Admittance spectroscopy of polycrystalline and epitaxially grown CuGaSe2

Using either single crystalline, epitaxially grown p-type CuGaSe₂ (CGSe) films in Schottky diodes or polycrystalline p-CuGaSe₂/n-CdS single-junction solar cells, we employed thermal admittance spectroscopy (TAS) to gain insight into the electronic transport mechanisms of CGSe. In both types of devices, the capacitance decreases about 50% to its geometrical value in a frequency dependent step between 250 and 150 K. For the Schottky diodes, this capacitance step reflects the response of the shallowest acceptors whose energy level is located 150 meV above the valence band. In the solar cells, a comparable response occurs but is superposed by carrier freeze-out outside the space-charge region.     

Photoluminescence of CdGeP2 and (Cd,Mn)GeP2

Photoluminescence of CdGeP₂ (112) single crystal and CdGeP₂ epitaxial film grown on GaAs (001) substrate have been studied and their spectral similarity found. Spectral bands associated with donor/acceptor transitions peak at close energies for both substances and all are lower than the energy gap of the chalcopyrite crystal.On the other hand, the growth of (Cd,Mn)GeP₂ ferromagnetic layer on CdGeP₂ (112) single crystal was performed to make it possible observation of PL from both the ferromagnetic layer and substrate. The green laser excitation (514, 532 nm) produces a proper photoluminescence similar to that in the undoped CdGeP₂ crystal and film. An extra emission from the ferromagnetic-nonmagnetic heterojunction occurs to extend up to photon energies exceeding E_g of the host semiconductor. The short wavelength photoluminescence is to be due to (Cd,Mn)GeP₂ dilute magnetic semiconductor (DMS). This fact states that Mn-doped II-IV-V₂ chalcopyrites are closer to II-VI DMS than to another group III-V DMS, where the heavy Mn-doping suppresses photoluminescence at all. Features of the observed short wavelength emission are discussing based on the temperature and spectral analyses.     

Synthesis of nanocrystalline and mesoporous zinc sulphide from a single precursor Zn(SOCCH3)2Lut2 complex

We report the formation of mesoporous zinc sulphide, composed by the fine network of nanoparticles, which was formed via a single precursor Zn(SOCCH₃)₂Lut₂ complex. The complex was chemically synthesized using zinc carbonate basic, 3,5-lutidine and thioacetic acid, in air. The metal precursor complex was characterized using different conventional techniques. Thermogravimetric analysis (TGA) result indicates that the decomposition of the complex starts at 100 °C and continues up to 450 °C, finally yielding ZnS. ZnS nanocrystals were characterized by powder X-ray diffraction (XRD) technique, field emission scanning electron microscopy (FESEM), N₂-sorption isotherm, UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The grain diameter of nanocrystals was found to be 4-5 nm. The material followed Type-IV N₂-sorption isotherm, which is the characteristic of mesoporous materials. The band gap energy, as obtained from optical measurements was around 3.8 eV.     

Study of molybdenum coordination state and crystallization behavior in MoO3-La2O3-B2O3 glasses by Raman spectroscopy

The ternary MoO₃-La₂O₃-B₂O₃ glasses containing a large amount of MoO₃ (10-50 mol%) are prepared, and their structure and crystallization behavior are examined from the Raman scattering spectrum measurements and X-ray diffraction analyses. It is found that the glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing MoO₃ content. It is suggested that the main coordination state of Mo⁶⁺ ions in the glasses is isolated (MoO₄)²⁻ tetrahedral units giving strong Raman bands at 830-860 and 930 cm⁻¹. It is found that the crystalline phases in the crystallized glasses are mainly LaMoBO₆ and LaB₃O₆, and the main crystallization mechanism in MoO₃-La₂O₃-B₂O₃ glasses is surface crystallization. LaMoBO₆ crystals are found to give strong Raman bands at 810-830 and ∼910 cm⁻¹.     

Experimental confirmation by galvanomagnetic methods of a complex transport model in In0.53Ga0.47As layers deposited by MBE on SI-InP

At low temperatures In_0.53Ga_0.47As samples show an increase of carrier concentration, which can be explained in terms of a two carriers transport model. This type of problem exists since the beginning of the semiconductor era, dating back to monocrystalline germanium.We propose that in all the investigated layers, there are X atoms or charged dislocations in the region of the first monolayers, which are built in during epitaxial growth. The layers were intentionally undoped. They form an impurity band in which low mobility carriers dominate over the localised electron scattering due to the s-d exchange interaction. These carriers do not freeze out at liquid helium temperature and give rise to two transport media for electrons; a conduction band at higher temperatures and an impurity band at lower temperatures. The electron which fall down onto the previously ionised X atoms, then move by thermally activated hopping. We show that the two carriers model for In_0.53Ga_0.47As epitaxial layers are confirmed by the carrier concentration-temperature, carrier concentration-magnetic field, resistivity-magnetic field behaviour, and also by YKA theory also. The differences between the two transport models are so distinctive that observed phenomena may exist. This paper presents experimental results, which constitute comprehensive evidence for the complicated structure of the semiconductor epitaxial layers on the sample of n-type In_0.53Ga_0.47As/InP layer with n=2.2×10¹⁵/cm³.     

