New class of holographic materials based on CdF<Subscript>2</Subscript> semiconductor crystals with bistable centers. I. Role of covalence in the formation of bistable centers

Calculations of the electronic structure of In, Ga, and Al impurity centers in a CdF₂ crystal in the cluster approximation using the method of scattered waves are made. The first two impurities form in additively colored crystals bistable centers having a ground two-electron (deep) state and a metastable hydrogen-like (shallow) state. A change in the nature of the chemical bond on doping a crystal with these impurities is traced, which consists in a considerable increase of its covalent component. A change for deep In and Ga centers is shown to be caused by the reconstruction of centers in their ground state, and a conclusion about the character of reconstruction is made. This conclusion agrees with recent calculations made for the center structure using the pseudopotential method. Conditions of formation of bistable centers in CdF 2 and their structure in different charge states are discussed.     

Dynamics of the transformation of bistable centers and lattice in CdF<Subscript>2</Subscript> crystals under femtosecond pulsed photoexcitation

The kinetics of photoinduced absorption spectra of CdF₂ crystals with bistable indium and gallium centers under femtosecond pulsed excitation has been experimentally investigated. Based on the example of indium ions, it is shown that the transmission band in the absorption spectrum of deep centers is formed for 0.8–1 ps, which significantly exceeds the photon absorption time. This process is interpreted as a result of displacement of indium ion from the initial interstitial position to a site of neighboring unit cell; the displacement velocity is estimated to be 200–250 m/s, a value close to the thermal velocity of this ion at room temperature. The times characteristic of the formation of free polarons as a result of the displacement of neighboring lattice ions have been experimentally estimated for the first time at a level of 0.8–1.2 ps. The capture times of free polarons by trivalent gallium and indium ions are estimated (5 and 10 ps, respectively), as well as the corresponding cross sections (2 × 10⁻¹⁶ and 8 × 10⁻¹⁶ cm²).     

Dynamic wavefront-conjugating mirror based on CdF2 crystals with bistable in centers

The wavefront reversal upon degenerate four-wave interaction in a CdF₂ crystal with bistable In centers is experimentally investigated using a pulsed ruby laser as a pump source. The reflectance and operating speed of the wavefront-conjugating mirror are measured and the quality of the reflected wave, as well as of the compensation of model phase distortions, is estimated. An operating speed of about 15 ns is obtained for such a mirror with a reflectance of up to 2% at room temperature. Compensation of model large-scale distortions yields a gain in the beam divergence of 20 and a quality of compensation of 1.05.     

Microwave measurements of electrical conductivity of CdF<Subscript>2</Subscript> semiconductor crystals

The electrical conductivity of CdF₂ semiconductor crystals is measured using the microwave intracavity technique at a frequency of ～35 GHz. The crystals are activated with yttrium donor impurities and indium and gallium ions forming bistable one-electron donor impurity and two-electron DX centers. The conclusion is drawn that the concentration of electrons in the conduction band of CdF₂: Ga crystals has an anomalously high value. This confirms the results obtained in earlier NMR investigations of CdF₂ semiconductor crystals at room temperature.     

Effective room-temperature broad-band recording of 3D dynamic holograms in CdF<Subscript>2</Subscript>:Ga crystals

Photochromic CdF₂:Ga crystals with bistable impurity centers were effectively used for the dynamic recording of holograms and readout over the visible and near IR spectral regions at spatial frequencies of up to 5000 mm^?1 at room temperature. The diffraction efficiency of the dynamic holograms was as high as 60% at maximum and exceeded 1% when the beams’ intensities were in the ratio 1:100. As one goes from the low temperatures (≤200 K) to 300 K, the peak diffraction efficiency of the dynamic holograms decreases approximately by a factor of 1.5, while the speed of their response and photosensitivity in the long-wavelength spectral region increases by more than an order of magnitude. For the sake of comparison, the dynamic holograms were recorded under the same conditions as the widely used electrooptical SBN crystals. Comparative analysis ascertained a unique combination of the useful features offered by CdF₂:Ga crystals in holography.     

