Fe deep level optical spectroscopy in InP

The optical cross-section σ_n⁰(hv) and σ_p⁰(hv) associated with the (Fe³⁺ ? Fe²⁺) deep level have been measured by Deep Level Optical Spectroscopy in n-type Fe doped samples of InP. Optical transitions are interpreted as transitions from the Fe²⁺ ground state to the Γ and L point minima of the conduction band for σ_n⁰(hv) and from the valence band to the ground and excited state for Fe²⁺ for σ_p(hv). A theoretical model which accounts for the main features of the experimental data is proposed.     

The determination of hopping rates and carrier concentrations in ionic conductors by a new analysis of ac conductivity

The a.c. conductivity σ(ω) of ionic materials takes the form, σ(ω) = σ(0) + Aωⁿ. The carrier hopping rate, ω_p, is obtained from the new expression σ(0) = A ω_pⁿ and the carrier concentration is estimated from σ(0). The contribution of creation and migration terms to the activation energy for conduction may be determined from the thermal activation of σ(0) and ω_p and the corresponding entropy terms quantified. Data have been analyzed for four widely different ionic materials: single crystal Na β-alumina, polycrystalline Li₄SiO₄, Ag₇l₄AsO₄ glass and Ca(NO₃)₂/KNO₃ glass and melt. For each, the carrier concentration and hopping rates have been obtained.     

An XPS and UPS investigation of the adsorption of ethylene on the (111) surface of silver

Monolayer adsorption of pure ethylene on the (111) surface of saver at 80 K has been studied by X-ray (hv = 1486.6 eV) and ultraviolet (hv = 21.2 and 40.8 eV) photoelectron spectroscopy. The density of the adlayer is approximately 5 × 10¹⁴ molecules/cm² at saturation, multilayer formation being prohibited by the ultrahigh vacuum of the spectrometer. The molecular orbitals designated σ¹_CH, σ_CC, σ_CH and 2ss¹ by Demuth are observed at 7.0, 9.0, 10.3 and 13.6 eV below the Fermi level, respectively, but the higher lying π level is obscured by the silver d-band emission. The data are consistent with an undistorted molecule, adsorbed with the molecular axis parallel to the surface. Desorption occurs below 200 K without significant decomposition products remaining on the surface in agreement with the conventional notion that clean silver is relatively inert with respect to olefin adsorption.     

Optical properties of amorphous CuInSe2

Optical absorption spectra of polycrystalline and amorphous CuInSe₂ thin films were measured at room temperature in the photon energy range from 0.8 to 2.1 eV. In amorphous CuInSe₂ the absorption coefficient follows the relation α(hv) = A(hv?E₀)/hv characteristic of optical transitions between extended states in both the valence and conduction band. The optical gap of E₀ = 1.38 ± 0.01 eV is larger than the fundamental gap energy of E_g = 1.01 ± 0.01 eV in crystalline CuInSe₂. A comparison of the results for CuInSe₂ with those for ZnSe is given.     

The valence and conduction band structure in Cd1−xMnxF2 crystal by means of UPS

The density of states distribution in the valence and conduction band was determined for Cd_1?xMn_xF₂ crystals (x = 0; 0.02 and 0.1) on the basis of the EDCs obtained for hv = 21.2 eV and hv = 40.8 eV. The smooth changes of the shape of EDCs were obtained for different alloy compositions for hv = 40.8 eV while for the hv = 21.2 eV EDCs drastic changes occur due to the structure of the final density of states. The peaks of density of states obtained for CdF₂ valence band in X₅^′, L_2,1 and X₅, points and conduction band in X₁ and L₁ points of the B.Z. changes with the increase of x in Cd_1?xMn_xF₂ alloy.     

Observation of the internal luminescence of Cr2+(3d4) in GaAs under hydrostatic pressure

Observation of the internal luminescence of Cr²⁺(3d⁴) in GaAs under hydrostatic pressure is reported. The activation of this luminescence is correlated to the lifting of the degeneracy between the excited level of Cr²⁺ and the conduction band of the host material. The possible mechanisms giving rise to this luminescence are discussed.     

