Band structure and optical spectra of RbNH4SO4 crystals

First-principal density functional theory (DFT) calculations of the band structure, density of states and dielectric functions ε(E) of the rubidium ammonium sulfate (RAS) crystal, RbNH₄SO₄, in the orthorhombic phase Pnma have been carried out using the CASTEP code. Valence electron bands of the crystal are flat in k-space, that responds to the relatively great effective mass, m*?5m_e. The top valence band of the crystal has been found to be the most flat, what might be an evidence of a weak chemical bonding of the sulfate complexes (SO₄) in the crystal and therefore for the predisposition to structural instability and phase transitions. The characteristic feature is that two top valence bands are originated almost entirely from p-electrons of oxygen. The bottom part of the conduction band is formed mainly by the hydrogen atoms, the higher parts of this band—by a mixed set of chemical elements and orbital moments. The calculated refractive indices in the range of crystal's transparency agree satisfactorily with the experiment considering that the infrared absorption is not taken into account in calculations.     

Absorption spectra of Ni2+ in (NH4)2Mg(SO4)2·6H2O and Co2+ in Na2Zn(SO4)2·4H2O

Optical absorption spectra of Ni²⁺ in (NH₄)₂Mg(SO₄)₂·6H₂O and Co²⁺ in Na₂Zn(SO₄)₂·4H₂O single crystals have been studied at room and liquid nitrogen temperatures. From the nature and position of the observed bands, a successful interpretation could be made assuming octahedral symmetry for both the ions in the crystals. The splitting observed for ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band in Ni²⁺ and ${}^4\text{T}{}_{\mathrm{2g}}\text{(F)}$ band in Co²⁺ at liquid nitrogen temperature have been explained as due to spin-orbit interaction. The extra band observed at 16,325 cm^-1 in the case of Ni²⁺ at low temperature has been interpreted to be the superposition of vibrational mode of SO^2-₄ radical on ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band. The observed band positions in both the crystals have been fitted with four parameters B, C, Dq and ζ.     

Optical absorption due to transitions between bands and local levels in CdCr2Se4

The theory of optical absorption due to transitions between a valence band and a hydrogen-like local level associated with a conduction band is modified to permit an arbitrary power-law dependence of energy on the magnitude of the wave-vector of carriers in the valence band. The observed absorption for photon energies below 1.6 eV in the ferromagnetic semiconductor CdCr₂Se₄ is discussed in terms of a combination of two types of terms. The first type of absorption is due to transitions to a local level from a band with two branches, in each of which there is an energy region with a width of 0.28 eV or more beginning 0.10–0.16 eV from the band edge, in which the energy measured from some origin near but not necessarily equal to the band-edge is approximately proportional to (wave-vector)^{($\text{1}\text{3}$)}. The second type of absorption has a dependence on photon energy ?ω of the form (?ω ? E₃)², where E₃ is a threshold energy probably connected with indirect transitions between bands as suggested by Sakai, Sugano and Okabe. After constraints on parameters appearing in the theory are imposed by use of results of these authors and of Shepherd, it is found that curves of Harbeke and Lehmann on optical absorption in CdCr₂Se₄ at 4.2, 78, 130 and 298 K in the photon-energy range 1.14–1.42 eV can be fitted to a mean accuracy of 3%, using an average of 3.75 adjustable parameters for each curve. The strength of the indirect band-to-band absorption does not have the temperature dependence expected for phonon-assisted indirect band-to-band transitions, but can be described by a term independent of temperature plus another term proportional to the square of the deviation of the magnetization from saturation. The fitting of the absorption curves requires that the ratio of the widths of the two branches of the bands varies from about 1.6 at low temperatures to 1.35 at 298 K and that the total width of the bands involved is less than 1 eV.     

Brillouin scattering study of phase transitions in LiK0.80(NH4)0.20SO4 mixed crystals

Brillouin spectroscopy was used to study the phase transitions of LiK_0.80(NH₄)_0.20SO₄ mixed crystals in the temperature range 10-300 K. The relevant elastic stiffness coefficients were evaluated at room temperature. The quasi-longitudinal γ₁₆ and the quasi-transverse γ₁₇ mode frequencies were measured in the above temperature range. From their frequency vs. temperature curve, three different phase transitions were determined. Two of the four phases presented by the crystal were found to be ferroelastic. The observed phases are tentatively assigned through a comparison with the phase transitions undergone by LiKSO₄ and LiK_0.96(NH₄)_0.04SO₄ crystals. An anomalous behavior of the Brillouin linewidth near the 260 K phase transition was observed.     

Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH₄)₂S/(NH₄)₂SO₄) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (?_b) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at −0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb–O, present on the as-received material is effectively removed on treating with ([(NH₄)₂S/(NH₄)₂SO₄]+S) and (NH₄)₂S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.     

H nuclear magnetic resonance study of the ferroelastic and superionic phase transitions of (NH4)4LiH3(SO4)4 single crystals

We investigated the temperature dependences of the line shape, spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, of the ¹H nuclei in (NH₄)₄LiH₃(SO₄)₄ single crystals. On the basis of the data obtained, we were able to distinguish the “ammonium” and “hydrogen-bond” protons in the crystals. For both the ammonium and hydrogen-bond protons in (NH₄)₄LiH₃(SO₄)₄, the curves of T₁ and T₂ versus temperature changed significantly near the ferroelastic and superionic phase transitions at T_C (=232 K) and T_S (=405 K), respectively. In particular, near T_S, the ¹H signal due to the hydrogen-bond protons abruptly narrowed and the T₂ value for these protons abruptly increased, indicating that these protons play an important role in this superionic phase transition. The marked increase in the T₂ of the hydrogen-bond protons above T_S indicates that the breaking of O-H?O bonds and the formation of new H-bonds with HSO₄^- contribute significantly to the high-temperature conductivity of (NH₄)₄LiH₃(SO₄)₄ crystals.     

A nuclear magnetic resonance study of the structural properties and molecular motions of Li2KH(SO4)2 and LiKSO4 single crystals

The structural properties and relaxation mechanisms of Li₂KH(SO₄)₂ crystals were determined using the temperature dependences of NMR spectra and the spin-lattice relaxation times (T₁) of their ¹H, ⁷Li, and ³⁹K nuclei. The results obtained were compared with the previously reported physical properties of LiKSO₄ crystals. The substitution of the potassium ions with protons in the LiKSO₄ crystals were variations in the phase transition temperatures, and the non-appearance of ferroelastic properties. The ⁷Li T₁ for the Li₂KH(SO₄)₂ crystals was much shorter than the ⁷Li T₁ for the LiKSO₄ crystals, and these findings indicate that the presence of the protons in Li₂KH(SO₄)₂ causes the Li ions to move with greater freedom.     

Low temperature electrical conductivity,dielectric constant,and phase transitions in (NH4)2SO4 and (ND4)2SO4

Careful axiswise measurements of d.c. conductivity and dielectric constants of (NH₄)₂SO₄ from 50 to - 196°C establish two distinct phase transitions, instead of one, at temperatures -49.5 and -58°C which remain unchanged in (ND₄)₂SO₄. Explanation based on successive distortions of non-equivalent (NH₄)⁺ is offered. Low temperature transport process in the crystal also is discussed.     

Energy band structure and Frenkel excitons in PbGa2S4

Optical reflection spectra are measured and calculated in PbGa₂S₄ crystals in the region of resonances related to excitons with large oscillator strength and binding energy (Frenkel excitons). The splitting of the upper valence band in the center of the Brillouin zone due to crystal field (Δ_cf) and spin orbit (Δ_so) interaction are determined. Optical reflection spectra are measured and calculated according to Kramers-Kronig relations in the region of 3-6 eV in Е⊥с and Е∥с polarizations, and the optical constants n, k, ε₁ and ε₂ are determined. The observed electronic transitions in PbGa₂S₄ crystals are discussed in the frame of theoretical energy band structure calculation for thiogallate crystals.     

