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.     

Coloration under two-phonon excitation of KCl crystals containing halogen impurities

Color centers induced in KCl:I and KCl:Br crystals by N₂ laser irradiation have been studied at 9 K. It is found that the absorption spectra observed in both crystals are similar to that obtained in undoped KCl X-rayed at low temperatures. Resulting color centers are of the intrinsic lattice involving the F- and the H-centers in host KCl.     

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.     

Shallow Donors and Deep-Level Color Centers in Bulk AlN Crystals: EPR, ENDOR, ODMR and Optical Studies

The results of studies of shallow donors and deep-level color centers in bulk AlN crystals are presented. Two shallow donors (presumably oxygen located on the nitrogen site and carbon located on the aluminum site) are suggested to exhibit the DX-relaxation. Third shallow donor (presumably silicon on the Al site) shows the shallow donor behavior up to the room temperature and can be observed without light excitation at temperatures above 200 K. The values of the Bohr radius of the shallow donors are estimated. The structure of deep-level color centers (neutral nitrogen vacancy V _N) in bulk AlN crystals is determined and analyzed by electron paramagnetic resonance, electron-nuclear double resonance, optical absorption and thermoluminescence induced by X-ray irradiation. Spin-dependent recombination processes in AlN crystals are studied by means of optically detected magnetic resonance.     

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.     

Optical properties of UV-induced color centers in a KY3F10:Ce3+ crystal

The evolution of color centers induced in a KY₃F₁₀:Ce³⁺ crystal by UV radiation has been observed and interpreted. It has been revealed that, initially, the UV irradiation of the KY₃F₁₀:Ce³⁺ crystal induces the formation of color centers predominantly of the F-type, which, in a short time period of about ten minutes, are transformed into complex color centers of the F ₂-type, as well as into impurity color centers. Based on the data obtained, a diagram of energy states of the crystal, dopant, and color centers has been constructed, on which most probable processes that are caused by electronic transitions occurring in the KYF:Ce³⁺ crystal after its UV irradiation have been indicated.     

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⁺.     

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.     

Radiation induced defects in KBr:Tl+ crystals

The defects produced in KBr:Tl⁺ crystals during x-irradiation at 77 K were studied using thermoluminescence (TL), thermally stimulated currents (TSC), and absorption and emission spectra. Three main glow peaks at 165, 193 and 258 K were observed both in the TL and in the TSC curves. A variety of irradiation induced absorption bands were observed in the UV, visible and infrared up to about 2 microns. The 165 K TL peak was found to emit only the 440 nm band assigned to thallium dimers, while the peaks at 193 and 258 K exhibited the UV bands at 310 and 365 nm as well as the 440 nm band.The defects produced during the irradiation were the V_k hole center, the Tl° and the Tl⁺₂ electron centers. Smaller concentrations of Tl²⁺ and (Tl⁺)⁺₂ centers were also produced.An analysis of the results including measurements on lightly and heavily doped crystals enabled to draw conclusions on the nature of the defects and on the recombination processes involved. A close correlation has been found between the temperatures at which changes in the various absorption bands take place and the temperatures of the TL peaks. The analysis enabled also a full classification of the absorption bands.     

Structural and radiation color centers and the dielectric properties of doped yttrium aluminum garnet crystals

The results of experimental and theoretical studies of the spectral and dielectric properties of garnet Y₃Al₅O₁₂ crystals are analyzed. The crystals studied were grown under different conditions and were either pure or contained iron-group ion impurities (Ti, Cr, Fe). The crystals were studied before and after irradiation by γ rays and high-energy electrons. A model is proposed for the formation of color centers and their influence on luminescent and other optical and dielectric properties.     

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.     

Thermal decay of photochromic color centers in CaF2, SrF2, and BaF2 crystals doped by La and Y impurities

The absorption spectra of photochromic centers in CaF₂, SrF₂, and BaF₂ crystals doped by La and Y impurities and thermal decay of the centers in the temperature range 80–600 K are investigated. Under low-temperature x-ray irradiation, ionized photochromic color (PC⁺) centers are generated in La- and Y-doped CaF₂ crystals and in a La-doped SrF₂ crystal. It is revealed that, upon heating of the CaF₂-LaF₃ crystal, PC⁺ centers are transformed into photochromic color (PC) centers. In the SrF₂-YF₃ crystal irradiated at room temperature, photochromic color centers are generated as well. All color centers decay at a temperature of approximately 600 K. After irradiation of the BaF₂-YF₃ crystal at a temperature of 80 K, absorption bands are observed at energies of 2.25 and 3.60 eV, which are related to neither PC centers nor PC⁺ centers.     

Elektronenspin-Resonanz und Photochemie des U2-Zentrums in Alkalihalogenid-Kristallen

The photochemical reactions involved in the production and in the bleaching of U₂ centers (interstitial hydrogen atoms) in KCl, KBr and NaCl crystals are investigated by measuring the optical absorption spectra of the crystals at low temperatures. The U₂ centers are prepared by UV irradiation of hydroxide- and hydride-doped crystals. The electron spin resonance of KCl, KBr and NaCl crystals with U₂ centers at low temperatures reveals a well-resolved hyperfine splitting due to interactions of the hydrogen atom with four neighbouring halogen ions. The U₂ center can be described as a tetrahedal [HX₄]^4?-molecule ion, in which one hole, bound mainly at the hydrogen atom and partially at the surrounding halogen ions, gives rise to the spin resonance.     

