Electron transfer from excited F centres to F+, F+A and F+AA centres in CaO studied by optically detected magnetic resonance (ODMR)

ODMR measurements via the magnetic circular polarization of the emission (MCPE) of F_A(Mg) centres in CaO at 1.6 K showed besides the known F_A-ODMR lines a non zero MCPE, which vanishes at g ? 2. From the dynamical behaviour of this MCPE and the F_A luminescence is shown that an electron tunneling takes place from the excited T_1u F centre state to F⁺_A centres forming excited F_A centres. The ground state back tunneling rate is 10⁷ times smaller and cannot explain the observed electron transfer cycle. The back tunneling is also going via excited states. The results can be understood assuming a random centre distribution. A new luminescence band at 785 nm could be identified by ODMR as being due to tetragonal F_AA centres. The electron transfer is also observed between F and F⁺ and F⁺_AA centres.     

Electron trapping and untrapping during the dark decay of flash-produced KC1 F′ and F′ > A(Na) bands between 290–350°K

Both the thermal lifetimes of the F′(F′_A) centers and the ratios of the electron trapping cross-sections of (F_A) to α(α_A) centers were derived from the decay kinetics of flash-produced F′(F′_A) bands. In particular, the ratios dropped steeply with the temperature possibly due to a thermally activated de-excitation following excited state pre-trapping of the electron by the anion vacancy.     

Formation time of F centers in alkali halides

It is argued that in most alkali halides an appreciable fraction of the self-trapped excitons may undergo non-radiative transitions from vibrationally excited states of B_3u to the A_1g state during the relaxation of the self-trapped excitons created by ionizing radiation. Numerical calculations show that the non-radiative transition probabilities, from vibrational levels of B_3u near or above the crossing point of the A_1g and B_3u potential curves to the A_1g state, are consistent with the observed formation times of F centers in various alkali halides. The exceptional case of KI is also discussed.     

Electron-lattice coupling of F centers: Particular case of NaI: F

Absorption and magnetic circular dichroism studies of the F centers in NaI reveal a strong electron-lattice coupling with the vibration modes of Γ₁⁺ symmetry in comparison with those of Γ₃⁺ and Γ₅⁺ symmetry. On the other hand, the F electron exhibits in its first excited state a large spin-orbit coupling, in agreement with the value previously calculated. These results are confirmed by the Raman spectra which show a predominant intensity for the Γ₁⁺ modes, particularly for the resonant mode at 113 cm^?1.First and second-order Raman spectra have been calculated using a “quasi-resonant” theory in which the vibrations of the ions up to the fifth shell have been taken into consideration. We have been able to determine from these calculations absolute values for the contributions of the different types of vibration modes to the broadening of the F-absorption band.     

Radioluminescence of ionized electron color centers in LiF crystals

Photoluminescence (PL) and temporal variation of optical absorption and radioluminescence (RL) of LiF crystals after irradiation with an electron impulse are investigated by pulse spectrometry methods using different irradiation regimes and different degrees of initial radiation damage. The difference in the RL and PL characteristics of ionized F ₂ ⁺ and F ₃ ⁺ centers is revealed. Several mechanisms for inducing these centers by irradiation, which differ in energy and kinetic parameters and in temperature dependence, are proposed. It is established that the ionized centers in the radiation active state are created due to the interaction of the respective neutral centers with holes of different thermalization extent. A mechanism for the excitation of these radiation-active centers is proposed.     

(F2+)A centers in lithium-doped KCl

Optical properties of the lithium (F₂⁺)_A center are reported and compared to those of the sodium (F₂⁺)_A and the intrinsic F₂⁺ centers.     

FA(Ga+,In+,Tl+) tunable laser activity and interaction of halogen atoms (F,Cl,Br,I,At) at the (001) surface of KCl crystal: ab initio calculations

An attempt has been made to examine F_A(Ga⁺,In⁺,Tl⁺) tunable laser activity and adsorptivity of halogen atoms (F,Cl,Br,I,At) at the (0 0 1) surface of KCl crystal using an embedded cluster model, CIS and density functional theory calculations with effective core potentials. The ion clusters were embedded in a simulated Coulomb field that closely approximates the Madelung field at the host surface. The nearest neighbor ions to the defect site were then allowed to relax to equilibrium. Based on the calculated strength of electron–phonon coupling and Stokes-shifted optical transition bands, The F_A(Tl⁺) center was found to be the most laser active in agreement with the experimental observation that the optical emissions of F_A(In⁺) and F_A(Ga⁺) centers were strongly quenched. The disappearance of the anisotropy and np splitting observed in the absorption of F_A(Ga⁺,In⁺,Tl⁺) centers were monotonically increasing functions of the size of the impurity cation. The F_A(Ga⁺,In⁺,Tl⁺) defect formation energies followed the order F_A(Ga⁺)>F_A(In⁺)>F_A(Tl⁺). The Glasner–Tompkins empirical relationship between the principal optical absorption of F centers in solids and the fundamental absorption of the host crystal was generalized to include the positive ion species. As far as the adsorptivity of the halogen atoms is concerned, the F and F_A(In⁺,Tl⁺) centers were found to change the nature of adsorption from physical adsorption to chemical adsorption. The adsorption energies were monotonically increasing functions of the electronegativity of the halogen and the amount of charge transferred from the defect-free surface. The calculated adsorption energies were explainable in terms of the electron affinity, the effective nuclear charge and the electrostatic potentials at the surface. The spin pairing mechanism played the dominant role in the course of adsorbate–substrate interactions and the KCl defect-free surface can be made semiconducting by F or F_A(In⁺,Tl⁺) surface imperfections.     