Electrical properties of narrow gap semiconductor PtSb2

Results of measurements of conductivity, Hall and Seebeck coefficients of tellurium doped n-type crystals of platinum antimonide are presented. The Hall coefficient and the Seebeck coefficient undergo sign inversion twice, below and above room temperature. The detailed analysis of the experimental results revealed that below 200 K PtSb₂ can be described by a simple conduction and valence band model. The energy gap E_g = (110?0.15 × T) (meV), the electron conductivity mass m_n^c/m₀ = 0.35, acoustic phonon limited electron mobility 〈μ_a〉_n = 3 × 10⁶ T^{?$\text{3}\text{2}$} ($\text{cm}{}^2\text{V · s}$) and mobility ratio 〈μ_a〉_n/〈μ_a〉_p = 0.4 are determined. However, at higher temperatures a more complicated valence band model is needed to account for the experimental results. The arguments for the existence of subsidiary valleys in the valence band are presented.     

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.     

Proton conduction in (NH4)3 H(SO4)2 single crystals

D.C. electrical conductivity, DTA and coulometric studies on (NH₄)₃ H(SO₄)₂ single crystals are made. Conductivity is markedly anisotropic with maximum along c¹ direction. A sudden jump in the conductivity plot along c¹ direction at 413 K is supported by a large endothermic peak in DTA, confirming the presence of transition at this temperature. The values of activation energy calculated from conductivity measurements indicated that the charge carriers are protons. This was further confirmed by coulometric experiment where the gas evolved was hydrogen, as established by a gas chromatograph and the volume of H₂ released agreed with that expected from electrolysis. The mechanism of protonic conduction in this crystal is discussed.     

Dependence of the fundamental absorption edge of CdInGaS4 on hydrostatic pressure

The optical absorption of CdInGaS₄ single crystals has been measured over a hydrostatic pressure range up to 40 kbar in the 2.0–3.0 eV photon energy range at room temperature. The interband gap for the indirect allowed transition was found to have a pressure coefficient, dEg/dP, of +6.4 × 10^-6ev/bar.     

Derivation of the optical constants of spin coated CeO2-TiO2-ZrO2 thin films prepared by sol-gel route

Ternary thin films of cerium titanium zirconium mixed oxide were prepared by the sol-gel process and deposited by a spin coating technique at different spin speeds (1000-4000 rpm). Ceric ammonium nitrate, Ce(NO₃)₆(NH₄)₂, titanium butoxide, Ti[O(CH₂)₃CH₃]₄, and zirconium propoxide, Zr(OCH₂CH₂CH₃)₄, were used as starting materials. Differential calorimetric analysis (DSC) and thermogravimetric analysis (TGA) were carried out on the CeO₂-TiO₂-ZrO₂ gel to study the decomposition and phase transition of the gel. For molecular, structural, elemental, and morphological characterization of the films, Fourier Transform Infrared (FTIR) spectral analysis, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) were carried out. All the ternary oxide thin films were amorphous. The optical constants (refractive index, extinction coefficient, band gap) and thickness of the films were determined in the 350-1000 nm wavelength range by using an nkd spectrophotometer. The refractive index, extinction coefficient, and thickness of the films were changed by varying the spin speed. The oscillator and dispersion energies were obtained using the Wemple-DiDomenico dispersion relationship. The optical band gap is independent of the spin speed and has a value of about E_g≈2.82±0.04 eV for indirect transition.     

Effect of gamma doses on the optical parameters of Se76Te15Sb9 thin films

The effect of γ-radiation dose on the optical spectra and optical energy gap (E_opt.) of Se₇₆Te₁₅Sb₉ thin films was studied. The dependence of the absorption coefficient (α) on the photon energy (hν) was determined as a function of radiation dose. The films show indirect allowed interband transition that is influenced by the radiation dose. Both the optical energy gap and the absorption coefficient were found to be dose dependent. The indirect optical energy gap was found to decrease from 1.257 to 0.664 eV with increasing the radiation dose from 10 to 250 krad, respectively. The results can be discussed on the basis of γ-irradiation-induced defects in the film. The width of the tail of localized states in the band gap (E_e) was evaluated using the Urbach edge method. The refractive index (n) was determined from the analysis of the transmittance and reflectance data. Analysis of the refractive index yields the values of high frequency dielectric constant (ε_∞) and the carrier concentration (N/m^*). The dependence of refractive index on the radiation dose has also been discussed. Other optical parameters such as real and imaginary parts of the dielectric constant (ε₁, ε₂) and the extinction coefficient (k) have been evaluated. It was found that the spectral absorption coefficient is expected to a suitable control parameter of γ-irradiation-sensitive elements of dosimetric systems for high energy ionizing radiation (0.06-1.33 MeV).     