V color centers in electrolytically colored hydroxyl-doped sodium chloride crystals

Hydroxyl-doped sodium chloride crystals were successfully colored electrolytically by using pointed anode and flat cathode at various temperatures and under various electric field strengths. V₂ and V₃ color centers were produced in the colored crystals. Current-time curves for the electrolytic colorations were given, and activation energy for the V₂ and V₃ color center migration was determined. Production of the V₂ and V₃ color centers and formation of current zones for the electrolytic colorations of the hydroxyl-doped sodium chloride crystals are explained.     

Time-resolved optical spectroscopy of CsI(Tl) crystals by pulsed electron beam irradiation

Properties of the color and emission centers induced with an electron pulse beam at temperature within 80-300 K have been studied in CsI(Tl) crystals. It has been established by optical spectrometry with time resolution that initial color centers in this crystal are only Tl⁰ and V_k centers, which spontaneously recombine emitting visible light at 2.25 and 2.55 eV. It has been shown that the emission decay kinetics at 80 K include two fast exponential components with decay constants 3 and 14 μs as well as slow hyperbolic component with the power index depending on the wavelength of the emitting light. The temperature effect on the emission kinetics has been studied and it has been directly proved that the emission rise stage at the temperature above 170 K is caused by the recombination of electrons, which are thermally released from single Tl⁰ centers, with V_kA centers. The origin of scintillations in CsI(Tl) crystal is discussed in terms of the tunnel electron transitions from ground state of Tl⁰ centers to ground state of V_k centers at different distances from each other.     

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.     

Elektronenspin-Resonanz von Stickstoffzentren in Alkalihalogenid-Kristallen

Paramagnetic nitrogen centers are produced in nitrate doped single crystals of KCl, KBr, KJ, and NaCl by introduction of F-centers. The electron spin resonance is studied at low temperature. The hyperfine structure of the lines is caused by interaction with two N¹⁴ nuclei. The angle dependence of the resonance spectra is measured by rotating the crystals about several crystallographic axes. The results can be fitted to a spin-Hamiltonian with orthorhombic symmetry. The components of theg-tensor and theA-tensor are determined. The centers are believed to be N ₂ ^? -ions in negative ion vacancies.     

Formation of H<Subscript><Emphasis Type="Italic">a</Emphasis></Subscript><Superscript>-</Superscript> hydrogen centers upon additive coloration of alkaline-earth fluoride crystals

The mechanism of coloration of alkaline-earth fluoride crystals CaF₂, SrF₂, and BaF₂ in calcium vapors in an autoclave with a cold zone is studied. It was found that the pressure in the autoclave upon constant evacuation by a vacuum pump within the temperature range of 500–800°C increases due to evaporation of metal calcium. In addition to the optical-absorption bands of color centers in the additively colored undoped crystals or to the bands of divalent ions in the crystals doped with rare-earth Sm, Yb, and Tm elements, there appear intense bands in the vacuum ultraviolet region at 7.7, 7.0, and 6.025 eV in CaF₂, SrF₂, and BaF₂, respectively. These bands belong to the H_a ^- hydrogen centers. The formation of hydrogen centers is also confirmed by the appearance of the EPR signal of interstitial hydrogen atoms after X-ray irradiation of the additively colored crystals. Grinding of the outer edges of the colored crystals leads to a decrease in the hydrogen absorption-band intensity with depth to complete disappearance. The rate of hydrogen penetration inside the crystal is lower than the corresponding rate of color centers (anion vacancies) by a factor of tens. The visible color density of the outer regions of the hydrogen-containing crystals is several times lower than that of the inner region due to the competition between the color centers and hydrogen centers.     

Photo- and radiation-chemical transformations of carbonate ions in CsI and CsI(Tl) crystals

It is shown that irradiation of CsI and CsI(Tl) crystals containing carbonate and hydroxyl ions induces radiation defects there in the form of color centers, HCO ₃ ^- ions, and H₂O molecules. HCO ₃ ^- ions are formed in the bulk of crystals, whereas water molecules are formed only in the surface layer. IR spectra offered no evidence of decomposition of CO ₃ ^2- ions into CO and CO ₂ ^- and of formation of CO ₃ ^- ions in the course of growth nor in the course of irradiation of CsI(CO₃) and CsI(Tl, CO₃) crystals. Electron activator color centers in CsI(Tl, CO₃) crystals are likely to be stabilized by hole near-activator centers and by HCO ₃ ^- ions produced in radiation-induced chemical reactions.     

EPR study of the effect of ionizing radiation on chromium centers in Mg2SiO4: Cr,Li laser crystals

Forsterite single crystals doped with chromium and lithium and exposed to ionizing radiation have been studied using multifrequency electron paramagnetic resonance (EPR) spectroscopy. It has been found that ionizing irradiation up to a dose of 10⁸ rad does not lead to a significant change in the concentration of single chromium impurity centers. At the same time, γ-ray irradiation of the crystal leads to a decrease in the concentration of active laser centers, which form an associate of trivalent chromium and monovalent lithium in the crystallographic positions M2 and M1, respectively, and to the formation of new centers of divalent chromium. The structure and magnetic properties of the new centers have been discussed.