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.     

Recording dynamic holograms in a semiconductor crystal CdF<Subscript>2</Subscript>:In

The kinetics of decay of a phase hologram in a semiconductor CdF₂ crystal with bistable In centers is studied. Kinetic constants of the hologram decay are found, and the potential relief of the bistable center is plotted. The resolving power of the crystal is evaluated and recording of a transparency is demonstrated.     

Recording of dynamic information holograms in a CdF<Subscript>2</Subscript>:In crystal

It is shown that CdF₂:In crystals can be used to record amplitude-phase information holograms in real time. The diffraction efficiency of these holograms is several percent, but they are characterized by a much higher sensitivity in comparison with phase holograms recorded in the transparency region of the crystal. A model experiment on pattern recognition is performed.     

Location of the energy levels of the rare-earth ions in BaF<Subscript>2</Subscript> and CdF<Subscript>2</Subscript>

The location of the energy levels of rare-earth (RE) elements in the energy band diagram of BaF₂ and CdF₂ crystals is determined. The role of RE ³⁺ and RE ²⁺ ions in the capture of charge carriers, luminescence, and the formation of radiation defects is evaluated. It is shown that the substantial difference in the luminescence properties of BaF₂: RE and CdF₂: RE is associated with the location of the excited energy levels in the band diagram of the crystals.     

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.     

Local structure of Gd<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> impurity centers in a CdF<Subscript>2</Subscript> crystal

The local crystal structure of Gd³⁺ and Eu²⁺ cubic impurity centers in cadmium fluoride is calculated within the shell model in the pair potential approximation. The local compressibility of the cationic and anionic sublattices of the host lattice is determined in the vicinity of the Gd³⁺ (Eu²⁺) impurity ion.     

Methane sensor based on SnO<Subscript>2</Subscript>/In<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanostructure

Two sets of samples of SnO₂/In₂O₃/TiO₂ system have been fabricated with different concentrations of component materials. In the first set TiO₂ with rutile structure was used, while in the second set it has the structure of anatase. Thin films (up to 50 nm) of obtained mixtures were deposited. Their sensitivity and selectivity with respect to methane (CH4) were studied. Nanostructure on the basis of 70%SnO₂ — 10%In₂O₃ — 20%TiO₂(anatase) exhibits sufficient sensitivity to methane.     

Jahn-teller chromium ions in CdF<Subscript>2</Subscript> and CaF<Subscript>2</Subscript> crystals: An EPR spectroscopic study in the frequency range 9.3–300 GHz

The bivalent chromium impurity centers in CdF₂ and CaF₂ crystals are investigated using electron paramagnetic resonance (EPR) in the frequency range 9.3–300 GHz. It is found that Cr²⁺ ions in the lattices of these crystals occupy cation positions and form [CrF₄F₄]^6? clusters whose magnetic properties at low temperatures are characterized by orthorhombic symmetry. The parameters of the electron Zeeman and ligand interactions of the Cr²⁺ ion with four fluorine ions in the nearest environment are determined. The initial splittings in the system of spin energy levels of the cluster are measured.     

Electrical instability of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

The temperature behavior of I-U curves and the field and temperature dependences of the electrical resistivity and dielectric permittivity of crystals of the LiCu₂O₂ phase have been studied. It was established that the crystals belong to p-type semiconductors and that their static resistivity in the range 80–260 K follows the Mott law ρ=Aexp(T₀/T)^1/4 describing variable-range hopping over localized states. At comparatively low electric fields, the crystals exhibit threshold switching and characteristic S-shaped I-U curves containing a region of negative differential resistivity. In the critical voltage region, jumps in the conductivity and dielectric permittivity are observed. Possible mechanisms of the disorder and electrical instability in these crystals are discussed.     

