Electron statistics in CdF2 semiconductor crystals with DX centers

The degree of compensation and ionization energy of two-electron DX centers in CdF₂: In and CdF₂: Ga semiconductors are determined by studying the statistical distribution of electrons localized on impurity levels. The sharp temperature dependence of the concentration of neutral donors observed in CdF₂: Ga over the temperature range T = 250–400 K is explained by a high compensation degree, K ≥ 0.996. Thus, all Ga ions introduced into a CdF₂ crystal lattice during crystal growth form shallow donor levels. However, the concentration of Ga ions that can form bistable DX centers is rather low and is close to the concentration of electrons injected into the crystal during additive coloring. In CdF₂: In crystals, the degree of compensation is smaller than that in CdF₂: Ga but is sufficiently high and the number of bistable DX centers is not limited. It is concluded that an extremely narrow impurity band forms in the CdF₂: Ga semiconductor. For a total charged-impurity concentration of ～10²⁰ cm^?3, the width of the impurity band in CdF₂: Ga is not likely to exceed ～0.02 eV.     

Photodielectric effect and “Configuration” modes of bistable centers in the CdF<Subscript>2</Subscript>: Ga crystal

A photoinduced increase in the real (?′) and imaginary (?″) parts of the permittivity (Δ?′ ≈ 0.23 and Δ?″ ≈ 0.10 at a frequency of 15 cm^?1) is revealed experimentally. This photodielectric effect is adequately described by the predicted configuration modes at the frequencies gv ₁ = 354 cm^?1 and gv ₂ = 123 cm^?1, which correspond to the potential-energy curves previously calculated for deep and shallow impurity states in CdF₂: Ga crystals. The dielectric contributions of these modes are determined, and the corresponding concentrations of Ga ions in deep (N ₁) and shallow (N ₂) impurity states are calculated. It is found that, unlike the CdF₂: In crystals, the changes in the quantities ?′ and ?″ before and after illumination of the CdF₂: Ga crystals are predominantly determined by the change in the contribution from the configuration mode of the shallow state, because the contribution from the configuration mode of the deep state is very small. A photoinduced decrease in the lattice reflection in the CdF₂: Ga crystals due to the change in the dielectric contribution from the impurity mode of the lattice is predicted.     

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.     

Energy barrier between states of a bistable center in photochromic crystals CdF2:Ga and CdF2:In

The establishment of thermal equilibrium between photoinduced (shallow) and ground (deep) states of bistable DX centers in photochromic crystals CdF₂:In and CdF₂:Ga, which are used as real-time holographic media, is studied based on the notions of chemical kinetics. Two mechanisms of mutual transformation of shallow and deep centers—the tunnel mechanism and the mechanism with the participation of free charge carriers—are considered. Equations describing the decay of a photoinduced shallow state are obtained. These equations take into account the distribution of electrons between the photoinduced and ground states and the conduction band. Analysis of the experimental kinetic curves of the decay of photoexcited shallow centers makes it possible to determine the activation energies and barrier height for thermally activated processes of mutual transformation of shallow and deep centers. In CdF₂:In and CdF₂:Ga, this barrier, which determines the decay kinetics of holograms, lies above the bottom of the conduction band by ～10 and ～500 meV, respectively.     

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.     

Electroluminescence in CdF2 crystals

Electroluminescence is observed in CdF₂: Eu and CdF₂: Gd single crystals at liquid nitrogen temperature. The comparison of the emission spectra with those obtained from the same materials under X-ray excitation shows that the electric field stimulates either the intrinsic luminescence amd that due to the doping substance. The dependence of the brightness on the temperature is also reported and compared with the intrinsic luminescence efficiency. The effect is used for measuring the rare earth luminescence decay times.     

Dynamic reflection holograms in CdF2 crystals with bistable centers

The diffraction efficiency and the recording and relaxation times of dynamic reflection holograms, recorded in CdF₂ crystals with bistable centers are studied experimentally in the temperature range 20–100°C. In the model experiments which measured the quality of the wave reflected from the hologram, the dynamic wavefront distortions are demonstrated to be efficiently compensated using a holographic corrector based on these crystals. CdF₂ crystals with bistable centers are likely to be useful in solving problems of correction of laser light wavefront and image correction in observation telescopes with nonideal primary mirrors.     