Simulation of elasto optical properties of K2SO4 crystals

The electronic optical spectra of the mechanically free and stressed crystals of potassium sulfate, K₂SO₄, in the orthorhombic phase Pnma have been calculated by the Cambridge Serial Total Energy Package (CASTEP) code. On the basis of these calculations, the components of stress elasto optical tensors based on the changes of refractive index n (π_im) and birefringence Δn () (i, k, m=1, 2, …, 6) have been obtained for the indices i, k ,m=1, 2, 3. Absolute magnitudes of the calculated tensor π_im are probably underestimated because the magnitudes of the calculated elastic stiffness tensor c_rm are found to be overestimated about two times. Features of the spectral dependences n(E) and k(E) of refractive and absorption indices of the mechanically free and stressed potassium sulfate crystals have been analyzed.     

Intraband and interband optical transitions in Zn3AS2

Absorption measurements were made on single crystals and thin films of Zn₃As₂; within the photon energy range of 0.12–1.16 eV at temperatures of 300, 80 and 5 K and reflectivity was measured in the range of 1.0–5.5 eV at 300 K. Absorption below the fundamental edge has been interpreted as a process involving three mechanisms: (i) free-carrier absorption, (ii) intraband transitions between levels in the valence band, and (iii) direct transitions from valence levels to the acceptor level/band. The fundamental absorption edge has been ascribed to direct interband transitions from three valence levels to one conduction level. An isotropic three-level Kane band model has been used to interpret the experimental data, modified by introducing the light-hole level split from the heavy-hole level due to the tetragonal crystal field. A reasonable fit of the model to the experimental results has been obtained in the region of both intraband and interband absorption for the following set of parameters: E_g = 0.985 eV, Δ_SO = 0.30 eV, Δ_CF = 0.05 eV, m^*_hh = 0.36 m₀ and P = 4 × 10^?10eVm (at 300 K). A proposed Zn₃As₂ energy-band model near the Γ point is described to interpret the observed absorption.     

Ferroelectric properties of partly deuterated NH4HSeO4 crystals

Partly deuterated NH₄HSeO₄ crystals were grown from solutions containing 10, 20, 30, 40, 50 and 60% molar deuterium. The deuteration process leads to an increase in the phase transition temperatures. The extrapolated value of ΔT_c(∞) for completely deuterated crystals is 25 K. The I2 ? B2(C³₂) (if a axis is parallel to [110]) symmetry and the ferroelectric transition related to it is observed only in crystals growing from solution containing less than 50% deuterium. The crystals growing from solution containing more than 50% deuterium have a P2₁2₁2₁(D⁴₂) symmetry.     

Absorption spectrum of Cs2Mg(SO4)2 · 6H2O:Ni2+ single crystals

The absorption spectrum of Ni²⁺ doped in Cs₂Mg(SO₄)₂ · 6H₂O single crystals has been studied at room and liquid nitrogen temperatures in the range 7000–34000 cm^?1. The observed spectrum is satisfactorily interpreted in terms of cubic ligand field model including spin-orbit coulping. The ligand field parameters evaluated to best fit the observed spectrum are B = 955 cm^?1, C = 3572 cm^?1, Dq = 910 cm^?1 and ξ = 550 cm^?1. The non-ligand field band observed at 77K has been interpreted to be the superposition of vabrational mode of SO₄^2? radical on ₃T_1g(F) band.     

Electrical and thermal studies in the commensurate incommensurate phase region of (NH4)2ZnCl4 single crystal

DC electrical conductivity for a virgin and poled annealed (NH₄)₂ZnCl₄b-axis single crystal shows a defect controlled property. A Schottky mechanism is a probable mechanism of conduction in regions of strong structural transitions. The rise of conductivity in the incommensurate and paraelectric phases is linked to an increase in discommensurations density. The activation energies (ΔE) in the three phases region were calculated. DTA measurements shows that the crystal is stable up to 200 °C and the phase transition temperatures were observed at 42, 94.8 and 137 °C. The effective activation energy (E_e) was obtained using Kissinger and Mahadevan equations. It was found to be equal to 0.49 eV. This correlates with the value obtained through DC conductivity.