Structure relations in the x-ray photoelectron spectra of three chromium compounds

The chemical shift in electron binding energy, magnetic splitting of electron shells, and structures in the valence band are examined for chromium in the 3 + and 6 + oxidation states.The splitting of the Cr 3s energy level is associated with the appearance of a sharp Cr 3d line in the valence band. The relative chemical shift in the Cr 2p_{$\text{3}\text{2}$} line between Cr₂O₃ and K₂Cr₂O₇ is verified in the mixed compound KCr₃O₈ which contains both types of Cr ions, and the structure of this compound is verified by the X-ray photoelectron spectra. The spin-orbit intensity ratio of the 2p doublet of Cr⁶⁺ is 3, instead of the theoretical value of 2, and the spin-orbit splitting is less than for Cr³⁺. In the 3p level of Cr the relative chemical shift is 3.5 eV whereas for the 2p_{$\text{3}\text{2}$} level the shift is only 2.4 eV. The differences in chemical shift and intensity ratio can not be explained.     

Photoluminescence studies of γ-irradiated CaF2:Dy:Pb:Na single crystals

The optical absorption (OA) and photoluminescence (hereafter referred to as luminescence) studies were made on CaF₂:Dy:Pb:Na single crystals (Dy—0.005 at%, Pb—0.188 at% and Na—0.007 at%) before and after γ-irradiation. The unirradiated crystal exhibited a strong OA band around 6.36 eV attributed to the ‘A’ band absorption of Pb²⁺ ions. The γ-irradiated crystal exhibited OA bands around 2.06, 3.28, 3.75 (broad shoulder) and 2.48 eV. The first three bands could be tentatively attributed to M_Na centre when compared with that of the coloured CaF₂:Na. The origin of 2.48 eV band was not explicitly known. Luminescence emission and excitation of Pb²⁺ and Dy³⁺ ions were negligible in the unirradiated crystal. Irradiated crystal exhibited a strong excitation spectrum with overlapping bands, due to different colour centres, in the UV-vis region for the 2.15 eV emission characteristic of Dy³⁺ ion. When excited, the absorbed energy (may be a part) was transferred from a colour centre to nearby Dy³⁺ ions and Dy³⁺ characteristic emission was observed. Exciting the irradiated crystal around 3.28 eV yielded emission at 2.56, 2.15 and 1.76 eV. The first two emission bands were due to Dy³⁺ ions. The excitation spectrum for the 1.76 eV emission showed two prominent bands around 2.02 and 3.08 eV and hence the emission was attributed to the M_Na centre. The luminescence mechanism was described.     

Effect of Cr implantation on structural and optical properties of AlN thin films

Molecular beam epitaxy (MBE) grown AlN thin layer on sapphire substrates have been implanted with Cr⁺ ions for various dose from 10¹³ to 10¹⁵ cm⁻². The analyses were carried out by an X-ray diffractometer (XRD), Raman spectroscopy, a spectrophotometer and spectroscopic ellipsometry (SE) for structural and optical analyses. E₂(high) and A₁(LO) Raman modes of AlN layer have been observed and analyzed. The behavior of Raman shift and the variation in intensity and in peak width of Raman modes as a function of ions flux are explained on the basis of chromium substituting aluminum atom and implantation-induced lattice damage. Both Raman and X-ray analyses reveal that the incorporation of chromium atoms increases in the host lattice with the increasing of Cr ions fluence. The band gap energy was determined by using transmission spectra. It was found that the band gap energy decreases as the ion dose increases. The band gap of the unimplanted AlN is 6.02 eV and it decreases down to 5.92 eV for the Cr⁺-implanted AlN with a ion dose of 1×10¹⁵ cm⁻². Optical properties such as optical constants of the samples were examined by using a spectroscopic ellipsometer. It was observed that the refractive index (n) decreases with the increasing of ion dose.     

Luminescence characteristics of the Pr3+ ion in SrAlF5

The paper reports on a study of luminescence and excitation spectra of SrAlF₅:Pr³⁺ (0.5 mol %) polycrystals performed at 10 and 300 K with synchrotron radiation in the range from 5 to 25 eV. The Pr³⁺ ions in SrAlF₅ were shown to emit successively two photons in transitions from the ¹ S ₀ and ³ P ₀ levels. The main energy characteristics of the compound, namely, the position of the 4f → 5d excitation band (5.95–8.0 eV), the energy separation between the ¹ S ₀, 4f and the lowest 5d levels (～0.15 eV), and the SrAlF₅ band gap width (～12 eV), were determined. SrAlF₅:Pr³⁺ was found to possess a number of features not found in other Pr³⁺-activated fluorides.     

Experimental verification of Cr2+ models of photoluminescent transitions in GaAs:Cr and AlxGa1−xAs:Cr single crystals

LPE layers of Al_xGa_1?xAs:Cr:Sn single crystals were grown and the photoluminescence band due to Cr²⁺ was observed over the range 0≤x≤0.42 when measured at 77 K. Preliminary spectra which reveal the characteristic zero phonon line were obtained at 4.2 K for x=0.23. The experimental results support the model in which the 0.84 eV photoluminescence band in GaAs:Cr is attributed to intraimpurity transitions at Cr²⁺.     

