Paramagnetic defects in BaTiO3 and their role in light-induced charge transport — Optical studies

On the basis of a previous identification of paramagnetic defects in nominally undoped as grown BaTiO₃ single crystals, we have investigated the changes of the concentrations of these centers and their optical absorptions under illumination with light of varying wavelengths. The most pronounced charge transfers occur by hole ionization of Fe⁴⁺ and — to a lesser extent — of Cr⁵⁺ and Cr⁴⁺. At low temperatures the created holes are trapped in the form of O^–-ions next to Al³⁺ or unknown acceptor defects. Corresponding Fe⁴⁺ and O^– absorptions have been identified.     

Studies of EPR g factors of the isoelectronic 3d series Cr, Mn and Fe in SrTiO3 crystals

The g-shifts Δg(=g−g_s, where g_s≈2.0023 is the free-ion value) of the isoelectronic 3d³ series Cr³⁺, Mn⁴⁺ and Fe⁵⁺ in SrTiO₃ crystals are calculated from the high-order perturbation formula based on the cluster approach for 3d³ ion in cubic octahedral site. The formula includes not only the contribution from the crystal-field (CF) mechanism, but also that from the charge-transfer (CT) mechanism (which is omitted in the CF theory). From the calculations, it is found that the contribution Δg_CT from the CT mechanism in sign is contrary to the corresponding Δg_CF from the CF mechanism and the relative importance of CT mechanism (characterized by |Δg_CT/Δg_CF|) increases with the increasing valence state (and hence the atomic number) of 3d³ ion. The positive g-shift Δg of SrTiO₃:Fe⁵⁺ is due mainly to the contribution of CT mechanism. So, for the explanations of g factors of the high valence state 3dⁿ ions (e.g. Mn⁴⁺ and Fe⁵⁺) in crystals, the contributions from both CF and CT mechanisms should be taken into account.     

Triplet bound excitons in copper-doped gallium phosphide

This review describes a particular class of neutral defect complexes in GaP, represented by the variety of Cu-related centres, which are observed to bind excitons in a spin-like singlet-triplet configuration. The reasons for this are discussed and two subgroups are defined. One of these consists of centres which bind holes in localized orbitally nondegenerate spin states, but give rise to highly structured optical spectra. The other group is characterized by featureless photoluminescence spectra in the mid-gap spectral region due to a tight binding of both the electron and hole in spin-like states. Both groups are well described with an essentially identical spin-Hamiltonian formalism, as detailed optically detected magnetic resonance measurements have revealed. The relation of this class of neutral defects in GaP to similar complexes in other semiconductors is discussed.     

Light-induced charge transport processes in photorefractive barium titanate doped with rhodium and iron

Absorption, light-induced absorption changes, photo and dark conductivities, bulk photovoltaic currents and two-beam coupling gain coefficients are measured for oxidized, as grown and reduced BaTiO₃:Rh,Fe crystals. Theoxidized sample shows hole conductivity and three photorefractive levels are present: Rh^4+/5+ Fe^4+/5+ and Rh^3+/4+. The measurements indicate that Rh^3+/4+ is responsible for the photo conductivity and that its energy level is located (0.9 ± 0.1) eV above the valence band edge. Theas grown sample also shows hole conductivity and two photorefractive levels are involved: Rh^3+/4+ and Fe 3+/4+. The results yield that the Fe^3+/4+ level is located (0.95 ± 0.05) eV above the valence band edge. In thereduced sample electrons are the dominant charge carriers and two levels are of importance. The shallow one is located (0.39 ± 0.05) eV below the conduction band edge. Here the performance of this crystal is strongly impaired by a pronounced sublinear photo conductivity.Dedicated to O. F. Schirmer on the occasion of his 60th birthday     

Theoretical explanation of the g factor for Cr in Y2SiO5 crystal

The g factor of Cr⁴⁺ in Y₂SiO₅ crystal is calculated from a completed high-order perturbation formula, in which not only the conventional contribution to the g-shift Δg(=g−g_e) from the crystal-field mechanism, but also the contribution from the charge-transfer mechanism (which is neglected in the crystal-field theory) are considered. The calculated result shows good agreement with the observed value. It is found that the calculated Δg due to the charge-transfer mechanism is opposite in sign and about 38% in magnitude, compared with that due to the crystal-field mechanism. So, in the studies of the g factor for a 3dⁿ ion having high valence state in crystals, the contribution due to the charge-transfer mechanism should be taken into account.     

