UV absorption of thin-film RbAg4I5-RE (Sm, Yb) systems

UV-spectra of samples obtained by vacuum deposition of RE (Sm, Yb) thin films onto films of the solid electrolyte RbAg₄I₅ (300 – 350 K, thickness 100 – 200 nm) exhibit bands of strong absorption with maxima at 4.3 and 5.0 eV. After the deposition of Sm (≈ 5 nm), the ionic conductivity σ of the samples decreases to ≈ 0.9 σ₀ and the lattice parameter from 11.24 to 11.15 Å. The halfwidth of X-ray reflections increases from 0.5 to 0.8⁰. Further increase of the concentration of Sm in the samples changes the X-ray diffraction pattern. Under such conditions, the absorption in the regions of 4.3 and 5.0 eV further increases; a new single edge of absorption at 3.8 eV appears and σ declines to ≈10^?2 σ₀. It is supposed that a genetic relation exists between the UV-bands of strong absorption in the highly defective silver-halides of the RbAg₄I₅-RE system and the electronic transitions 4d¹⁰ ?4d⁹ 5s in free Ag⁺ ions.     

Influence of samarium on optical absorption in thin films of the solid electrolyte RbAg4I5

The fundamental optical absorption of films of the solid electrolyte RbAg₄I₅ electrolyte films decreases (by approximately 25%) after vacuum evaporation of Sm films onto them, and a broad strong-absorption band with a maximum at 2.4 eV appears within the bad gap. The films bleach after 5–10 days in dry air. The observed phenomena are attributed to a high concentration (∼3×10²⁰ cm⁻³) of point defects, including F-centers, in nonstoichiometric RbAg₄I₅:Sm, and also to the oxidation of Sm. In colored films the ionic conductivity is σ⋍0.9σ ₀, and in bleached films it is close to the initial value σ ₀. Fiz. Tverd. Tela (St. Petersburg) 39, 1544–1547 (September 1997)     

Observation of occupied 5d states in f.c.c. Yb metal

We propose experimental evidences for the sd character of the occupied band states of f.c.c. Yb metal. Photoionization cross-section σ¹ in the range 24–65 eV, covering the 5p core electron energies have been measured for both Yb (4ƒ¹⁴6s²5d⁰) and Lu (4ƒ¹⁴6s²5d¹). Both the hv dependence of σ¹ for the Yb valence band and the presence of photoemission resonances above the 5p edges of Lu and Yb indicate the presence of occupied 5d states at the top of the valence band of solid Yb. The Yb 4ƒ σ¹ is presented in order to distinguish the 5d band resonances from the 5p-5d giant dipole autoionization decays. L_{2, 3} X-ray absorption white lines for Yb provide a measure of the 5d bandwidth.     

The absence of a measurable hall effect in the superionic conductor RbAg4I5

Thin film samples of RbAg₄I₅ have been prepared by evaporation and several of their electrical properties have been determined. The behavior of the conductivity of these films is identical to that found in bulk RbAg₄I₅. An attempt to reproduce the Hall effect results of Kaneda and Mizuki was unsuccessful, and we conclude that the Hall mobility of silver ions in this material is less than 2 × 10^-3cm²/V·sec.     

Raman measurements of the superionic conductor KAg4I5

Raman measurements of the superionic conductor KAg₄I₅ are reported between 77K and 296K and compared to similar data of RbAg₄I₅. The mode frequencies for the two materials are very similar and a mode at 22.7 cm^?1 abruptly and reversibly disappears at the transition temperature, T_c=137 K, as is observed in RbAg₄I₅, at 121 K.     