Thermal conductivity of single crystals with a fluorite structure: Cadmium fluoride

The thermal conductivity of Ca, Sr, Ba, and Cd difluoride single crystals and the CdF₂ samples doped by 3 mol % NdF₃, 15 mol % HoF₃, and 10 mol % ErF₃ has been studied using the method of steady longitudinal heat flow in the temperature range 50–300 K. The thermal conductivity of the matrices of these compounds decreases in the order CaF₂-SrF₂-BaF₂-CdF₂. The temperature dependences of the phonon mean free path for these crystals have been calculated from experimental data and exhibit different behaviors. It has been assumed that the intense phonon scattering observed in the undoped CdF₂ sample is caused by the specific features of the processes of phonon-phonon scattering. The formation of heterovalent solid solutions of cadmium difluoride and rare-earth trifluorides is accompanied by a drastic decrease in the thermal conductivity and a change in its character from that typical of dielectric single crystals to that typical of glassy materials.     

Clusters of group-III ions in activated fluorite-type crystals

The data on optically detected EPR in absorption bands of alkaline-earth fluoride crystals doped with rare-earth (Er, Tm, Yb, Lu) or yttrium activators indicate that these crystals contain clusters similar to Y₆F₃₇, which is the structural unit of the naturally occurring mineral tveitite and of synthetic yttrofluorite [(CaF₂)_1?y(YF₃)_y] crystals, whose lattices exhibit a superstructure at certain values of y. Starting from a rare-earth ion concentration of the order of 0.1%, the greater part of the rare-earth impurity is concentrated in these clusters, having a tendency to aggregate into larger clusters. Clusters are also of considerable importance in semiconducting fluorite-structure crystals of CdF₂ doped with Ga, In, or Y ions, as indicated by microwave and IR radiation absorption in these crystals.     

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.     

Photoemission studies of Cd1−xPbxF2 mixed crystals

Mixed Cd_1−xPb_xF₂ and pure PbF₂, CdF₂ crystals have been investigated using UPS spectroscopy. The CdF₂ valence density of states, due mainly to F _2p electrons, is reconstructed due to the presence of Pb 6s states. The width of the valence band increases from 3.9 eV for CdF₂ to 6.6 in PbF₂. The contributions of cationic s and anionic p electrons have been identified. The experimental results confirm the recent theoretical calculations of electronic states in mixed Cd_1−xPb_xF₂ crystals [1].     

Optical spectra of (CdF2)0.9(InF3)0.1 semiconductor solid solutions

The differences in the optical spectra of CdF₂:In semiconductors with bistable DX centers (concentrated (CdF₂)_0.9(InF₃)_0.1 solid solutions) and “standard” samples with a lower impurity concentration used to record holograms are discussed. In contrast to the standard samples, in which complete decay of two-electron DX states and transfer of electrons to shallow donor levels may occur at low temperatures, long-term irradiation of a (CdF₂)_0.9(InF₃)_0.1 solid solution by UV or visible light leads to decay of no more than 20% deep centers. The experimental data and estimates of the statistical distribution of electrons over energy levels in this crystal give the total electron concentration, neutral donor concentration, and concentration of deep two-electron centers to be ～5 × 10¹⁸ cm^?3, ～9 × 10¹⁷ cm^?3, and more than 1 × 10²⁰ cm^?3, respectively. These estimates show that the majority of impurity ions are located in clusters and can form only deep two-electron states in CdF₂ crystals with a high indium content. In this case, In³⁺ ions in a limited concentration (In³⁺ (～9 × 10¹⁷ cm^?3) are statistically distributed in the “unperturbed” CdF₂ lattice and, as in low-concentrated samples, form DX centers, which possess both shallow hydrogen-like and deep two-electron states.     

Radiation damage and annealing in Sb implanted diamond

The predicted, but as yet unobserved, intradonor absorption spectrum of the hydrogenic-like donors in CdF₂ crystals is presented. The role of phonon coupling in these spectra is discussed. From the data on the insulator-semiconductor transition in CdPbF₂ it is concluded that the dominant factor in convertibility of CdF₂ to a semiconducting state is its electron affinity, the largest among the fluorites (x≈4 eV).     

