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.     

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.     

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.     

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.     

Electronic level diagram and structure of metastable centers in CdF2:Ga and CdF2:In semiconducting crystals

A study is reported of the optical properties of wide-gap, predominantly ionic cadmium fluoride crystals in photo-and thermally stimulated transformations of metastable indium and gallium centers. An analysis of these properties leads one to a conclusion of gallium having two metastable states (two types of deep centers). The deep-center binding energies and the barriers separating the shallow (hydrogenic) and deep centers have been determined for both impurities. Configuration-coordinate diagrams are developed, and microscopic models for the deep centers are proposed. It is concluded that these centers are identical with the metastable DX centers in typical semiconducting crystals. Thus cadmium fluoride is the most ionic among the crystals where DX centers have thus far been found. The potential of using such crystals for optical information recording is discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 2130–2136 (December 1997)     

Thermo-and photostimulated depolarization in self-compensated CdF2:Ga and CdF2:In crystals

A study is reported of the conductivity of CdF₂ semiconductor crystals doped by indium and gallium donor impurities and residing in a semi-isolated state. The latter results from self-compensation of the impurities, in the course of which one half of them creates two-electron DX centers, and the second is ionized. Photo-and thermostimulated depolarization of these crystals has been studied. It was shown that the observed polarization/depolarization phenomena have a nonlocal nature and are due to the charges present in these crystals changing their positions. These changes may be formally considered as charge displacement to macroscopic distances considerably in excess of the interatomic ones. The mechanisms responsible for these phenomena are discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 1575–1581 (September 1999)     

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.     

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)     

Scanning of a laser beam and purification of materials through the use of light-induced particle drift in semiconductors

The light-induced drift of electrons, light-absorbing impurities, and defects in II-VI semiconductors is investigated experimentally, along with some potential practical applications of the phenomenon. It is shown that the light-induced drift of electrons induces a very pronounced change in the refractive index, |Δn|∼0.01, and can be used to implement effective scanning of nanosecond and picosecond laser pulses through frustration of total internal reflection. The light-induced drift of absorbing particles increases their density in the surface layer of the crystals, and this effect can be exploited in semiconductor technology. Zh. Tekh. Fiz. 68, 121–124 (April 1998)     

Experimental observation of “configuration” modes of bistable centers in CdF2:In crystals

New “configuration” modes, which were predicted by us for CdF₂:In crystals, have been revealed at the frequencies ν₁ ≈ 32.4 cm^?1 and ν₂ ≈ 96.3 cm^?1 for deep and shallow impurity states, respectively. The frequencies of these oscillations exactly correspond to the potential-energy curves calculated by us for shallow and deep states of In with regard to the reduced mass M = 2m ₁ m ₂/(m ₁ + 2m ₂) of the In ion (m ₁) and two F ions (2m ₂) per primitive fluorite cell. This correspondence confirms the correct choice of the height of the potential barrier between the impurity states of In in CdF₂ (0.02 eV), which was used in the calculations. The dielectric contributions of the noted modes were determined, which made it possible to calculate the concentrations of In impurity ions in the deep (N ₁) and shallow (N ₂) states. The obtained ratio N ₂/N ₁ ≈ 2 directly indicates that photoionization of deep In centers leads to the formation of a doubled number of shallow centers and that two electrons are localized in the deep state of the In ion; such behavior is characteristic of DX centers. A photoinduced increase in the real (ε′) and imaginary (ε″) parts of the dielectric constant has been found (at a frequency of 25 cm^?1, Δε′ ≈ 0.2 and Δε″ ≈ 0.06). These changes correspond to the changes in the dielectric contributions of the configuration modes under illumination. A photoinduced decrease in the lattice reflection of CdF₂:In, related to the impurity lattice modes, has also been revealed.     