Spin Hamiltonian parameters and structural disorder analysis for Cr ion in YGG crystals

A new crystalline lattice distortion model has been proposed, on the basis of it, the relations between spin Hamiltonian parameters and crystal micro structure have been established. By taking into account slight magnetic interactions, including spin-spin (SS), spin-other-orbit (SOO), and orbit-orbit (OO) interactions, the local structure of Cr³⁺ ion in YGG crystal has been studied using complete diagonalization method (CDM). The studies show that the local structure in the YGG:Cr³⁺ crystal is of the compressed trigonal distortion. The ligand oxygen plane moved 0.0138 nm toward Cr³⁺ ion along C₃-axis. Accordingly, the SH parameters in YGG:Cr³⁺ crystal are explained successfully.     

Fermi-level engineering of BaTiO3 by alkali codoping: increasing the near-infrared absorption by rhodium

Using electron paramagnetic resonance, optical absorption, and fast spectroscopy of light-induced absorption changes, it is shown that codoping BaTiO₃:Rh with Na_Ba acceptors raises the charge state of Rh³⁺ to Rh⁴⁺. Subsequent oxidation under high oxygen pressures can lower the Fermi level to Rh^4+/5+, leading to increased infrared absorption. The light-induced charge transfer in such specimens is characterised by “one center” behaviour. Received: 18 November 1998 / Revised version: 23 December 1998 / Published online: 7 April 1999     

Population inversion between the H4 and the F4 excited states of Tm investigated by means of numerical solutions of the rate equations system in Tm-doped and Tm, Ho-codoped fluoride glasses

Population inversion between the ³H₄ and the ³F₄ excited states of Tm³⁺ ions responsible for the 1.5 μm emission in Tm³⁺ singly doped (0.5%) and Tm³⁺, Ho³⁺-codoped fluoride (ZBLAN) glasses and its dependence on the Ho³⁺ concentration (x=0.2-1%) was investigated by means of numerical solution of the rate equations system for continuous pumping at 797 nm. Mean lifetimes of donor and acceptor states were evaluated by using the integration method applied to the best fitting of fluorescence curves previously reported. Lifetime values were used to obtain the rate constants of all non-radiative energy-transfer processes involved and a complete set of rate equations better describing the observations was given. The rate equations were solved by numerical method and the population inversion between the ³H₄ and the ³F₄ excited states of Tm³⁺ was calculated to examine the beneficial effects on the gain associated with Ho³⁺ codoping. The results have shown that Tm³⁺ population inversion is reached only for high Ho³⁺-codoping (?0.3 mol%). Highest population inversion (∼1.6×10¹⁸ Tm³⁺ ions cm⁻³) was obtained in Tm(0.5%), Ho(1%)-codoped (ZBLAN) pumped by 2.8 kW cm⁻². This population inversion density is ∼6.4 times higher than that one observed in Tm:Tb:GLKZ, Tm:Tb:Ge-Ga-As-S-CsBr and Tm:Ho:Ge-Ga-As-S-CsBr for a similar pumping condition (∼2.5×10¹⁷ cm⁻³). In addition, Tm(0.5%):Ho(1%):ZBLAN presents the highest population inversion that linearly increases with the pumping intensity; this behavior does not show saturation effect at least for the maximum intensity of 12 kW cm⁻² employed. The use of 1 mol% of Ho³⁺-codoping maximizes the potential gain of Tm³⁺-doped (0.5%) ZBLAN to produce stimulated emission near 1.5 μm, making this material suitable for using it as fiber optical amplifier and/or fiber laser operating in 1.4-1.5 μm region of the spectrum.     

Photochromic behaviour of doped Bi4Ge3O12 single crystal scintillators

The changes induced by ultraviolet (UV) illumination on the optical absorption and electron paramagnetic resonance (EPR) spectra of Bi₄Ge₃O₁₂ single crystals, doped either with Fe (and Gd) or Mn, have been followed at room temperature (RT). In both crystals several overlapping optical absorption bands develop under UV illumination, covering from 0.7 eV up to the band edge of the matrix. The optical damage can be bleached by heating the samples above RT or by illumination with visible light. Although these optical changes temporarily correlate with the variation of the Gd³⁺ and Mn²⁺ concentrations, it has been concluded that other defects are present and partially responsible for the optical damage.     

Theoretical studies of the optical and EPR spectra for V in Y2O3 crystal

In this paper, we give an alternative suggestion that both the observed optical and electron paramagnetic resonance (EPR) spectra of Yttrium oxide (Y₂O₃):V³⁺ are attributed to V³⁺ ions at the S₆ site of Y₂O₃. This suggestion is different from the opinion in the previous paper that the optical and EPR spectra are attributed to V³⁺ ions at the C₂ and S₆ sites, respectively. From the suggestion, the optical band positions and spin-Hamiltonian parameters are calculated by diagonalizing the complete energy matrix for 3d² ions in trigonal symmetry. The results are in good agreement with the experimental values, suggesting that both the observed optical and EPR spectra in Y₂O₃:V³⁺ may be due to V³⁺ at S₆ site of Y₂O₃ crystal.     

