Farbzentren und Kolloide in abschreckend kondensierten Schichten von NaJ,CaF2 und SrCl2

By a simultaneous evaporation of NaI with excess alkali or alkaline earth metal onto a cooled substrate (T _K =20–150 K) highly disordered thin films are produced, which contain electron excess centers up to a concentration of more than 10²⁰ cm^?3. A complex optical absorption band peaking at 600 and 530 nm is found. The 600 nm band is mainly due to unperturbed F centers, whereas the 530 nm band is ascribed to perturbed F centers, whose symmetry is lowered to C_3v by a nearby Frenkel defect. Another optical transition of this F* center appears at about 600 nm in the dichroic spectrum, which is induced by polarized illumination at 20 K. The transition energies of the F* center are calculated by means of a semi-continuum model. A photochemical transformation of F* and F centers into one another is possible at 20 K. AboveT _K =220 K the excess metal is forming colloidal centers. Two absorption peaks at about 600 and 400 nm, respectively, are ascribed to different colloids, which are either embedded in the crystalline material (600 nm) or only adsorbed to the crystallites (400 nm). By annealing up to 350 K a particle growth and transformation take place. Amorphous quenched films of CaF₂ and SrCl₂ with excess alkaline earth metal reveal mainly colloidal absorption (except a weak F band in CaF₂). The colloids disappear by annealing above 150 K. This is believed to be closely connected with the crystallisation of the films.     

The absorption spectrum and excitons in an Ag2CdI4 ionic conductor

The electron absorption spectrum of thin stochiometric Ag₂CdI₄ films produced by thermal vacuum deposition on a quartz substrate in is investigated. The spectrum shape is sensitive to the method of preparation (the substrate temperature and deposition rate). Under optimal preparation conditions, the films are free of AgI and CdI₂ impurities and the fundamental absorption edge is at 3.28 eV. The long-wavelength exciton A band at 3.31 eV (90 K) is associated with the excitation of excitons in the AgI sublattice of the compound. An investigation of the temperature dependence of the spectral position and half-width of the A band in the range 90–430 K revealed that the exciton-phonon interaction makes the major contribution to the broadening of the band at T ≤360 K. At higher temperatures, the contribution associated with the generation of Frenkel defects with activation energy U _F=0.200±0.025 eV appears.     

Color centers in irradiated MgF2

Abstract

Color centers in rutile-structured MgF₂ single crystals irradiated at 20K/360K by reactor neutrons are investigated spectroscopically at LNT. Four different types of the F-F vacancy bond in MgF₂ are possibly identified to the observed absorption bands as due to the F₂ centers; instead of previous assignments, the 300nm band to the F₂(D_2h), the 325nm band to the F₂(C₁), the 355nm band to the F₂(C_2v), and the 400nm band to the F₂(C_2h) centers.     

F-Zentren und Kolloide in der amorphen,hexagonalen und kubischen Phase von LiJ

By simultaneous evaporation of LiI and Li onto a cooled substrate F centers can be produced in the hexagonal (78 K<T _K <200 K) and amorphous (T _K <78 K) phase of one and the same salt. In both modifications there exist two types of centers F and F^*. The F^* center differs from the cubic F center (T _d -symmetry) by a nearby Frenkel defect. In hexagonal films the normal F band peaks at 2.58 eV, whereas the transitions of the F^* center appear at 2.92 and 2.58 eV too. Polarized irradiation at 20 K causes a dichroic behaviour of the F^* centers. Both types of centers can be transformed into one another photochemically. In the amorphous phase all transitions are shifted to lower energies by about 0.1 eV. After the phase change amorphous→hexagonal the absorption bands shift back by the same amount of energy. AboveT _K =230 K the excess metal forms colloids. The absorption bands are due to colloidal centers embedded in the crystalline material (2.25 eV) and films adsorbed to the crystallites (3.1 eV), respectively. By annealing a particle growth can be observed. After electrolytic colouration cubic single crystals of LiI exhibit an absorption band peaking at 2.36 eV. However, it is not yet sure, if this band is allowed to be ascribed to F centers.     