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.     

Thermostimulated luminescence of CdF2:Eu crystals

Using the method of fractional thermostimulated luminescence (FTSL), the temperature dependence of the mean activation energy of recombination processes in CdF₂:Eu³⁺ crystal was obtained. After thermal annealing of the crystal, thermostimulated luminescence peaks were identified. Anomalously low frequency factor (s=10⁷ s ^–1) of the recombination processes can be explained by the dependence of the resonance energy transfer probability on intercentre distance.The authors are very grateful to Dr. E. Kotomin for valuable comments and Dr. C. Paracchini for supply of CdF₂:Eu crystals.     

Fabrication of surface relief gratings on transparent dielectric materials by two-beam holographic method using infrared femtosecond laser pulses

Fabrication of surface relief-type gratings in transparent dielectrics, which are hard to machine, has been achieved by a holographic technique using two infrared femtosecond (fs) pulses from a mode-locked Ti:sapphire laser. The present method can be applied for a variety of transparent dielectrics, Al₂O₃ (sapphire), TiO₂, ZrO₂, LiNbO₃, SiC, ZnO, CdF₂, MgO, CaF₂ crystals, and SiO₂ glass. It is found that the grating formation is due primarily to laser ablation processes. Planar surface relief gratings can be fabricated by colliding two fs laser pulses on the surface of substrates which move at a constant speed, synchronized with the laser repetition rate. Received: 1 March 2000 / Published online: 7 June 2000     

Paramagnetic susceptibility of additively colored CdF2:In photochromic crystals

The paramagnetic susceptibility K _para of CdF₂:In crystals with metastable indium centers has been measured in darkness after photobleaching the crystals in visible light in the temperature interval 4–300 K. For crystals cooled in darkness to liquid-helium temperature K _para is wholly determined by the accompanying impurity Mn²⁺ with magnetic moment J=5/2. Illumination of the crystals leads to the appearance of an induced signal δ K _para due to the formation of centers with J=1/2. The results of the experiments indicate the absence of paramagnetism in the deep state of the indium center and its existence in the shallow (donor) state, i.e., they confirm the two-electron (negative-U) nature of the deep indium level in CdF₂. Fiz. Tverd. Tela (St. Petersburg) 39, 1205–1209 (July 1997)     

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.     

Characterization of Cu(In,Ga)Se2 thin films prepared by evaporationfrom ternary compounds

Thin films of Cu(In,Ga)Se₂ were fabricated by evaporation from ternary CuGaSe₂ and CuInSe₂ compounds for photovoltaic device applications and their properties were investigated. From XRF analysis, the Cu:(In+Ga):Se atomic ratio in all thin films was approximately 1:1:2. The Ga/(In+Ga) atomic ratio in the thin films changed linearly from 0 to 1.0 with increasing the [CGS]/([CGS]+[CIS]) mole ratio in the evaporating materials. However, for thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio above 0.4, the composition by EPMA analysis was not consistent with that by XRF analysis. The result of EPMA analysis showed that the surface of a thin film was Cu-rich. XRD studies demonstrated that the thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio under 0.2 had a chalcopyrite Cu(In,Ga)Se₂ structure and the preferred orientation to the 112 plane. On the other hand, XRD patterns of the thin films produced at the [CGS]/([CGS]+[CIS]) mole ratio above 0.6 showed the diffraction lines from a chalcopyrite Cu(In,Ga)Se₂ and a foreign phase. The separation of a peak was observed near 2θ=27°, indicative the graded Ga concentration in Cu(In,Ga)Se₂ thin film.     

X-ray determination of thermal expansion of cadmium fluoride and lead fluoride

The lattice parameters of CdF₂ andβ-PbF₂ have been determined over the temperature range 300–670 K. The coefficient of expansion at room temperature is 21·3 × 10⁻⁶ K⁻¹ and 25·4 × 10⁻⁶ K⁻¹ for CdF₂ and PbF₂ respectively and it increases linearly with temperature over the range of temperature covered. The Grüneisen parameter decreases with temperature in both the crystals.