Luminescence of color centers formed in alkali-earth-doped yttrium orthoaluminate crystals

Alkali-earth-doped yttrium orthoaluminate crystals grown in a reducing atmosphere are found to show bright photoluminescence (PL) in visible wavelength regions under the excitation by UV light source. From the results of transmission, PL, PL excitation and time-resolved PL spectra for the samples with different types and concentrations of dopants and the comparison to the results for the samples grown under different conditions, the origin of principal emission is determined to be color centers stabilized by heterovalent ions. The observed fast lifetime and high quantum yield of the luminescence can be explained by dipole-allowed transition between the levels localized in a vacancy. Comparing the effects on the optical properties from several types of dopant ions and taking influence from the UV irradiation into account, a model for the structure of emission centers is proposed.     

A high-stability medium based on CaF<Subscript>2</Subscript>:Na crystals with colloidal color centers: I. Photothermochemical conversion of colloidal color centers in CaF<Subscript>2</Subscript>:Na crystals

Photothermochemical conversion of simple color centers (which include from one to four anionic vacancies) and highly aggregated ones in additively colored crystals of calcium fluoride doped by sodium is studied. The annealing of crystals with a low sodium content in a reducing atmosphere (additive coloration) leads to the predominant formation of simple color centers, which convert into highly aggregated centers under the joint action of heating and irradiation in absorption bands of simple centers. The irradiation of highly aggregated centers into their absorption bands and simultaneous heating causes these centers to convert into simple centers. The additive coloration of crystals with a relatively high sodium content leads to the predominant formation of highly aggregated centers. The heating of these crystals along with the irradiation in absorption bands of highly aggregated centers causes these centers to convert into simple centers. The formation of different color centers in the course of additive coloration of crystals with different impurity content and different results of photothermochemical conversion of centers in these crystals are connected with the dual action of impurities. Anion vacancies, which compensate the charge of the impurity alkali metal, facilitate the aggregation of color centers. At the same time, the alkali impurity stabilizes simple color centers.     

Thin-film aggregate color centers as media for frequency domain optical storage

Thin films of aggregate color centers have been produced by electron and ion irradiation of bulk alkali halide crystals. The transverse spatial distribution of the centers was controlled on a submicron scale using electron lithography. Photochemical hole burning has been accomplished for the first time in a thin film of color centers, using the 6070 Å zero-phononN ₁ line produced by ion and electron irradiation of NaF crystals.     

Enrichment centers in sodium bromide crystals

The primary products of irradiation of alkali halide crystals are anion and cation Frenkel pairs [1–4]. Interaction of these products among themselves and with structural defects existing before irradiation leads to the appearance of various structural defects, the majority of which are optically active. The present study will treat enrichment centers which can be formed from the components of Frenkel cation pairs. Studies of this type are important in providing information on states in which radiation-created cation defects can exist stably in the lattice.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 119–121, August, 1979.     

Color centers in heavily irradiated CsI(Tl) crystals

The absorption and luminescence properties of CsI(Tl) crystals colored by irradiation are studied by the method of the time-resolved spectroscopy. The scheme of the electron transitions in CsI(Tl) crystal is suggested to explain the appearance of the color centers under exposure to the near-UV light. It is established that either of the two types activator color centers holds the charge carrier with opposite sign. The model of the hole Tl²⁺v_c⁻ activator color center is suggested. According to the model the positive charge of Tl²⁺ ion is compensated by the negative charge of a close cation vacancy v_c⁻. The color center emission reveals in the cathode-luminescence spectrum of the colored CsI(Tl) crystal. The high-dose irradiation of CsI(Tl) crystal results in the reduction of the decay time of the near-thallium self-trapped excitons (STE) emission. The decay kinetics of Tl²⁺v_c⁻ emission contains the time components typical for the decay kinetics of near-thallium STE emission. The reason of the observed effects is the energy transfer from the near-thallium STE excitons to the color centers via the inductive-resonant mechanism.     