ESR spectra of Eu centers in defect Ga2S3 single crystals

In this paper, the author presents the results of measurements of the low-temperature and angular dependences of the ESR spectra of Eu²⁺ centers in defect Ga₂S₃ single crystals in the temperature range 8–29 K and for 0–180° orientations of the static magnetic field. The electron structure of impurity ¹⁵¹Eu atoms in Ga₂S₃:Eu single crystals has been studied by using the ESR method at different doping proportions of Eu atoms. Ga₂S₃ single crystals were grown from the melt using the Bridgman method. The Eu concentration was determined by atomic absorption analysis and X–ray fluorescence analysis (XRFA). By investigation on the ESR spectra, the author has first determined the values of charge states for Eu, which have turned out to be a Eu²⁺(4f⁷) ion with spin S=7/2, g=4.18±0.02 and concentration of the states of Eu N=6.3×10¹⁴ cm⁻³.     

Light-induced charge transfer and kinetics of the NIR absorption of Nb4+ polarons in SBN crystals at low temperatures

Sr_1-xBa_xNb₂O₆ (SBN) crystals with open tungsten-bronze structure show enhanced photorefractive properties with doping of impurities such as Ce, Cr, Rh etc. Under illumination with Kr⁺ laser (647 nm) or Ar⁺ laser light (488 nm or 514 nm) or UV light at low temperature, pure and doped SBN crystals show a broad polaron absorption band around 0.7 eV (6000 cm^-1). The first step of a theoretical model involves the excitation of electrons by illumination from Cr³⁺/Ce³⁺ to higher excited states or the conduction band. The excited electrons can then be trapped by Nb⁵⁺ to form Nb⁴⁺ polarons and further on can directly tunnel through or hop over the potential barrier (with a value Δ≈0.15±0.02 eV) to recombine with Cr⁴⁺/Ce⁴⁺ ions. The experimental intensity dependence, temperature dependence, and decay process of the light-induced Nb⁴⁺ polarons can be fitted with the help of this model. Small, but systematic, differences lead to the additional assumption of different recombination rates of polarons at distinct distances from the Cr⁴⁺/Ce⁴⁺ recombination centers and therefore many parallel decay channels are active where each decay channel obeys a monoexponential decay law. A stretched exponential decay function is employed to fit in this case the decay process of the Nb⁴⁺ polarons at different temperatures and under illumination with different intensities. Due to the high dielectric constant value (ε₃₃ and ε₁₁ have values in the 10²-10³ range) at low temperature, the long range Coulomb attraction (to Ce³⁺ _Sr/Ba) or repulsion (from Cr³⁺ _Nb) of the electronic polaron is suppressed. The leading role in the attraction and the following trapping of the electronic Jahn–Teller polaron, both on Cr³⁺ _Nb and Ce³⁺ _Sr/Ba centers, is played by the indirect dipole–dipole interaction via the soft TO-mode. Received: 27 November 1998 / Revised version: 22 January 1999 / Published online: 7 April 1999     

Light-induced absorption change in Fe-doped GaN

The properties of a light-induced absorption (LIA) change were investigated in a semi-insulating Fe-doped GaN crystal. The temporal profile and a spectrum of the LIA were measured in the temperature range from 15 K to 300 K. The LIA was almost proportional to the light intensity and showed slight saturation behavior. The relaxation time constant, in the range of milliseconds, was equal to the lifetime of infrared photoluminescence related to the Fe³⁺ internal transition Fe³⁺(⁴T₁)→Fe³⁺(⁶A₁). The LIA was attributed to an excited-state absorption from Fe³⁺(⁴T₁). Some of the peak energies observed in the LIA spectrum showed good agreement with transition energies expected from an energy diagram of Fe-doped GaN crystal.     