Enhanced photo-response of thin-film structures with nanocrystals

Thin-film multilayers with dielectric and semiconductor nanolayers of 200-10 nm thicknesses have been deposited by thermal evaporation onto irradiation-resistive substrates using pure crystals as evaporated targets. Some multilayers were γ-irradiated in air at room temperature with dose of 83 kGy. X-ray diffraction and microscopy studies reveal that the multilayers consist of nanometer-sized crystals with cubic structure and defined size. Film structures were oriented along the (1 1 1) plane. Absorption spectra of non-irradiated LiF nanocrystals of 100 nm size and those of initial crystals give evidence of metal colloids presence. Photoluminescence spectra of γ-irradiated nanostructures with various LiF content show the enhancement of F₃⁺-colour centres excitation in the region of metal colloids absorption and the increase is observed between emission intensities of F₃⁺ and F₂ centers with respect to initial crystals γ-coloured in identical conditions. Emission intensities of both centers under excitation in the M band correlate with LiF content. These effects, which are related to high-quality nanocrystals, but at the same time depend strongly on the defect content, especially as far as their 1-2 ps nonlinearities are concerned, could depend on nanocrystal purity and metal excess collection in their boundaries regions.     

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.     

Optical absorption spectrum of the U centre in SrCl2

Studies of the correlation between i.r. and u.v. absorption spectra show that the u.v. absorption band of U centres is peaked at 212.3 nm. The weak peak observed at 233 nm is probably due to an impurity and some of the experimental results allow us to assume that it can be O^2-.The absorption band shape of U centres is very similar to that of F centres in SrCl₂. The second moment variations of these bands vs temperature can be interpreted in terms of an effective phonon frequency of 93 cm^-1.     

Line emission of SrBe2Si2O7:Eu2+ and BaBe2Si2O7:Eu2+

The compounds SrBe₂Si₂O₇ and BaBe₂Si₂O₇ both have the barylite structure. With 254 nm excitation, the Eu²⁺-activated compounds give UV emission peaking at 360 nm (Sr) and at 375 nm (Ba). Maximum quantum efficiencies of 40% (Sr) and 65% (Ba) were measured. The emission consists of a 5d-4f band emission as well as 4f-4f line emission, in contrast to many other Eu²⁺-activated oxides which generally show only 5d-4f band emission. At 77°K, both compounds show only the 4f-4f line emission peaking at 360 nm. At higher temperatures, 5d-4f band emission shows up at the cost of the line emission. A thermal equilibrium is assumed between the lowest excited 5d and 4f levels. The energy difference between these levels, calculated from the variation in the line-band intensity ratio with temperature, was computed to be 0.15 eV (Sr) and 0.09 eV (Ba). The occurrence of the line emission in the barylites is correlated with the weakness of the crystal field at the Eu²⁺ ions and with the high quenching temperature of the 5d-4f band emission.     

A novel method to synthesize ordered porous SnO2 nanostructures and their optical properties

Three-dimensional porous ordered SnO₂ nanostructures have been fabricated by templating a sol–gel precursor solution against the polystyrene nanospheres for the first time. Field emission scanning electron micrography (FESEM) indicates that the surface of the nanostructures is highly regular and the porous structures are perfectly ordered. Besides a broad emission band at 600 nm, the porous SnO₂ nanostructures show an additional emission band at 430 nm, which is seldom seen in the bulk SnO₂ materials. Spectral examinations and analyses reveal that the 430 nm band is induced by the interfacial effects between the porous frameworks.     

Phenyl substituted Mg porphyrazines: The effect of annulation of a chalcogen-containing heterocycle on the spectral-luminescent properties

We have performed complex experimental and theoretical investigations of the spectral-luminescent properties and electronic structure of new phthalocyanine analogs, Mg octaphenylporphyrazine and its derivatives with an annulated thiadiazole or selenadiazole ring instead of two phenyl groups. Fluorescence characteristics have been determined at 293 and 77 K: emission, excitation, and fluorescence polarization spectra; fluorescence quantum yield ?? _F , and lifetime ?? _F . Annulation of a five-membered chalcogen-containing heterocycle leads to splitting of the long-wavelength absorption band Q(0-0) and to the bathochromic shift of its longest wavelength component Q _x (0-0), which increase upon passage from S to Se. At the same time, the fluorescence quantum yield ?? _F and lifetime ?? _F decrease, which is related to the intramolecular heavy-atom effect. The geometric structure of the ground state of the Mg porphyrazine molecules has been determined based on the density functional theory (DFT), and excited electronic states have been calculated with modified parametrization of the INDO/S method, INDO/Sm. Semiquantitatively, the calculated level positions of the lowest Q states and spectral shifts of Mg octaphenylporphyrazine and S-derivative agree with experimental data. For the range of the Soret band, calculated transition energies and their intensity distributions substantially depend on the dihedral angle ?? between a phenyl ring and porphyrazine macrocycle. We show that, based on calculations at the angle ?? = 60°, bands in the observed absorption spectra can be assigned with an accuracy of ??2000 cm^?1.     