Optical Detection of magnetic resonance without microwaves via MCD of F-centers in doped alkali halides

Abstract

By monitoring the magnetic circular dichroism (MCD) of F-centers in irradiated alkali halides EPR of impurity centers was detected without microwaves due to a cross-relaxation of the impurities with optically pumped F-centers. Cross-relaxation effects were also observed in magnetic resonance detected via MCD in absorption and the intensity of spin-dependent recombination emission in ionic crystals doped with transition and rare earth ions.     

Characteristics of the fast electron emission produced during the cleavage of crystals

The present paper reports the fast electron emission produced during the cleavage of alkali halide crystals and models the dynamics of the process. The mechano-emission arises as a result of the ionization of surface traps at the expense of the energy which is released in the annihilation of the defects which are formed during cleavage. The slow electrons which appear upon the ionization of surface traps are subsequently accelerated in the field of negatively charged segment of the freshly cleaved surface. Considering the basic mechanism of fast electron emission, expressions are derived which are able to explain satisfactorily the temporal, thermal, charge, surface, coloration, water adsorption and other characteristics of the fast electron emission produced during the cleavage of crystals. The decay time of the charges on the newly created surfaces, and the velocity of cracks can be determined from the measurements of fast electron emission produced during the cleavage of crystals. It is shown that two types of diffusing centres are responsible for the charge relaxation and thereby for the emission of fast electrons produced during the cleavage of alkali halide crystals.     

Radiation-induced E″ centers in crystalline SiO2

Electron spin resonance has been used to study three similar, but distinct, S = 1 defects (labelled E″ centers) in high-quality synthetic quartz crystals. These centers are produced by electron irradiation and their concentrations depend on the irradiation temperature, the nature of previous irradiations and thermal anneals, and whether the sample is swept or unswept. The radiation-induced mobility of interstitial alkali ions (Li⁺ and Na⁺) correlates with the production of E″ centers.     

Tunneling recombination luminescence under excitation of PbWO4:Mo crystals in the defect-related absorption region

Time-resolved emission and excitation spectra and luminescence decay kinetics were studied at 150-300 K for the green emission of PbWO₄:Mo crystals. It was found that the slow (μs-ms) decay component observed under excitation in the defect-related absorption region (around 3.8-3.9 eV) arises from the G(II) emission which appears at the tunneling recombination of optically created electron and hole centers. The study of the emission decay kinetics at different temperatures and excitation intensities allowed concluding that both the monomolecular and the bimolecular tunneling recombination process can be stimulated in the mentioned energy range. The monomolecular process takes place in the isolated spatially correlated pairs of electron and hole centers produced without release of electrons into the conduction band. The bimolecular process takes place in the pairs of randomly distributed centers created at the trapping of free electrons from the conduction band. The formation of electron centers under irradiation in the defect-related absorption region was investigated by the electron spin resonance (ESR) and thermally stimulated luminescence (TSL) methods. The possibility of various photo-thermally stimulated defects creation processes, which take place with and without release of free electrons into the conduction band, was confirmed.     

Optical absorption of irradiated quartz in the near i.r.

The effects of irradiation with 10 MeV electrons on the absorption spectra in the 3 μm region of both natural and synthetic quartz were investigated in the temperature range from 12 to 300°K. Six different types of synthetic crystals were included in this study. It was found that the spectra of samples that were treated by electrodiffusion were least affected by the irradiations, whereas large changes were observed in the spectra of untreated specimens. Lines were introduced by irradiation in some synthetic samples at 3306 and 3367 cm^?1. The dependence of the spectra on radiation dose was studied up to 6700 MRad. The largest spectral changes saturated above a dose of 200 MRad. The sharp, intense lines at 12°K were observed to broaden and weaken as well as to shift to shorter wavelengths as the temperature was raised to 300°K. Some of these effects can be described in terms of a model involving charge compensation of the aluminum defect by hydrogen and alkali metal ions. It is also found that, based on the spectra of unirradiated material, one can differentiate between natural, synthetic and swept synthetic crystals.     

