Electrolytic coloration of O2-doped NaCl crystals

O₂²⁻-doped NaCl crystals are colored electrolytically by using a pointed cathode and a flat anode at various temperatures and voltages, which mainly benefit from appropriate coloration temperatures and voltages as well as anode structure of used electrolysis apparatus. Characteristic OH⁻, U, V₂^m, U_A, V₂, V₃, O²⁻-V_a⁺ complex, F, R₁, R₂ and M absorption bands are observed in absorption spectra of the colored crystals. Production and conversion of color centers in electrolytic coloration is explained. Current-time curves for electrolytic colorations and their relationships with electrolytic colorations were given.     

Electrolytic coloration of air-grown sodium fluoride crystals

Air-grown sodium fluoride crystals were colored electrolytically by using a pointed cathode at various temperatures and electric field strengths, which should mainly benefit appropriate coloration temperatures and electric field strengths. , F, M, N₁, N₂ color centers and O²⁻-F⁺ complexes were produced in the colored crystals. Current-time curves for the electrolytic colorations were given, and activation energy for the V color center migration was determined. The formation of the color centers was explained.     

Electrolytic coloration and spectral properties of hydroxyl-doped potassium chloride single crystals

Hydroxyl-doped potassium chloride single crystals are colored electrolytically at various temperatures and voltages using a pointed cathode and a flat anode. Characteristic OH⁻ spectral band is observed in the absorption spectrum of uncolored single crystal. Characteristic O⁻, OH⁻, U, V₂, V₃, O²⁻-V_a⁺, F, R₂ and M spectral bands are observed simultaneously in absorption spectra of colored single crystals. Current-time curve for electrolytic coloration of hydroxyl-doped potassium chloride single crystal and its relationship with electrolytic coloration process are given. Production and conversion of color centers are explained.     

Electrolytic coloration and spectral properties of OH- and Cu-codoped NaCl crystals

OH⁻- and Cu⁺-codoped NaCl crystals are colored electrolytically by using a pointed anode and a flat cathode at various temperatures and under various voltages. Absorption and fluorescence spectral properties of colored crystals are investigated. Absorption, excitation and fluorescence spectra reveal existence of V₂, V₂^m, V₃, OH⁻, U, U_A, O²⁻–V_a⁺, O₂⁺, Cu⁺, Cu⁰, Cu⁻ and OH⁻-perturbed Cu⁺ color centers in colored crystals. Formations of color centers are explained.     

Low-temperature electrolytic coloration and spectral property of ammonium alum crystals

Ammonium alum crystals are colored electrolytically using a pointed cathode and a flat anode at low temperatures and under various voltages. SO₃^?, SO₂^? and O₃^? hole-trapped centers are produced in colored ammonium alum crystals. Characteristic absorption bands of SO₃^?, SO₂^? and O₃^? hole-trapped centers are observed in absorption spectra of colored ammonium alum crystals. Production and conversion of hole-trapped centers are explained. Current–time curves for electrolytic coloration of ammonium alum crystal and their relationship with electrolytic coloration process are given.     

Electrolytic coloration and spectral properties of OH-doped KBr polycrystals

OH⁻-doped KBr polycrystals were colored electrolytically by using a pointed cathode and a flat anode. Characteristic O⁻, OH⁻, U, Cu⁺ and absorption peaks were observed in resolved absorption spectrum of uncolored polycrystals. Herein the position of the absorption peak at room temperature was determined by using a Mollwo-Ivey plot. Characteristic V₂, V₃, Cu⁺, , I₂ and F spectral bands were observed in Kubelka-Munk functions of colored polycrystals. Current-time curve for electrolytic coloration of an OH⁻-doped KBr polycrystal and its relationship with electrolytic coloration process were given. Formation and conversion of color centers were explained.     

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.     