Y-Absorptionsbande im bestrahlten LiF

The absorption measurements at a constant and uniformly increasing temperature and the thermostimulated electron emission and luminescence of with α-, cathode- andγ-rays irradiated LiF crystals were performed and the conditions of the formation of a new absorption band at about 500 nm investigated. It turned out that the band in α-irradiated samples is composed from two and inγ-irradiated from three bands. In this case the short-wave-length-band with the zero-phonon-line at 491 nm is very probably the well knownF ₃ ^t -band. The long-wave-length-band with the zero-phononline at 507 nm (theX band) is of unknown nature. TheY band lies at 494,3 nm (at 77 ?K) and its nature could consist in the colour centre agglomerates.     

Photoluminescence of F2+2 centres in additively coloured magnesium oxide

The principle luminescence bands excited in additively coloured MgO by radiation in the wavelength range 170–400 nm are observed at wavelengths of 520, 475, 441 and 375 nm. Polarised luminescence and uniaxial stress measurements on the 441 nm band, the radiative lifetime of 25 msec at 1.6 K and temperature dependence of luminescence intensities of the 375, 441 and 375 nm bands are consistent with the 441 nm band being due to ³B_1u → ¹A_g transitions of the F²⁺₂ centre.     

Optical properties of Cu+ centers in NaCl

Different aggregation-precipitation states of Cu⁺ have been characterized by absorption bands peaked at 305, 350 and 372–383 nm.The absorption bands at 372–383 nm, observed exclusively in the most doped crystal, have been associated with the Z₁₂, Z₃ excitons of CuCl microcrystals incorporated into the NaCl matrix Their positions shift to low energies with increasing concentration, as expected for a decrease in the stress over the precipitate.The Z1₁₂, Z₃ exciton bands of CuCl microcrystals precipitated in NaCl can be observed by the optical absorption spectrum without reaching saturation Therefore, this technique could be an alternative method to studies of CuCl thin-film depositions or reflectivity of CuCl single crystals.The red emission band observed at 600 nm is a long-lived emission (τ? 29 ms) at variance with the behavior reported for the Cu⁺ emission It is related to energy transfer processes from Cu⁺ to Mn²⁺.     

Electronic absorption and emission spectra of Alq3 in solution with special attention to a delayed fluorescence

Tris(8-quinolinolato)aluminum(III) (Alq₃) shows electronic absorption bands at 378, 360 (in a 1:1 mixed solvent of methanol and ethanol (ME) at 77 K), 334, 316, 300, 263, 255.8, and 233 nm in ethanol at room temperature. According to the polarized fluorescence excitation spectrum together with MO calculations, for instance, the 360 nm band is assigned to an LL CT transition (an intramolecular charge transfer transition between two ligands), and the 378 nm band to an LM/ML CT one (an intramolecular charge transfer transition between ligand and metal). Alq₃ shows a broad fluorescence band peaking at around 478 nm in the ME matrix at 77 K. The emission spectrum measured with a phosphoroscope has two emission bands at 567 and 478 nm. The 567 nm band accompanies vibronic bands at 578 and 605 nm, being safely assigned to a phosphorescence of Alq₃. The lifetimes of the 478 and 567 nm bands are both 5.4 ms. The lifetime of the 478 nm band together with the band position and its band shape indicate that this band can be assigned to a delayed fluorescence.     

Uniaxial stress and polarisation studies of F2 centre luminescence in MgO

Uniaxial stress and polarised luminescence measurements of additively coloured MgO show that the 375 nm luminescence band is associated with pairs of F centres in nearest neighbour sites along 〈110〉 crystal directions (i.e. F₂ centres).     