Optical properties of CdF<Subscript>2</Subscript> in a wide energy range

For either of the two reflection spectra of cadmium difluoride that are known from experiments, a complete set of the fundamental optical functions is calculated in the energy range 4–45 eV with the Kramers-Kronig relationships. The basic features of the optical spectra are established, and a hypothesis for their origin is suggested based on the known theoretical results for the band structure.     

Magnetic properties of Pb<Subscript>2</Subscript>Fe<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>9</Subscript> single crystals

Single crystals of Pb₂Fe₂Ge₂O₉ have been grown. They were subjected to X-ray diffraction, magnetic, neutron diffraction, Mössbauer and spin resonance studies. It has been established that Pb₂Fe₂Ge₂O₉ is a weak ferromagnet with a Néel temperature T _N = 46 K, and the exchange and spin-flop transition fields have been estimated. It has been demonstrated that the weak ferromagnetic moment is actually the result of the single-ion anisotropy axes for the magnetic moments of different magnetic sublattices being not collinear.     

Spectral-kinetic characteristics of crystals and nanoceramics based on BaF<Subscript>2</Subscript> and BaF<Subscript>2</Subscript>: Ce

Optical characteristics of BaF₂ and BaF₂: Ce single crystals and nanoceramic materials prepared from these single crystals by uniaxial hot pressing have been studied. It has been shown that the introduction of Ce₃₊ ions into BaF₂ hardly affects the ultrafast (∼0.9 ns) luminescence component. The integrated luminescence intensity of the BaF₂: Ce nanoceramics is higher than that of the corresponding single crystal and considerably higher that the intensity of the undoped BaF₂ crystal. It has been demonstrated that the slow (several hundred nanoseconds) component of the luminescence decay of BaF₂: Ce is due to the energy transfer from excitons to Ce³⁺ ions.     

Luminescence and electronic excitations in crystals K<Subscript>2</Subscript>Al<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> with defects

This paper reports on the results of the comprehensive study of the dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals, obtained by low-temperature luminescence vacuum ultraviolet spectroscopy with nanosecond time resolution upon photoexcitation by synchrotron radiation. For the first time, the data have been obtained on the photoluminescence (PL) decay kinetics, PL spectra with time resolution, PL excitation spectra with time resolution, and reflection spectra at 7 K; the intrinsic nature of PL at 3.28 eV has been established; luminescence bands of defects have been separated in the visible and ultraviolet spectral regions; an intense long-wavelength PL band has been detected at 1.72 eV; channels of the formation and decay of electronic excitations in K₂Al₂B₂O₇ crystals have been discussed.     

Coherent semilinear oscillator with Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript>:Sb crystals

We present experimental results for the semilinear oscillator geometry based on Sn₂P₂S₆:Sb photorefractive crystals. The samples with strong two-wave mixing gain demonstrate degenerate oscillation regime. A mirrorless oscillation is also observed.     

Relaxation processes upon photoexcitation of semiconductor CdF<Subscript>2</Subscript> by laser pulses

The microwave-cavity-based technique is used to study the processes of photoionization of electrons from donor levels to the conduction band in semiconductor CdF₂ crystals doped with Y, In, or Ga. The samples were excited by periodic pulses of Nd-laser (λ = 1.06 μm, pulse width ～10 ns) in the temperature range 6–77 K. The transient processes were detected in the absorption and dispersion modes related to variation of the imaginary and real parts of the complex permittivity ?₁ ? i?₂ induced by the light pulses. The observed signals consisted of short peak at t ～ 0, approximately 40–70 ns in length, and a long tail with a duration of ～100 ms. The short peak is likely to be related to the stay of the photoexcited carriers in the conduction band, while the long tail is associated with the processes of excitation relaxation after the electrons coming back to the donor levels of the impurity band. The weak temperature dependence of the width of the peak at t ～ 0 is explained by the tunneling mechanism of relaxation of electrons through the energy (or, probably, spatial) barrier separating the bound and free states of the carriers in the semiconductor CdF₂.