Energy transfer among color centers in LiF crystals

In colored LiF crystals there are many absorption and emission bands which cover a wide region of the spectrum from 200 up to 1 300 nm without breaking the continuity. In the frame of these favourable conditions we have performed some experiments of energy transfer among various color centers. The results indicate the existence of efficient exchanges of radiative energy among several bands by using only one exciting wavelength. In particular, the emissions of the F₃ ^- and F₂ ^- color centers centered at 900 and 1 100 nm, respectively, have been observed by pumping at 672 nm completely outside their absorption bands. Received 25 June 2001 and Received in final form 16 July 2001     

溴化钾晶体电注入着色和光谱特性

用自行研制的电注入装置,在693 K温度下施加DC 1 200 V电压、对溴化钾晶体进行电注入并使之有效着色。在着色溴化钾晶体中产生大量F,R,M,N类和一些新的未知色心,并给出色心形成和转化机理。对着色晶体进行系统光谱测量和分析,用解谱法将相应色心光谱带从测得光谱中合理地分解出来,并精确确定其光谱参数。     

V3+∶YAG晶体的生长、色心与光谱性能研究

采用石墨电阻加热的温梯法生长了V∶YAG晶体，晶体的不同部位呈现两种不同的颜色：浅绿色和黄褐色.通过对比分析不同颜色V∶YAG晶体的室温吸收光谱，推断出石墨发热体高温下扩散出来的C可以起到还原作用，提高晶体中V³⁺_tetra离子的浓度，同时诱导了F心的形成.在1300℃下，对不同颜色的V∶YAG晶体进行真空退火处理，发现处于八面体格位中的V³⁺离子在热激发作用下与近邻的四面体格位Al³⁺离子存在置换反应，由此产生一定浓度的四面体格位V³⁺离子.同时，F心在退火过程中被完全消除，释放出来的自由电子被高价态的V离子俘获，可以进一步提高晶体中四面体格位V³⁺离子的浓度. 关键词： V∶YAG晶体 四面体格位 碳还原 真空退火 F心     

Thermal equilibrium concentrations and effects of negatively charged Ga vacancies in n-type GaAs

We have calculated the thermal equilibrium concentrations of the various negatively charged Ga vacancy species in GaAs. The triply-negatively-charged Ga vacancy, V _Ga ^3– , has been emphasized, since it dominates Ga self-diffusion and Ga-Al interdiffusion under intrinsic and n-doping conditions, as well as the diffusion of Si donor atoms occupying Ga sites. Under strong n-doping conditions, the thermal equilibrium V _Ga ^3– concentration, , has been found to exhibit a temperature independence or a negative temperature dependence, i.e., the value is either unchanged or increases as the temperature is lowered. This is quite contrary to the normal point defect behavior for which the point defect thermal equilibrium concentration decreases as the temperature is lowered. This property provides explanations to a number of outstanding experimental results, either requiring the interpretation that V _Ga ^3– has attained its thermal equilibrium concentration at the onset of each experiment, or requiring mechanisms involving point defect non-equilibrium phenomena.     

Additive coloring of CaF<Subscript>2</Subscript> optical ceramic

The specificity of additive coloring of CaF₂ optical ceramic (formation of color centers in it and photothermochemical transformation of these centers in colored ceramic samples) has been considered. Under the same coloring conditions, this process occurs more slowly in ceramics rather than in crystals; at the same time, the limiting concentration of color centers that can be introduced into ceramics is much higher. The photothermochemical transformations of color centers in crystals and ceramics, which occur under illumination at different wavelengths and upon heating, have been studied. The specific features of introduction of color centers into ceramic and their transformation under illumination and heating are likely to be related to the mass twinning of ceramic grains.     

OH-absorption properties of the optical damage region in codoped In/Mg:LiNbO3 crystals with various Li/Nb ratios

OH-absorption properties of the optical damage region in a series of codoped In/Mg:LiNbO₃ crystals with various Li/Nb ratios have been investigated. The OH⁻-associated vibrational peak at 3507 cm⁻¹ is confirmed to occur in crystals with Li/Nb ratio of 0.94. For codoped In/Mg:LiNbO₃ crystals with Li/Nb ratio of 1.05 and 1.20, the OH⁻-associated vibrational peaks are detected at 3536 and 3507 cm⁻¹ as well. A new peak at 3518 cm⁻¹ attributed to a (In_Nb)²⁻-OH⁻-(Mg_Nb)³⁻ defect center is revealed in crystals with Li/Nb ratio 1.38. When the “In-Mg threshold” concentration is reached, the optical damage resistance ability of codoped In/Mg:LiNbO₃ crystals is greatly improved.     