Possibility of investigation the metastable donor states in ii-vi semiconductors under hydrostatic pressure

Abstract

The model of bistable donor centers was proposed for describing the metastable electron traps in cubic semiconductors. The detailed analysis of the model suggests that the bistable donors should be very common in II-VI semiconductors doped with VII group impurities. Under normal conditions the additional metastable states are degenerated with the conduction band. However, the analysis of the energy bands pressure coefficients for II-VI materials shows that under hydrostatic pressure the donor traps can change the electrical properties of the sample.     

The effects of core structure on radiative and non-radiative recombinations at metal ion substituents in semiconductors and phosphors

Carrier binding and recombination processes at transition metal (TM) and post-transition metal impurities in solids are reviewed. The presence of low-lying empty core orbitals in these impurities introduces novel binding and recombination phenomena and leads naturally to a classification of impurity centres as ‘simple’ or ‘structured’. ‘Simple’ impurities, generally the main group elements, introduce only effective-mass-like states into the forbidden gap of the host lattice, whereas ‘structured’ impurities show localized atomic-like transitions below the lattice absorption edge. The fact that donor or acceptor centres generated by TM ions in semiconductors are usually deep is discussed with reference to a simple oxidationstate correlation diagram based on the variable chemical valency characteristic of these ions. Many metal ion impurities in solids generate iso-electronic centres however, and evidence is assembled to show how the normally accepted range of iso-electronic centres can be extended to include such impurities. It is emphasized that the formation of bound states at these ‘structured’ cationic iso-electronic centres is fairly common, in contrast to the situation normally found for anionic substituents in semiconductors. A possible explanation for this general property of structured iso-electronic centres is given in terms of the low-lying core levels which they may introduce in the band gap and their enhanced polarizability. Simple arguments then suggest that those centres showing electron ionization thresholds or atomic inter-configurational transitions just below E _g should be hole-attractive, whereas those showing charge transfer transitions should be electron-attractive. It is shown that two kinds of defect Auger recombination (DAR) may be significant for excitons localized at structured impurities. The first involves hole ionization at a deep neutral acceptor, and the conditions which must be met to make this process significant at room temperature are reviewed. The second DAR process involves the transfer of carrier recombination energy to the core electrons of the structured impurity. A simple model developed for this energy transfer process predicts that the coupling between exciton and core states will be larger if the impurity shows strong, broad dipole-allowed transitions quasi-resonant with the lattice absorption edge. Throughout the paper we stress the importance of recombination processes at structured impurities to the problems of phosphor activation and of shunt recombination mechanisms in semiconductor LEDs. In the final sections this general framework of ideas is used to explain the relative cathodoluminescence efficiencies of different rare-earth activators in crystals of Y₃Al₅O₁₂, with good agreement between the theoretical predictions and the experimental observations. Possible evidence for the occurrence of bound exciton states at structured TM impurities is found in the appearance of anomalously weak zero-phonon lines in the near-edge luminescence of GaP crystals prepared under special conditions.     

Electronic and magnetic properties of SiC nanoribbons by F termination

By using the first-principles calculations, the electronic properties are studied for the F-terminated SiC nanoribbons (SiCNRs) with either zigzag edges (ZSiCNRs) or armchair edges (ASiCNRs). The results show that the broader F-terminated ZSiCNRs are metallic and the edge states appear at the Fermi level, while the F-terminated ASiCNRs are always semiconductors independent of their width but the edge states do not appear due to the Si-C dimer bonds at the edges. The charge density contours analyses shows that the Si-F and Si-C bonds are all ionic bonds due to the much stronger electronegativities of the F and C atoms than that of the Si atom. However, the C-F bonds display a typical non-polar covalent bonding feature because of the electronegativity difference between the F and C atoms of 1.5 is a much smaller than that of between the F and Si atoms of 2.2, as well as the tighter bounded C 2s ²2p ² electrons with smaller orbital radius than the Si 3s ²3p ² electrons. For both the F- and the H-terminated ZSiCNRs, the ground state is a ferromagnetic semiconductor.     