Luminescence study of the 4f5d configuration of Nd in LiYF4, LiLuF4 and BaY2F8 crystals

Ultraviolet fluorescence of Nd³⁺ ions induced by triphotonic excitation process was studied in Nd-doped LiYF₄, LiLuF₄ and BaY₂F₈ crystals using a technique of time-resolved spectroscopy. The observed ultraviolet luminescence was due to transitions between the bottom of 4f²5d configuration and 4f³ states of Nd³⁺ ions. Narrow emission lines superposed to the broadband emissions were observed. A detailed analysis of luminescence spectrum revealed that the narrow emissions are due to parity and spin allowed radiative transitions from the Stark levels of ⁴K_11/2(5d) state created by the electrostatic interaction between the 5d electron and the two electrons of the 4f² configuration. The narrow emissions are related to the high spin state (S=3/2) which gives f-f characteristics to the f-d broadband emissions. The narrow emissions superposed to the wide emission correspond to 18%, 34% and 43% of the integrated broadband emission at 262 nm observed in LiYF₄, LiLuF₄ and BaY₂F₈ crystals, respectively. Although the 5d-4f² interaction is observed to be weaker than 5d-crystal field interaction, it is stronger enough to select only the radiative transitions from 4f²5d configuration to 4f³ states that preserves the total spin S=3/2.     

Iron-aluminum pairs in silicon

Iron-aluminum pairs in silicon are investigated with conventional and optically detected electron paramagnetic resonance (EPR). For the trigonal and orthorhombic pairs known from previous EPR measurements we found for the first time optical absorption bands by measuring their magnetic circular dichroism of the absorption (MCDA). Direct experimental evidence is presented for the configurational bistability of both pairs by showing that the MCDA of the trigonal configuration can be transformed into that of the orthorhombic configuration by the combined effect of light and temperature. A new trigonal pair was discovered by conventional EPR having the same EPR intensity as the known one. Total energy calculations of various (Fe_i-Al_s) pair configurations show that two trigonal (Fe_i-Al_s)⁰ pairs with different Fe_i-Al_s separations have almost the same binding energy and should occur with the same probability. Fe _i ⁺ is always on a tetrahedral interstitial site, while Al _s ^– is nearest neighbor along 111 in one pair, second nearest neighbor in the other one with one silicon lattice site in between.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

Tunneling recombination luminescence under excitation of PbWO4:Mo crystals in the defect-related absorption region

Time-resolved emission and excitation spectra and luminescence decay kinetics were studied at 150-300 K for the green emission of PbWO₄:Mo crystals. It was found that the slow (μs-ms) decay component observed under excitation in the defect-related absorption region (around 3.8-3.9 eV) arises from the G(II) emission which appears at the tunneling recombination of optically created electron and hole centers. The study of the emission decay kinetics at different temperatures and excitation intensities allowed concluding that both the monomolecular and the bimolecular tunneling recombination process can be stimulated in the mentioned energy range. The monomolecular process takes place in the isolated spatially correlated pairs of electron and hole centers produced without release of electrons into the conduction band. The bimolecular process takes place in the pairs of randomly distributed centers created at the trapping of free electrons from the conduction band. The formation of electron centers under irradiation in the defect-related absorption region was investigated by the electron spin resonance (ESR) and thermally stimulated luminescence (TSL) methods. The possibility of various photo-thermally stimulated defects creation processes, which take place with and without release of free electrons into the conduction band, was confirmed.     

Photothermal detection of surface states in amorphous silicon films

A new method for the determination of surface states in amorphous silicon films is proposed. The method is based on the observation of enhancement of the interference fringe amplitude in photothermal deflection spectra, due to the presence of surface states.A theoretical approach is presented, together with the experimental results and an evaluation of the density of surface states. The method proves to be adequate, in most cases, to yield results in good agreement with those reported in literature.     

Vibrational modes and infrared absorption of interstitial oxygen in silicon

A quasi-linear Si₂O molecule model (QLMM) is suggested from an analysis of the configuration and the interactions of an isolated oxygen atom with its neighbor silicon atoms. The vibrational modes are assigned and the infrared absorption spectra are calculated in detail with the model. The theoretical results are in reasonably good agreement with reported experimental values. This agreement shows that for the analysis of the vibrational modes of the interstitial oxygen atom in silicon crystals it is not necessary to consider the coupling of the molecule with the rest of the lattice. The interaction of the oxygen atom with its six second-nearest silicon atoms only causes the level separation of the ₂ mode and the formation of the fine structure.     

Twinned EPR spectra of Fe centers in ternary layered TlGaS2 crystal

TlGaS₂ single crystal doped by paramagnetic Fe³⁺ ions has been studied by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra reveal a nearly orthorhombic symmetry of the crystal field (CF) on the Fe³⁺ ions. Two groups each consisting of four equivalent Fe³⁺ centers were observed in the EPR spectra. The local symmetry of the crystal field on the Fe³⁺ centers and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of the GaS₄ tetrahedrons. The rhombic distortion of the sulfur ligand CF is attributed to the effect of Tl ions located in the trigonal cavities between the tetrahedral complexes. The observed twinning of the resonance lines indicates a presence of two non-equivalent positions of Tl ions that confirms their zigzag alignment in the TlGaS₂ crystal structure.