Anomalous luminescence of impurity-bound excitons in lithium borate crystals doped with cerium ions

The spectra and relaxation kinetics of the anomalous (?? < 10 ns) luminescence of Li₆GdB₃O₉:Ce³⁺ crystals have been experimentally detected. The time-resolved vacuum ultraviolet spectroscopy study has shown that optical transitions at 6.2 eV, caused by the transfer of an electron from the 4f ¹ ground state of Ce³⁺ to autoionizing states near the conduction band bottom of a crystal, lead to the formation of an impurity-bound exciton with the hole component localized on the 4f state of Ce³⁺ and the electron localized on states of the conduction band bottom. It has been found that the decay of such an exciton in Li₆GdB₃O₉:Ce³⁺ occurs through radiative recombination, leading to fast luminescence at 4.25 eV. The energy threshold for the formation of the impurity-bound exciton has been determined. The distribution functions of elementary relaxations over the reaction rate constants H(k), which determine the relaxation kinetics and luminescence quenching processes, have been calculated.     

Europium luminescence in fluorite upon high-energy excitation

The reflection and luminescence excitation spectra of CaF₂ crystals containing europium ions in divalent (Eu²⁺) and trivalent (Eu³⁺) states were measured in the range from 4 to 16 eV. It was established that, in CaF₂ : Eu³⁺ crystals, luminescence of Eu³⁺ ions (the f-f transitions) is effectively excited both in the charge-transfer band (at ～8 eV) and in the region of the 4f–5d transitions (at ～10 eV) but is virtually not excited in the fundamental region of the crystal (at an energy higher than 10.5 eV). Luminescence of Eu²⁺ ions (the 427-nm band) in CaF₂ : Eu³⁺ is effectively excited in the fundamental region of the crystal; i.e., luminescence of divalent europium ions occurs through the trapping mechanism. Emission of Eu²⁺ ions in CaF₂ : Eu²⁺ crystals is characterized by the excitation band at an energy of 5.6 eV (the 4f → 5d,t _2g transitions), as well as by the exciton and interband luminescence excitations. The results obtained and data available in the literature are used to construct the energy level diagram with the basic electron transitions in the CaF₂ : Eu crystals.     

Origin of green luminescence in PbWO4 crystals

Characteristics of two green emission bands, G(I) and G(II), and their origin were investigated within 0.4-300 K under photoexcitation in the 3.4-6.0 eV energy range for undoped and Mo⁶⁺-, Mo⁶⁺ , Y³⁺-, Mo⁶⁺, Nb⁵⁺-, Mo⁶⁺, Ce³⁺-, Cr⁶⁺-, La³⁺-, Ba²⁺- and Cd²⁺-doped PbWO₄ crystals with different concentrations of impurity and intrinsic defects, grown by different methods and annealed at different conditions. The G(I) emission band, observed at low temperatures, located around 2.3-2.4 eV and excited around 3.9 eV, is usually a superposition of many closely positioned bands. The G(I) emission of undoped crystals is assumed to arise from the WO₄²⁻ groups located in the crystal regions of lead-deficient structure. In Mo⁶⁺-doped crystals, this emission arises mainly from the MoO₄²⁻ groups themselves. The G(II) emission band located at 2.5 eV is observed only in the crystals, containing the isolated oxygen vacancies — WO₃ groups. This emission appears at T>160 K under excitation around 4.07 eV as a result of the photo-thermally stimulated disintegration of localized exciton states and subsequent recombination of the produced electron and hole centres near WO₃ groups. The G(II) emission accompanies also thermally stimulated recombination processes in PbWO₄ crystals above 150 K. Mainly the G(II) emission is responsible for the slow decay of the green luminescence in PbWO₄ crystals.     

Optical and theoretical investigations of V ions in CdZnTe crystal

High-resistivity CdZnTe:V crystals are investigated by photoluminescence (PL) and by time-resolved PL in the infrared spectral range. A double peaked emission band is detected around 0.8 eV and it is related to vanadium doping. No-phonon lines of the internal transitions were detected. This emission is interpreted as a balance between the ⁴T₁(⁴P)→⁴T₁(⁴F) internal transition and an electronic transition from the conduction band to the ⁴T₁(⁴F) ground state of V²⁺. The corresponding decay time after laser excitation gives evidence to the contribution of two different recombination processes. These two emission bands are separated by time-resolved luminescence. Crystal-field calculations of the detected transition energies based on Tanabe-Sugano scheme are presented and the Racah parameter B and crystal-field intensity D_q were determined.In addition, a model is developed in terms of one-electron orbital, to explain the characteristics of the PL excitation processes of V²⁺. Excitations with above and below band edge energy confirm the proposed schemes.     