Dissociative multiple photoionization of Br2, IBr,and I2 in the VUV and X-ray regions: a comparative study of the inner-shell processes involving Br(3d,3p,3s) and I(4d,4p,4s,3d,3p)

Dissociative multiple photoionization of the bromine, the iodine monobromide, and the iodine molecules in the Br(3d,3p,3s) and I(4d,4p,4s,3d,3p) inner-shell regions has been studied by using time-of-flight (TOF) mass spectrometry coupled to synchrotron radiation in the ranges of 90∼978 eV for Br₂, 60∼133 eV for IBr, and 86∼998 eV for I₂. Total photoion and photoion–photoion coincidence (PIPICO) yields have been recorded as functions of the photon energy. Here, giant shape resonances have been observed beyond the thresholds of the inner-shells owing to the Br(3d¹⁰)→Br(3d⁹ϵf), I(4d¹⁰)→I(4d⁹ϵf), and I(3d¹⁰)→I(3d⁹ϵf) transitions. The dissociation processes of the multiply charged parent ions have also been evaluated from variations of photoelectron–photoion coincidence (PEPICO) and PIPICO spectra with the photon energy. From each Br(3p_3/2) (189.9 eV) and I(4p_3/2) threshold (129.9 eV), quintuple ionization of the molecules begins to play important roles in the photoionization, subsequently yielding ion pairs of X³⁺–X²⁺ (X=Br, I). From the I(3d_5/2) threshold (627.3 eV), loss of six electrons from iodine molecule additionally begins to play a minor role in the multiple photoionization, giving rise to the formation of ion pairs of either I³⁺–I³⁺ or I⁴⁺–I²⁺. A direct comparison of the strengths and the ranges of the I(4d) and Br(3d) giant resonances was successfully made from dissociative photoionization of IBr. Over the entire energy range examined, 60<E<133 eV, biased charge spread relevant to the specific core-hole states of IBr is observed, presumably reflecting the fact that charge localizes mostly in the excited atoms, which can be accounted for mainly by a two step decay via a fast dissociation followed by autoionization upon the VUV absorption.     

Infrared absorption spectra of amorphous silicon with gold

We determined the optical constants below the absorption edge of amorphous films of Si_1?xAu_x (x between 0.07 and 0.30) prepared by getter sputtering in argon. In the range 0.15 to 0.5 eV we found that the absorption increased with increasing Au content and could be described by Mott's formula for a.c. conductivity σ(ω) ≈ ω²[In (I₀/ω)]⁴ with I₀ ? 4.5 eV at x = 0.11 and 3.8 eV at x = 0.29; in the range 10–100 K it changed only slightly with temperature. The absorption is interpreted as due to direct transitions involving Au atoms.     

Yb掺杂C60薄膜的x射线光电子能谱研究

在超高真空系统中制备了C₆₀的Yb填隙化合物薄膜.用x射线光电子能谱研究了Yb和C₆₀结合过程中C 1s，Yb 4f和Yb 4d的变化.利用Yb 4f和C 1s的谱峰强度确定出相纯样品的化学组分接近Yb_2.75C₆₀，这一结果与晶体x射线衍射结果一致.Yb 4f和Yb 4d的峰形与峰位表明化合物中Yb的价态为Yb²⁺.相纯样品（Yb_2.75C₆₀）的C 关键词： 60的Yb填隙化合物薄膜')" href="#">C₆₀的Yb填隙化合物薄膜 x射线光电子能谱 Yb价态     

The effect of point defects on the ionic conductivity of RbAg4I5 solid electrolytes

Abstract

The effect has been studied of additive coloring on the magnitude of ion conductivity of RbAg₄I₅ crystals. It has been found that slight changes of silver stoichiometry of 10^?3 at.% can lead to considerable variations of the ionic conductivity Δ[sgrave]_i/[sgrave]_i ? 0.1. The dependence has been observed of the magnitude of ion conductivity on the ratio between the integral intensities of the main bands in the photoluminescence spectrum of the γ-phase of RbAg₄I₅ which associated with the luminescence centres containing vacancies and interstitials of silver cations.     

Divalent rare-earth ions in LaF<Subscript>3</Subscript> crystals

The optical spectra and electric conductivity of LaF₃ crystals doped with 0.01, 0.1, and 0.3 mol % YbF₃, where Yb was partly or completely recharged to the divalent state, are studied. The long-wavelength absorption band of 370 nm is caused by electrons transitioning from state 4f ¹⁴ to the level of anion vacancies. The remaining bands at 300–190 nm are caused by 4f ¹⁴–5d ¹4f ¹³ transitions in Yb²⁺. The bulk electric conductivity and peaks of the dielectric losses of LaF₃–Yb²⁺ crystals are caused by Yb²⁺–anion vacancy dipoles. The activation energy of the reorientation of Yb dipoles is 0.58 eV. The optical and dielectric properties of Yb²⁺ centers are compared to those of Sm²⁺ and Eu²⁺ centers studied earlier in LaF₃ crystals.     