Short-lived primary radiation defects in LiF crystals

The spectral and kinetic parameters of electron-pulse-initiated transient absorption and emission of LiF crystals were studied using pulsed spectrometry with a nanosecond time resolution. The measurements were performed in the spectral region of 6 eV, the temperature range of 11–150 K, and within 10^?8–10 s after the termination of an electron pulse. It is shown that the electron-pulse irradiation not only gives rise to F, V _k , and H centers in the LiF crystal but also to certain short-lived defects of two types that differ in the spectral positions of the absorptive and radiative transitions, the lifetime, and the temperature dependence of the production efficiency. Defects of type I feature absorptive transitions at 5.5 and 5.1 eV and a radiative transition at 5.8 eV, whereas the absorptive transitions at 5.3 and 4.75 eV and a radiative transition at 4.4 eV are characteristic of type-II defects. It is found that a variation in the ratio between the concentrations of the different types of short-lived centers in the range of 11–150 K does not affect the quantum efficiency of the F centers. It is assumed that the observed centers are self-trapped excitons of various types.     

Particle track phenomena and radiation power effects at the formation of radiation defects in ionic crystals

The mechanisms of the radiation defect formation in alkali halide crystals are studied in an extremely wide range of the absorbed radiation dose rate (10¹–10¹² Gy/s). It is found that the power dependence of color centers accumulation is described by a curve with a maximum at a dose rate of about 10¹⁰ Gy/s. The electron and proton track parameters for ionic crystals are calculated in the context of the theory of ionization losses of charged-particle energy. Proceeding from the concept of the charged-particle track overlap, the theoretical relations are obtained that explain the radiation power effect in all dielectric materials including alkali halide crystals. The suppression of color center accumulation in these crystals under high-power electron irradiation is due to a more regular topography of the radiation defect formation. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 10–21, February, 2007.     

Decay kinetics of the green emission in tungstates and molybdates

Luminescence characteristics of a number of undoped and variously doped PbWO₄ crystals were studied at 0.4–400 K by the time-resolved spectroscopy and compared with those of ZnWO₄,CdWO₄ and PbMoO₄ crystals. Two types of green emission centres are detected in PbWO₄ crystals. The centres of the first type are responsible for the low-temperature 2.3–2.4 eV emission observed under excitation around 3.90–3.95 eV. The structure and parameters of their relaxed excited states were determined. It was concluded that the origin of defects responsible for the green emission of the first type could vary for different crystals. The centres of the second type with the emission around 2.5 eV appear in crystals containing oxygen vacancies after the thermal destruction of Pb⁺-WO₃ centres at T>180 K. Decomposition of the exciton and various defect-related states was also studied, and activation energies of this process were calculated.     

EPR of trivalent iron centers in SrF<Subscript>2</Subscript>: Fe crystals

Paramagnetic centers of three types are found in SrF₂: Fe(0.2 at. %) crystals. Two types are observed in the untreated crystals, and the third type appears only in the crystals irradiated by x-rays. The EPR spectra of one type of centers in a nonirradiated crystal and of the centers that appear after irradiation are described by the orthorhombic Hamiltonians with an effective spin S _eff = 5/2. In both cases, the centers are observed at 4.2 and 77 K. The principal axes of the spin Hamiltonians for them are along the 〈001〉, 〈1 \(\overline 1 \) 0〉, and 〈110〉 axes. However, the fine-structure parameters of their EPR spectra differ significantly. An analysis of the superhyperfine structure (SHFS) of the EPR spectra shows that the radiation center forms through substitution of a Fe²⁺ ion for a Sr²⁺ cation. Under x-ray irradiation, the Fe²⁺ ion transforms into the Fe³⁺(⁶ A _1g ) state and is displaced to an off-center position along the C ₂ axis of its coordination cube. The absence of a SHFS in the EPR spectra of the orthorhombic centers in a nonirradiated crystal makes it impossible to determine their molecular structure unambiguously. The most probable model is proposed for this structure. The EPR spectra of centers of the third type were observed only at 4.2 K, and the structure of these centers was not studied.     