Thermoluminescence and recovery processes in pure and doped NaCl after 20 K irradiation

The thermoluminescence (TL) spectra after X-ray irradiation at 20 K have been investigated for pure as well as divalent cation doped NaCl. The F-centre decay has also been determined in pure and Ca and Mg doped NaCl for comparison purposes. A clear decrease in F-centre concentration appears to correlate with glow peaks at 44 and 50 K for pure and Ca-doped samples. Main glow peak appearing at 69 K is not associated to any appreciable F-centre decay step. Below liquid nitrogen temperature (LNT) all peaks show both σ and π exciton emission bands. Above LNT, the glow peaks for doped samples show the σ emission together with another band at 410 nm, whereas pure samples still present the intrinsic emission bands.     

The examination of the Faraday effect and location of the Cr level in Cr doped PbTe

Faraday effect, absorption coefficient and Hall effect have been examined in Cr doped PbTe single crystals. The effective masses of carriers m_F and then values of effective masses at the bottom of conductivity band m_F(0) have been calculated. It is shown that m_F in Cr doped PbTe is comparable with m_F in n-type PbTe not doped with chromium, with the same free carrier concentration, and the relative temperature variation of m_F(0) corresponds to relative variation of Eg. In the absorption spectrum the additional absorption maximum is found at the energy 0.11–0.14 eV. The long-wave side of the peak is shifted towards longer waves as the temperature is increased. Calculation shows that chromium level is located in the conduction band at ΔE = 0.11 eV in the limit T → 0, and is shifted down towards the bottom of the conduction band with a constant rate of $\text{0.8 × 10}{}^{\mathrm{?4}}\text{eV}\text{K}$ within the temperature range of 4.4–300 K and $\text{3.3 × 10}{}^{\mathrm{?4}}\text{eV}\text{K}$ within the temperature range 300–800 K.     

The effect of concentration on the thermo-optical properties of colloidal silver nanoparticles

The thermo-optical properties of colloidal silver nanoparticles (AgNPs) are investigated under a low power laser irradiation at 532 nm. Colloidal AgNPs are synthesized by nanosecond pulsed laser ablation of a pure silver plate in distilled water. The morphology and size of the AgNPs are determined by transmission electron microscopy. Closed Z-scan measurements reveal that nonlocal thermo-optic process is responsible for the nonlinear refractive index of colloid containing different concentrations of silver nanoparticles. The Z-scan behavior of the nanoparticle samples has been investigated based on a nonlocal thermo-optic process and it is shown that the aberrant thermal lens model is in excellent agreement with the experimental results. Z-scan measurement fits have allowed the values of nonlinear refractive index (n₂) and thermo-optic coefficients (dn/dt) to be determined at different concentrations of silver nanoparticles. Large enhancement factors were measured for values of n₂ and dn/dt of the colloids at higher silver nanoparticle volume fraction. Our results suggest that nonlocal thermal nonlinear processes will play an important role in the development of photonic applications involving metal nanoparticle colloids.     

Studies of first-stage F-centre production in alkali halides doped with strontium

KBr crystals doped with strontium have been X-irradiated at 293 K. The reduction in single impurity-vacancy dipole concentration has been measured using I.T.C. techniques and is found to be proportional to and in quite close numerical agreement with F-centre growth in both first and second stage F-centre production, this being in agreement with previous results in KCl(Sr). The growth of the absorption band peaking at 263 nm was studied and was found to be proportional to F-centre growth during the earlier stages of colouration, indicating that the responsible centres are a major complement of the F-centres. Ionic conductivity experiments show little agreement between the decay of conductivity and the growth of F-centres during X-irradiation of KCl(Sr) crystals at 293 K.A model is developed in which interstitials are trapped at impurity-vacancy dipoles and in which the two stages of F-centre production is the result of dynamic processes involving modifications of the excitonic mechanism or of back reactions.     

The efficiency of formation of primary radiation defects in LiF and MgF2 crystals

Processes of radiation formation of primary defects—F centers and self-trapped excitons—in lithium and magnesium fluorides, which have crystal lattices of different types and similar widths of the band gap and valence band, have been studied in a wide temperature range (11–500 K). It is shown that, along with qualitative similarity of the regularities of formation of the defects under study, LiF and MgF₂ crystals are characterized at low temperatures (11–100 K) by different relationships between the energy dissipation channels for self-trapping electronic excitations and the types of self-trapped excitons arising.