Fabrication of p-CuGaS2/n-ZnO:Al heterojunction light-emitting diode grown by metalorganic vapor phase epitaxy and helicon-wave-excited-plasma sputtering methods

Greenish-white electroluminescence (EL) was observed from the heterojunction light-emitting diodes (LEDs) composed of p-type (001) CuGaS₂ chalcopyrite semiconductor epilayers and preferentially (0001)-oriented polycrystalline n-type ZnO thin films. The CuGaS₂ layers were grown on a (001) GaP substrate by metalorganic vapor phase epitaxy and the ZnO films were deposited by the surface-damage-free helicon-wave-excited-plasma sputtering method. The n-ZnO/p-CuGaS₂ LED structure was designed to enable an electron injection from the n-type wider band gap material forming a TYPE-I heterojunction. The EL spectra exhibited emission peaks and bands between 1.6 and 2.5 eV, although their higher energy portions were absorbed by the GaP substrate. Since the spectral lineshape resembled that of the photoluminescence from identical CuGaS₂ epilayers, the EL was assigned to originate from p-CuGaS₂.     

Temperature Raman scattering study of CaAl0.5Ta0.5O3 perovskite crystal

Temperature Raman scattering studies were performed for CaAl_0.5Ta_0.5O₃ crystal. This material features NaCl-type ordering of Al³⁺ and Ta⁵⁺ ions at the B-site superimposed onto b⁻b⁻c⁺ octahedral tilting. Because of the existing twin-related domains in crystal structure, the micro-Raman measurements were carried out at room temperature. Some differences in Raman spectra obtained using macro- and micro-Raman system were revealed. Most of the Raman modes show monotonous red-shift with the increase in temperature. Only the cubic-like fully symmetric A_1g mode slightly increases its frequency with an increase in temperature. There are no uncontinuous changes of mode frequency in the temperature range studied. It indicates the stable character of static distortions of crystal structure relying on changes of octahedra tilt angle.     

Raman spectra of the orthorhombic semiconductor compound Cu2SnTe3

The optical phonon spectrum of the semiconductor Cu₂SnTe₃, that crystallizes in the orthorhombic structure with space group Imm2 (), have been studied by measuring unpolarized Raman scattering between 10 and 300 K. The experimental frequencies of the phonon modes observed were compared to those calculated by using simplified lattice dynamical models reported in the literature. From combined analysis of these results together with the factor group analysis of the zone-center vibrational modes, valuable information about these modes was obtained and their possible symmetry was assigned. A₁ modes at 71, 123, 167, 176 and 190 cm⁻¹; A₂ modes 115 and 131 cm⁻¹; B₁ modes at 76, 142 and 152 cm⁻¹; B₂ modes at 89, 100 and 206 cm⁻¹; a overtone at 246 cm⁻¹, and combinations at 218, 270 and 292 cm⁻¹; have been observed in this compound.     

Raman spectroscopic analysis of sulphur-doped TiO2 by co-grinding with TiS2

Doping sulphur into titania has been tried using TiS₂ as a doper based on the mechanically induced solid-state reaction between TiO₂ and TiS₂. The prepared samples have been characterized by X-ray diffraction (XRD), Raman spectroscopy and UV-Vis reflectance spectroscopy. Raman analysis, particularly has been proved to be effective in assessing the sulphur doping by correlating the oxygen deficiency of the doped oxide with the change of active Eg mode of rutile phase.     

Optical characterization of gallium antimonide highly doped with manganese

Gallium antimonide crystals highly doped with Mn were prepared by a liquid-phase-electroepitaxy growth method. The crystals exhibited high hole concentrations up to 6×10¹⁸ cm⁻³. Photoluminescence (PL) and transmission techniques were used for their investigation. Spectral line-shapes typical for highly doped semiconductors were observed. The lines revealed the features corresponding to band gap narrowing and valence-band filling phenomena. Values of the band-gap narrowing ΔE_g and the degree of the valence-band filling ΔE_F were estimated from the PL spectra. The ionization energy of the Mn acceptor E_i was estimated to be approximately 15.1-15.6 meV. At low temperatures, the PL maxima shifted relatively strongly towards higher energy with temperature. The shifts most probably resulted from a dramatic change in the electron density of states near the bottom of the conduction band. The extent of low-energy tails of the PL bands correlates with the doping levels. The transmission spectra exhibited an absorption band centred at around 774-780 meV. The band most probably originated in electron transitions from the level of spin-orbit splitting to the top of the valence band.     