Electroluminescence of alkali halide crystals activated with europium ions

The prebreakdown electroluminescence of NaCl-Eu, KCl-Eu, and KBr-Eu crystals has been studied. The activator concentration in the crystals was on the order of 10¹⁸ ions per cubic centimeter. The emission spectra, the brightness wave during pulsed excitation, and the concentration dependence of the quantum yield were measured. The experimental results support the suggestion of an impact mechanism for the excitation of the electroluminescence of alkali halide crystals. Recombination and exciton mechanisms for energy migration play an insignificant role. There is no significant contribution from impurity-vacancy dipoles, which act as emission centers, in electric fields up to 10⁶ V/cm.Tomsk Academy of Control and Electronic Systems. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 105–109, February, 1994.     

Fluorescence properties of Bi4Ge3O12(BGO) single crystals under laser excitation: Excited state dynamics and saturation effects

Laser-excited techniques were used to investigate the optical properties of bismuth germanate crystals. Absorption, reflectivity, excitation, emission, lifetime, time-resolved fluorescence, photoconductivity, thermally stimulated conductivity measurements were performed at various temperatures on single crystals of different origins.The absorption is shown to occur in bismuth and germanate centers while both intrinsic and perturbed Bi³⁺ ions together with impurities contribute to the total fluorescence.The emission mechanism at room temperature involves a thermally activated energy migration, and at low temperature localized emitting centers. Formation of deep holes in the wide emission band at room temperature reveals saturation effects on various luminescent centers, promoted by energy migration. Trapped exciton models are proposed to explain the excited state dynamics occurring at low and room temperature.     

Ion-Beam-Induced Luminescence of LiF Using Negative Ions

Negative ion-beam-induced luminescence(IBIL) measurements of a pure LiF crystal using 20 keV H~-are performed to monitor the formation and annihilation of luminescence centers during ion irradiation. Several emission bands are observed in the IBIL spectra and the evolvement mechanisms of the corresponding centers are identified. The difference between the IBIL measurements using positive ions and negative ions is that the intensities of luminescence centers can reach the maxima at lower fluences under negative-ion irradiation due to free charge accumulation.     

Far-infrared spectra of color centers in alkali halides

Abstract

In this paper we wish to review some recent results on the effects of color centers on the vibrational properties of alkali halide crystals.     

Defect states in Lu 3 Al 5 O 12 :Ce crystals

Wavelength-resolved TSL measurements after x-ray irradiation at room temperature were performed on undoped, Ce- and (Ce, Zr)-doped Lu 3 Al 5 O 12 crystals. Several glow peaks were observed in the 20-450 v C temperature region, whose intensities and emission spectra are influenced by doping. Namely, the TSL spectra are governed by defect and trace impurity-related emissions in the undoped crystal, while only the Ce 3+ emission is detected in the doped crystals. Moreover, EPR measurements performed at 12 v K revealed typical spectra of Ce 3+ (4f 1 , S =1/2) occupying Lu 3+ substitutional positions. In situ light irradiation (250-330 v nm) of the crystals results in a step-like decrease of the Ce 3+ EPR intensity. Such a behaviour can reflect a creation of Ce 4+ ions under UV irradiation or an increase of the Ce 3+ population in the excited (5d) state.     

Luminescent patterns based on color centers generated in lithium fluoride by extreme ultraviolet radiation and soft X-rays

Primary and aggregate color centers in lithium fluoride (LiF) crystals and polycrystalline LiF films were produced by an innovative irradiation technique using extreme ultraviolet radiation and soft X-rays generated by a laser-plasma source. This irradiation facility allowed the efficient formation of active color centers on luminescent patterns with submicron spatial resolution on large areas and short exposure times. The method looks promising for the realization of low-dimensionality photonic devices. The optical characterization of the colored structures was performed by means of absorption and photoluminescence measurements on LiF samples colored under different irradiation conditions.