Proprietes electroniques et electrogalvaniques dutellurure d'argent β domaine d'existence

A study of the electronic and electrogalvanic properties of β silver telluride has been performed on samples whose non-stoichiometry has been determined by coulometric titration with the cell Ag/RbAg₄I₅/Ag₂Te/Pt. The data lead to the adoption of a model of Frenkel defects on the silver sublattice that are fully ionised. Their formation enthalpy is H_F′ = 0,70 eV. On the tellurium side this model is completed by the association V_AgV_Ag^x. Th homogeneity range is reported from ?10°C to 132°C: it extends essentially on the tellurium side of the stoichiometric composition.     

Proprietes electroniques et electrogalvaniques du seleniure d'argent β: Domaine d'existence

A study of the electronic and electrogalvanic properties of β silver selenide has been performed on polycrystalline samples whose non-stoichiometry is controlled by eoulometric titration with the cell Ag/RbAg₄I₅/Ag_2+? Se/Pt. The adoption of an electronic model according to which the Frenkel defects of the silver sublattice are completely ionised allows us to compute independently the non-stoichiometry with the two formulaes δ = [Ag^o_i] ? [V'_Ag] and δ = n ? p. The homogeneity range has been drawn at positive temperatures and the formation enthalpy of the Frenkel defects is H'_F = 0,40 eV.     

A tunneling spectroscopy study of the temperature dependence of the forbidden band in Bi2Te3 and Sb2Te3

Tunneling measurements of dI/dV, d ² I/dV ², and d ³ I/dV ³ were formed along the C ₃ axis (normally to layers) for Bi₂Te₃ and Sb₂Te₃ layered semiconductors in the temperature range 4.2<T>29 5 K. Temperature dependences of the forbidden band energy E _g were obtained. The forbidden band energy in Bi₂Te₃ was 0.20 eV at room temperature and increased to 0.24 eV at T=4.2 K. The E _g value for Sb₂Te₃ was 0.25 eV at 295 K and 0.26 eV at 4.2 K. The distance between the top of the higher valence band of light holes and the top of the valence band of heavy holes situated lower was found to be ΔE _V≈19 meV in Bi₂Te₃; this distance was independent of temperature. The conduction bands of Bi₂Te₃ and Sb₂Te₃ each contain two extrema with distances between them of ΔE _c≈25 and 30 meV, respectively.     

Light induced phenomena in superionic crystals

The phenomena of the reversible transformation of concentration and a structure of luminescence centers and of the concentration of mobile silver ions in local irradiated region of RbAg₄I₅ superionic crystals are studied. A new effect of illumination on ionic conductivity and activation energy of migration of mobile Ag⁺ cations in RbAg₄I₅ superionic crystals are observed. Reversible changes in the ionic conductivity due to illumination of superionic crystals are caused by reversible change in the structure of electronic centers caused by elastic strain around these centers. The effect of elastic deformation on the process of ionic transport and activation energy for diffusion of mobile silver cations are studied. Photostimulated recovery of the ionic conductivity after its change due to preliminary illumination of a RbAg₄I₅ superionic crystal with light of wavelength λ=430 nm are detected. This recovery of the ionic conductivity is due to excitation of centers in complexes generated by previous illumination of tested samples.     

The electrical response of RbAg4I5/graphite inhomogeneous interfaces

The ac impedance of the cell graphite/graphite + RbAg₄I₅/graphite + RbAg₄I₅/graphite was investigated in the frequency range from 10⁻⁴ to 3 × 10⁵ Hz. A model assuming the graphite + RbAg₄I₅ mixture to represent a porous interface could explain the observed dependences in nearly the whole frequency range with the exception of the lowest frequencies. Attempts to improve the agreement presuming adsorption, discharge of charge carriers or diffusion of neutral species failed. An excellent fit could be achieved assuming a frequency dependent ac conductivity of the interface, approximately proportional to the frequency, as in the bulk of many solids with low conductivity, such as amorphous semiconductors or dielectrics.     

