2 eV. The effect of multiplication of electronic excitations has been observed in the range of PL excitation energies higher than 13 eV (more than 2E _g ). Thermal activation studies have revealed channels of electronic excitation energy transfer to Ce³⁺ impurity centers.     

Dissymmetrization in X-irradiated RbTiOPO4 crystal

Electron paramagnetic resonance has been used to study the hole and electron paramagnetic centers formed in X-irradiated RbTiOPO₄, the crystals of the KTP family. X-irradiation of RbTiOPO₄ crystals at 77 K produced an oxygen hole center and four different trivalent titanium electron centers I₁, II, III and IV. Theg-tensors, their principal values and axes for the defects were calculated and compared with those for KTiOPO₄ centers. X-irradiation at 300 K produced another two oxygen hole centers and three electron centers I₁, I₂ and II. EPR spectra of the center II revealed dissymmetrization, i.e., irregular distribution of growth defects, between the physically equivalent sites lowering the point group symmetry of the local environment of paramagnetic centers Ti³⁺.     

Slow components of the emission decay in fluoride crystals doped with Ce3+

Spatially separated defects created by photons with energies 6–8 eV in alkali-earth fluoride crystals doped with cerium are investigated with the help of thermoluminescence. Measuring the spectra of creation of V_k and H peaks of thermostimulated luminescence inBaF ₂:Ce³⁺. we demonstrate that photons with energies higher than 6eV induce H centers (self-trapped holes captured by interstitialF ions), whereas the formation of self-trapped holes begins on exposure to photons with energies greater than 7 eV. The influence of photoionization on theCe ³⁺ luminescence inBaF ₂, SrF₂, CaF₂, andCeF ₃ crystals is investigated in the range of photon energies 4–8 eV. An exponentialCe ³⁺-emisson decay was observed for excitation energy lying in the range 4–6 eV. Slow and fast decay components were observed under excitation by photons with energies higher than 6 eV. We believe that the slow and fast components are due to the tunnel recombination of trapped electrons with hole centers. A. P. Vinogradov Institute of Geochemistry of the Siberian Branch of the Russian Academy of Sciences. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 43–49, March, 2000.     

Analysis of the Nonselective Spectra of Photostimulated Electron Emission from the Surface of Irradiated Dielectrics

The methodological aspects of PSEE spectroscopy of the surface of irradiated dielectrics have been considered. A generalized method for processing the nonselective photostimulated electron emission (PSEE) spectra taking into account the effects of radiation electrification and structural disordering is proposed and has been substantiated. The procedure of separation of the emission contribution of discrete radiation centers providing, in the stationary approach, estimation of a number of parameters and the concentration of emission-active defects of the surface layer of the material has been described. The potentialities of the method have been demonstrated with the example of Be₂SiO₄ phenacite crystals and crystalline and glassy SiO₂. Diamagnetic oxygen-deficient centers, body and surface E'-centers, as well as hole O ₁ ⁰ -centers on nonbridging oxygen atoms have been registered. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 381–385, May–June, 2005.     

Formation energies and electronic structures of native point defects in potassium dihydrogen phosphate

The formation energies and the equilibrium concentration of vacancies,interstitial H,K,P,O and antisite structural defects with P and K in KH 2 PO 4 (KDP) crystals are investigated by ab initio total-energy calculations.The formation energy of interstitial H is calculated to be about 2.06 eV and we suggest that it may be the dominant defect in KDP crystal.The formation energy of an O vacancy (5.25 eV) is much higher than that of interstitial O (0.60 eV).Optical absorption centres can be induced by defects of O vacancies,interstitial O and interstitial H.We suggest that these defects may be responsible for the lowering of the damage threshold of the KDP.A K vacancy defect may increase the ionic conductivity and therefore the laser-induced damage threshold decreases.