Mechanical and chemical bonding properties of ground state BeH<Subscript>2</Subscript>

The crystal structure, mechanical properties and electronic structure of ground state BeH₂ are calculated employing the first-principles methods based on the density functional theory. Our calculated structural parameters at equilibrium volume are well consistent with experimental results. Elastic constants, which well obey the mechanical stability criteria, are firstly theoretically acquired. The bulk modulus B, Shear modulus G, Young's modulus E, and Poisson's ratio υ are deduced from the elastic constants. The bonding nature in BeH₂ is fully interpreted by combining characteristics in band structure, density of states, and charge distribution. The ionicity in the Be-H bond is mainly featured by charge transfer from Be 2s to H 1s atomic orbitals while its covalency is dominated by the hybridization of H 1s and Be 2p states. The Bader analysis of BeH₂ and MgH₂ are performed to describe the ionic/covalent character quantitatively and we find that about 1.61 (1.6) electrons transfer from each Be (Mg) atom to H atoms.     

Role of order and disorder in covalent semiconductors and ionic oxides used to produce thin film transistors

This paper aims to discuss the effect of order and disorder on the electrical performances of covalent silicon semiconductors and ZnO based ionic oxide semiconductors used as active channel layers in thin film transistors. The effect of disorder on covalent semiconductors directly affects their electrical transport properties due to the asymmetric behaviour of sp states, while in ionic oxide semiconductors it is found that this effect is small due to the fact that angular disorder has no effect on the spherical symmetry of s states. To this we must add that the mobility of carriers in both systems is quite different, being also affected by electron–phonon interactions (weak in silicon and strong in ionic oxides leading to formation of polarons). Besides, the impurity doping effect and the presence of vacancies in disordered silicon and in ionic oxides behave differently, which will influence the thin film properties and so, the performances of the devices produced. PACS 81.05.Gc; 81.05.Hd; 85.30.Tv     

Investigating material trends and lattice relaxation effects for understanding electron transfer phenomena in rare-earth-doped optical materials

Rare-earth-doped insulators and semiconductors play an important role in a wide range of modern optical technologies. Knowledge of the relative energies of rare-earth ions’ localized electronic states and the band states of the host crystal is important for understanding the properties of these materials and for determining the potential material performance in specific applications such as lasers, phosphors, and optical signal processing. Current understanding of the systematic variations of electron binding energies in these materials is reviewed with analysis of how lattice relaxation affects the results obtained from different experimental techniques. Detailed examples are presented for rare-earth-doped YAG and LaF₃ material systems. A method for predicting the chemical shift of the 4f electrons of rare-earth impurities from the host crystal’s photoemission spectrum is also demonstrated. Furthermore, a simple model is presented that predicts host-dependent trends in the binding energies of the rare-earth ion states in materials ranging from the elemental metals to the ionic fluorides. By understanding the systematic changes in the relative energies for different states, different ions, and different host materials, insight is gained into electron transfer transitions, valence stability, and luminescence quenching that can accelerate the development of materials for optical applications.     

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.     

Hydrogen in semiconductors: The roles of μSR and theory

Hydrogen is an unavoidable impurity in all semiconductors. It interacts with intrinsic defects (from monovacancies to dislocations), with impurities (shallow dopants, deep centers, even electrically inactive impurities), with the crystal, and with otherH interstitials. These interactions profoundly affect the electrical and optical properties of the host. Conventional experimental techniques used to study the properties of hydrogen (EPR, IR or Raman spectroscopy, etc.) have provided information on a number ofH-related defects. Theory has played a major role in these studies, not only by confirming the models proposed on the basis of experimental data, but often by explaining the data altogether or predicting new features. So far,SR has provided fundamental information on isolated hydrogen-like species in many semiconductors. It would be wonderful if thespectroscopic signature of muonium-impurity pairs could be identified or ifquantitative information regarding the stability of the various charge states of muonium could be obtained.