Effect of gamma irradiation on undoped and uranium doped calcium fluoride crystals

Color centers in undoped and U³⁺-doped CaF₂ crystals induced by γ-irradiation with different doses were studied by differential absorption and Raman spectra. Multiple color centers and conversion among them were caused in undoped CaF₂ with the creation of radiation defects. In U³⁺:CaF₂ crystal, trivalent uranium was demonstrated to act as hole trap in the process of γ-irradiation, which was ionized to tetravalent. This process was accompanied by the formation of F₂⁺ centers, but without additional background absorption due to radiation defects.     

EPR investigation of the trivalent chromium complexes in SrTiO3

The trivalent chromium centers were investigated by means of electron paramagnetic resonance (EPR) in SrTiO₃ single crystals grown using the Verneuil technique. It was shown that the charge compensation of the Cr³⁺-V_O dominant centers in octahedral environment is due to the remote oxygen vacancy located on the axial axis of the center. In order to provide insight into spin-phonon relaxation processes the studies of axial distortion of Cr³⁺-V_O centers have been performed as function of temperature. The analysis of the trigonal Cr³⁺ centers found in SrTiO₃ indicates the presence of the nearest-neighbor strontium vacancy. The next-nearest-neighbor exchange-coupled pairs of Cr³⁺ in SrTiO₃ has been analyzed from the angular variation of the total electron spin of S=2 resonance lines.     

On the validity of the amphoteric-defect model in gallium arsenide and a criterion for Fermi-level pinning by defects

Using the theoretically calculated point-defect total-energy values of Baraff and Schlüter in GaAs, anamphoteric-defect model has been proposed by Walukiewicz to explain a large number of experimental results. The suggested amphoteric-defect system consists of two point-defect species capable of transforming into each other: the doubly negatively charged Ga vacancyV _Ga ^2– and the triply positively charged defect complex (AS_Ga+V _As)³⁺, with As_Ga being the antisite defect of an As atom occupying a Ga site andV _As being an As vacancy. When present in sufficiently high concentrations, the amphoteric defect systemV _Ga ^2– /(As_Ga+V _As)³⁺ is supposed to be able to pin the GaAs Fermi level at approximately theE _v +0.6 eV level position, which requires that the net free energy of theV _Ga/(As_Ga+V _As) defect system to be minimum at the same Fermi-level position. We have carried out a quantitative study of the net energy of this defect system in accordance with the individual point-defect total-energy results of Baraff and Schlüter, and found that the minimum net defect-system-energy position is located at about theE _v +1.2 eV level position instead of the neededE _v +0.6 eV position. Therefore, the validity of the amphoteric-defect model is in doubt. We have proposed a simple criterion for determining the Fermi-level pinning position in the deeper part of the GaAs band gap due to two oppositely charged point-defect species, which should be useful in the future.     

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.     

The electrical properties of zinc in silicon

Electrically active deep levels related to zinc in silicon are investigated in n- and p-type silicon using Deep-Level Transient Fourier Spectroscopy (DLTFS) measurements. While in n-type silicon a level at E _C–0.49 eV is observed, the main zinc-related levels in p-type silicon are determined to be E _V+0.27 eV and E _V+0.60 eV. The latter are associated with zinc situated on regular silicon lattice sites. The emission rate of these centers exhibits a field dependence which cannot be quantitatively explained with the Poole-Frenkel model. On the other hand, a shallow level at E _V+0.09 eV is observed only in boron-doped silicon which may be related to a zinc-boron complex. Other zinc-related levels are found at E _V+0.23 eV and E _V+0.33 eV, their concentration depending on that of zinc on substitutional sites. In addition, the evaluation of depth profiles and the analysis of the field dependence of the emission rate based on the DLTFS method is presented.     

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.     

EPR study of charge compensation of chromium centers in the strontium titanate crystal

Chromium centers and their charge compensation in two single strontium titanate crystals, i.e., SrTiO₃: Cr (0.05 at %) and Sr_0.9995TiO₃: Cr_0.0005 grown with strontium deficiency, have been studied by the electron paramagnetic resonance method. The crystals have been investigated both immediately after growth and after oxidation and reduction procedures. Oxidation and reduction are performed by crystal annealing in a corresponding gas atmosphere at high temperature. Chromium centers associated with oxygen vacancy (Cr³⁺-V _O) are detected in the reduced crystals. It is shown that strontium vacancies are formed in the crystal grown with strontium deficiency, which leads to a lowering of the tetragonal symmetry of (Cr³⁺-V _O) and Cr⁵⁺ centers to the orthorhombic symmetry. Possible compensation mechanisms for charges of various chromium centers are considered.