Electron-lattice interaction of Ag− and Cu− centers in alkali halides

Absorption, emission, and excitation spectra of Ag^? centers in KCl, RbCl, CsCl, and CsBr are measured at low temperatures. The positions of theA emission bands are slightly different afterC andA band excitation, respectively. This is believed to be due to the existence of two different types of minima in the adiabatic potential energy surface of the³ T _1u state. The symmetry of the energy minima in the¹ T _1u state is trigonal for KCl∶Ag^? and Cu^?, but tetragonal for CsBr∶Ag^?. This becomes evident from the polarization properties of the emission. The energy and temperature dependence of the polarization is discussed. Uniaxial stress causes polarized emission of Ag^? and Cu^? centers measured from LHeT to 100 K. This is due to a splitting and mixing of the relaxed excited states by the stress. The effects are used to calculate the coupling constants between thep electron and theE _g andT _2g lattice modes. They are compared with predictions from the point-charge model for different lattice structures. A new assignment of the absorption bands of KCl∶Cu^? to the excited states of Cu^? is established on measurements of emission spectra and lifetimes.     

Optical and thermal properties of F and F aggregate centers in KF

A detailed investigation has been carried out of the optical and thermal properties of centers such as F, F_A, M and M_A in pure, Na-doped and Li-doped KF. Most centers exhibit properties which are qualitatively similar to those produced in other potassium halides with the notable exception of the F_A (Na) center, which has both Type I and Type II behavior.     

Electronic color centers in SrF2-Na crystals

It was shown that optical bleaching of M _A ⁺ color centers at 80 K in SrF₂-Na crystals causes the core of an M _A ⁺ -center to transform into the V _a ⁺ Me ⁺ V _a ⁺ configuration, in which all three point defects are arranged diagnonally in the cube cell. Reirradiation of an optically bleached crystal by x-rays generates F _D centers in it: V _a ⁺ Me ⁺ V _a ⁺ + e ^? → V _a ⁰ Me ⁺ V _a ⁺ ≡ F _D. The F _D → M _A ⁺ transformation in SrF₂-Na crystals proceeds at T = 135 K, in contrast to the F _A → M _A ⁺ transformations, which take place at T > 200 K.     

Luminescence of F + and F centers in YAlO3

In YAlO₃ crystals grown in vacuum or reduced by annealing at low oxygen pressure, the luminescence of F centers in the band at 420 nm, with τ=30 ms at 9 K, excited in the bands at 212 and 242 nm, as well as the luminescence of F ⁺ centers in the band at 355 nm, with τ=2.7 ns, excited in the main band at 220 nm and weaker bands at 190 and 288 nm, was detected. On the basis of the results obtained and data in the literature, the behavior of the emission of F ⁺ and F centers in oxides of the Al₂O₃-Y₂O₃ system is analyzed on the example of the compounds α-Al₂O₃, YAlO₃, and Y₃Al₅O₁₂. The role of antisite defects in the stabilization of F-like luminescence and absorption centers in multisublattice oxides is discussed.     

Magneto-optical spectroscopy and optical detection of EPR spectra of Yb<Superscript>3+</Superscript> paramagnetic centers with cubic symmetry in single crystals <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Cd,Ca, Pb)

Cubic paramagnetic centers formed by Yb³⁺ impurity ions in fluorite-type crystals MeF₂ (Me = Cd, Ca, Pb) have been investigated using electron paramagnetic resonance, magnetic circular dichroism, magnetic circular polarization of luminescence, Zeeman splitting of optical absorption and luminescence lines, and optical detection of electron paramagnetic resonance. The g factors of the ²Γ₇ state in the excited multiplet ² F _5/2 of Yb³⁺ ions in Me F₂ crystals, the hyperfine interaction constant ¹⁷¹ A (¹⁷¹Yb) for the excited multiplet ² F _5/2 in the CaF₂ crystal, and the energies and symmetry properties of all energy levels of Yb³⁺ ions in MeF₂ crystals are determined. The crystal-field parameters for the crystals under investigation are calculated.     

Two-photon polarization spectroscopy of LiF crystals with F 2 laser color centers

The paper reports on a measurement and calculation of the dependence of LiF: F ₂ luminescence polarization and intensity on the polarization of high-power laser radiation (λ_ex=1064 nm) producing two-photon excitation of F ₂ centers. It is shown that the two-photon transition results in the excitation of a previously unknown electronic level of F ₂ centers of the A _1g symmetry.     