Photoemission investigations on nanostructured TiO2 grown by cluster assembling

Nanostructured titanium dioxide (ns-TiO₂) films were grown by supersonic cluster beam deposition method. Transmission electron microscopy demonstrated that films are mainly composed by TiO₂ nanocrystals embedded in an amorphous TiO₂ phase while their electronic structure was studied by photoemission spectroscopy. The cluster assembled ns-TiO₂ films are expected to exhibit several structural and chemical defects owing to the large surface to volume ratio of the deposited clusters. Ultraviolet photoemission spectra (hv = 50 eV) from the valence band unveil the presence of a restrained amount of surface Ti 3d defect states in the band gap, whereas Ti 2p core level X-ray photoelectron (hv = 630 eV) spectra do not manifestly disclose these defects.     

ESR and optical spectroscopy of copper-doped PLZT electro-optic ceramics

2+ spectra in axial and cubic crystal fields. Cu²⁺ substitutes for Ti⁴⁺ and the excess charge can be compensated by La³⁺ on a nearest-neighbor site, thus creating axial symmetry. The centers of cubic symmetry are those where the charge is compensated in distant spheres. In contrast to pure PLZT, PLZT:Cu exhibits a new luminescence band peaking at 1.18 eV. This emission is ascribed to the ²T₂(D)→²E(D) transition of Cu²⁺(3d⁹) which can be excited either in the resonant 1.87 eV band or via charge-transfer excitation bands at 2.40, 2.57, and 3.03 eV. The absorption band at 1.45 eV is assumed to be that of Cu⁺ ions. Annealing in hydrogen and in oxygen atmospheres caused decrease and restoration, respectively, of the ESR and luminescence intensities as a consequence of Cu²⁺ conversion into Cu¹⁺ and vice versa. Received: 14 November 1997/Accepted: 8 December 1997     

Luminescence of mercurylike impurities in single-crystal CdWO4 compounds

The processes of crystallization by the method of liquid epitaxy are studied for the first time for single-crystal films of CdWO₄ doped with the mercurylike ions Bi³⁺ and Pb²⁺, which can be used as thin-film components of combined scintillators for monitoring α- and β-activities. It is shown that in comparison with their solidcrystal analogs, the special features of these films consist in a longwave shift of the integral luminescence spectrum that is caused by high concentrations of the radiating complexes (V_Cd-WO₆) with hv_max=2.05–2.15 eV and the “distorted” complexes (WO₆)^* in them. It is found that in the case of luminescence of single-crystal films CdWO₄:Pb, radiation of mercurylike centers (PbO₆) prevails with hv_max=2.87 eV, while in luminescence of CdWO4, radiation of centers (BiO₆) with hv_max=2.16 eV and of complexes (V_Cd-WO₆). Institute of Applied Physics, Iv. Franko Lvov State University, 49, General Chuprynka St., Lvov, 290044, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 211–215, March–April, 1998.     

Combustion synthesized MgAl2O4:Cr phosphors—An EPR and optical study

Magnesium aluminate (MgAl₂O₄) doped with trivalent chromium (Cr³⁺) was synthesized by the combustion method. The prepared sample was characterized by X-ray powder diffraction, Brunauer-Emmet-Teller (BET) adsorption isotherms and diffuse-reflectance UV-vis spectroscopy techniques. Electron paramagnetic resonance (EPR) and photoluminescence (PL) studies have been performed at room temperature and at 110 K. The EPR spectrum exhibit resonance signals at g=5.37, 4.53, 3.82, 2.26 and 1.96 characteristic of Cr³⁺ ions. The luminescence of Cr³⁺-activated MgAl₂O₄ exhibits a red emission peak around 686 nm from the synthesized phosphor particles upon 551 nm excitation. The luminescence is assigned to a transition from the upper ²E_g→⁴A_2g ground state of Cr³⁺ ions. By correlating EPR and optical data the crystal field splitting parameter (D_q), Racah inter-electronic repulsion parameter (B) and the bonding parameters have been evaluated and discussed. The bonding parameters suggests that the ionic nature of Cr³⁺ ions with the ligands and the Cr³⁺ ions are in distorted octrahedral environment.