Pressure dependence of the absorption edge for Cd1-xMnxTe

The effect of pressure on the optical absorption edge of mixed crystals Cd_1-xMn_xTe with different manganese concentrations is reported. The observed absorption edge shifts to higher energy with increasing pressure at a rate of α=7?8×10^?3 eV/kbar and a second order coefficient of β=-4×10^?5 eV/kbar² for x<0.5, to lower energy with increasing pressure at a rate of α=-5.0 ×10^?3 eV/kbar for x?0.5. A phase transition occurs for all the samples studied. The absorption edge of the new phase is outside the wavenumber range of the instrument. The physical origins of different pressure coefficients are discussed in the light of the deformation potentials of energy band states and the hybridization of the Mn²⁺ 3d levels with the p-like states in the valence band.     

Electronic absorption spectra of Sm(II) and Yb(II) ions in a LiCl-KCl eutectic melt at 450 °C

We have measured the absorption spectra of Sm(II) and Yb(II) ions in LiCl-KCl eutectic at 450 °C. The UV spectra of Sm(II) and Yb(II) exhibited intense and broad peaks at around ∼260 nm, which is attributable to the 4f-5d transitions. With the aid of the UV-vis spectroscopic method, in-situ identification of spontaneous reduction of trivalent Sm and Yb ions to divalent ions was achieved.     

Optical transitions in Zn3P2 within the 0.06–1.4 eV energy range

Absorption measurements of single Zn₃P₂ crystals were made within the 0.06–1.4 eV energy range and at temperatures 300 and 80 K. The multiphonon absorption spectra were observed in the range 0.06–0.11 eV. Deep levels were found at the energies of 0.65, 0.87 and 1.28 eV for the samples with concentration p ≈ 10²² ÷ 10²³m⁻³ and at 0.55 eV for the samples with p ≈ 10¹⁹ ÷ 10²⁰m⁻³, as well as at the energies of 0.17, 0.26 and 0.36 eV for both types of samples. The observed optical transitions were described by means of the Quantum Defect Method.     

Nonlinear optical spectroscopy of electronic transitions in hexagonal manganites

The hexagonal rare-earth manganites RMnO₃ (R = Sc, Y, Ho, Er, Tm, Yb, Lu) are a group of materials with an unusual combination of magnetic, electric and optical properties. The electronic structure of these materials was studied by second harmonic (SH) spectroscopy in the range from 1.2 to 3.0 eV. Faraday rotation and absorption spectra were measured in the range from 1.0 to 1.6 eV. Broad bands at ∼1.7 eV and ∼2.7 eV are assigned to electronic transitions between Mn³⁺(3d⁴) levels. The SH spectra are discussed on the basis of a recently developed microscopic theory. Received: 26 April 2001 / Published online: 18 July 2001     

Spectral and luminescence properties of gadolinium gallium garnet epitaxial films doped with terbium

Gadolinium gallium garnet single-crystal films containing terbium are grown through liquid-phase epitaxy from a supercooled solution melt in the PbO-B₂O₃ system. The optical absorption spectra in the wavelength range 0.2–10.0 μm and the luminescence spectra excited by synchrotron radiation with energies in the range 3.5–30.0 eV are investigated at temperatures of 10 and 300 K. It is revealed that the optical absorption spectra contain an absorption band with the maximum at a wavelength λ ≈0.260 μm, which corresponds to the spin-allowed electric dipole transition between the electronic configurations 4f ⁸(⁷ F ₆) → 4f ⁷(⁸ S)5d of the Tb³⁺ ions. The narrow low-intensity absorption bands attributed to the 4f → 4f transitions from the ⁷ F ₆ ground level to the ⁷ F _0–5 multiplet levels of the Tb³⁺ ions are observed in the wavelength range 1.7–10.0 μm. In the luminescence spectra measured at a temperature of 10 K, the highest intensity is observed for a band with the maximum at a wavelength λ ≈ 0.544 μm, which is associated with the ⁵ D ₄ → ⁷ F ₅ radiative transition in the Tb³⁺ ion.