Photochemistry and reactions of OH− defects and F centers in Alkali Halides

Additively colored KCl:OH^? crystals show under combined UV and visible irradiation an irreversible destruction of F centers and visible absorption. This process, which is effective over the whole temperature range 4–300 K, was studied systematically in terms of the reaction efficiency and products using UV-visible and IR (local mode) spectroscopy. The UV photo-dissociation of OH^? defects and photo-ionization of F centers produce a combined net effect, in which at higher temperatures all F centers are converted into U centers, thus completely bleaching the colored crystal. By these photo-reactions, high contrast visible images can be produced which are stable under visible light at RT, and are thermally stable up to 650°C. Besides the optical information-storage aspect, these photo-reactions can be used for controlled production of U_A centers if the crystal contains alkali-ion impurities like Na⁺.     

Optical properties and stable,broadly tunable cw laser operation of new FA-type centers in Tl+-doped alkali halides

A new group of complex color centers with F_A-type properties, involving simple center production and high thermal and optical stabilities, has been found in six Tl⁺-doped alkali halides: NaCl, KCl, RbCl, KBr, RbBr and RbI. In its first tested examples, KCl and KBr, broadly tunable cw laser operation over the 1.4 to 1.7 μm range has been obtained, with output powers in the 100 mW range. In contrast to already existing F⁺₂ and F⁺₂-like centers, operating in the same wavelength range, the new F_A(Tl⁺) lasers are optically stable and do not show any bleaching effects under laser operation.     

Dominant Cr3+ centers in LiNbO3 under hydrostatic pressure

Low-temperature luminescence spectra of stoichiometric Cr: LiNbO₃ and of congruent Cr, Mg: LiNbO₃ were studied. Cr³⁺ impurity ions preferentially occupy Li⁺ sites (Cr_Li) in the LiNbO₃ crystal lattice, while Cr³⁺ ions substituting for Nb⁵⁺ ions (Cr_Nb) occur in addition to Cr_Li centers in codoped Cr, Mg: LiNbO₃ crystals. Application of a high hydrostatic pressure leads to a transformation of (dominant in concentration) Cr³⁺ centers from low-to high-crystal-field centers. Due to a strong pressure-induced blue shift of the ⁴ T ₂ state resulting in crossing with the ² E state, the replacement of the broad band ⁴ T ₂ → ⁴ A ₂ emission by a narrow R-line emission ² E → ⁴ A ₂ occurs in the luminescence spectra of the samples. This effect of level crossing was observed for the dominant Cr _Li ³⁺ and Cr _Nb ³⁺ centers at pressures which correlated well with estimations based on the ⁴ T ₂-² E energy gap (230 and 1160 cm^?1) and on the rate of their pressure-induced change (14.35 and 11.4 cm^?1/kbar, respectively).     

Spatial structures based on color centers created by electrons in lithium fluoride crystals: Absorption and luminescence characteristics

We have shown that in spatial structures based on color centers created by electrons in a lithium fluoride crystal, the distances between centers reach 1.6 nm and 3.6 nm for F₁ and F₂ centers respectively. This suggests considerable potential opportunities for using electron technology to form structures in the crystals with spatial resolution of such an order of magnitude. We measured the decrease in fluorine content on the irradiated surface of the crystal. We found the concentrations of F₁, F₂, F₃⁺, F₃(R₂), and F₄(N₁) centers. We established that the specific characteristics of color center formation by electrons leads to an increase in the efficiency of creation of F₃ and F₄ centers. We determined the decrease in the average luminescence lifetimes of F₂ and F₃⁺ centers as a result of concentration quenching. We observed distortion of the luminescence contour for F₂ centers as a result of absorption of its short-wavelength portion by other centers and emission of radiation by the latter in its long-wavelength portion. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 102–110, January–February, 2008.     

Determination of the Ni+-F- distance for square-planar and linear centers in LiF:Ni+ and NaF:Ni+

The distance R between Ni⁺ and the closest F^- anions for several square- planar and linear Ni⁺ centers observed in LiF and NaF has been derived from the isotropic superhyperfine constant A_s. R is smaller for linear than for square-planar centers according to Pauling's criteria. The knowledge of R for every square-planar center allows one to explain reasonably variations undergone by the experimental g_∥?g₀ values. Finally the present data reveal that the ionic radius of the unusual Ni⁺ ion is indeed quite close to that of Cu⁺.     

Lifetime of F2 and F+3 centers in LiF crystals doped with magnesium

The influence of Mg impurity in an LiF crystal on the lifetime of the relaxed excited state of the F₂ and F⁺₃ centers is investigated for the first time by using the time-correlated photon counting technique at room temperature (RT). It is found that the radiative lifetime of the excited F₂ centers is almost independent of the Mg impurity concentration, while that of the excited F⁺₃ centers varies strongly with the corresponding impurity concentration.