Phonon spectra of stoichiometric rare-earth compound of EuGa2S4

Investigations of EuGa₂S₄ have been done on the photoluminescence (PL) related to the transition between 4f⁶5d and 4f⁷ configuration of the Eu²⁺ ion and its excitation (PLE) spectra, Raman scattering and infrared absorption. The energies of phonons coupled to the ground and the excited states of the transition are analyzed to be 34 and 19 meV from the shapes of the PL and PLE bands, respectively. The former corresponds to the energy of the Raman line showing the highest intensity. The latter is close to the value obtained from analysis of the temperature dependence of the half width of the PL band. These correspondences indicate that the relevant emission of EuGa₂S₄ surely has phonon-terminated character.     

Epitaxial Cu(In,Ga)S2 thin film solar cells

Epitaxial layers of the quaternary compound Cu(In,Ga)S₂ and the ternary compound CuInS₂ were grown on Si(111) substrates via Molecular Beam Epitaxy. The layers were investigated for their morphological and structural properties using Rutherford backscattering spectroscopy, atomic force microscopy, reflection high-energy electron diffraction and X-Ray diffraction. Furthermore, complete solar cell devices were processed from these layers and their photovoltaic properties were investigated by means of I(U)-curves under illumination. Thus, efficiencies up to η=3.2% were achieved. The comparatively low performance of the solar cell devices is attributed to certain heterogeneities of the samples as a result of the growth process.     

Photoluminescence spectra of rare earth doped CaGa2S4 single crystals

Six kind CaGa₂S₄ single crystals doped with different rare earth (RE) elements are grown by the horizontal Bridgman method, and their photoluminescence (PL) spectra are measured in the temperature range from 10 to 300 K. The PL spectra of Ce or Eu doped crystals have broad line shapes due to the phonon assisted 4f-5d transitions. On the other hand, those of Pr³⁺, Tb³⁺, Er³⁺ or Tm³⁺ doped samples show narrow ones owing to the 4f-4f transitions. The assignments of the electronic levels are made in reference to the reported data of RE 4f multiplets observed in same materials.     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Raman spectroscopy of pseudomorphic Si0.989C0.011/Si superlattices

Raman spectroscopy is used here to study pseudomorphic Si_0.989C_0.011/Si superlattices grown by molecular beam epitaxy. The high crystalline quality of the samples was tested by a high resolution X-ray diffraction experiment. The lineshape of the LO Si-Si peak shows an asymmetry, which correlates with the increase of the alloy layer width. The Raman spectra show three additional peaks in the high energy side above the LO mode of Si. One of them is due to the local vibration of the C substitutional atoms, and the other two can be attributed to the formation of short range order with C atoms occupying second and third nearest-neighbor places. On the low energy side of the LO Si-Si mode, we have observed two other peaks associated with the relaxation of the Si atoms around the substitutional C. Although the X-ray experiments show clear evidence of superperiodicity, no indication of the superlattice formation could be observed in the parallel polarized Raman spectra, where the folded acoustic modes are allowed.     

Resonant Raman scattering in single crystal of congruent LiTaO3 : Effect of excitation energy

Large dispersion in the peak position of the OH⁻ stretching mode (∼687.9 and ∼2167.7 cm⁻¹/eV for fundamental and 3rd harmonic, respectively) is observed by Resonance Raman studies in congruent lithium tantalate single crystal under varying excitation energies. This is explained by considering the involvement of multiple LO phonons in the interaction with OH⁻ stretching vibration and the resonantly excited electrons. The intensity of the peaks is also found to vary with the excitation energy. FWHM increases with the increase in excitation energy because of individual contributions of the increasing number of resonance steps to the broadening.     

The pseudogap and superconducting gap in the ab-plane electronic Raman continuum of YBa2Cu4O8

We report plane-polarised Raman spectra from YBa₂Cu₄O₈ single crystals between 300 and 10 K. In the normal state we observe a gap-like depletion of intensity from the electronic continuum extending to around 1200 cm⁻¹ with an onset temperature of around 225 K. We remove the phonons and pseudogap depletion from the spectra using a simple model and recover a characteristic high-T_c superconductor continuum. In the superconducting state, intensity returns to the continuum in the form of a very broad pair-breaking peak.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

X-ray diffraction, Raman spectrum and magnetic susceptibility of the magnetic semiconductor Cu2FeSnS4

In an attempt to resolve the crystal structure and the corresponding space group of the magnetic semiconductor Cu₂FeSnS₄, samples of this compound were studied by X-ray diffraction, differential thermal analysis, Raman scattering and magnetic susceptibility. It was found that at room temperature this compound prepared by a careful crystal growth process, including annealing to equilibrium at a suitable temperature followed by slow cooling of the samples to 300 K, crystallizes in a tetragonal structure with space group .