Vibrational Raman spectra of CdSx Se1‐x magic‐size nanocrystals

Resonant Raman scattering spectra of ultrasmall (<2 nm) magic‐size nanocrystals (NCs) are reported. The spectra of CdS and CdS_x Se_1‐x NCs, resonantly excited with 325 nm and 442 nm laser lines, correspondingly, reveal broad features in the range of bulk optical phonons. The relatively large width, ～50 cm^‐1, and downward shift, ～20 cm^‐1, of the Raman bands with respect to the longitudinal optical phonon in bulk crystals and large NCs are discussed based on the breaking of the translational symmetry and bond distortion in these ultrasmall NCs. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic studies of thermal treatment effect on the composition and size of CdS1−xSex nanocrystals in borosilicate glass

The effect of heat treatment parameters on the chemical composition and average size of CdS_1−xSe_x nanocrystals obtained in borosilicate glass by diffusion-limited growth is studied by optical absorption and Raman scattering spectroscopy. An increase of selenium content from 0.75 to 0.83 in the nanocrystals with the heat treatment temperature and duration is observed. Three lowest-energy optical transitions in CdS_1−xSe_x nanocrystals are assigned to corresponding electronic transitions based on the observed dependence of the confinement-related absorption maxima on the nanocrystal size.     

Raman scattering in CdTe1-xSex and CdS1-xSex nanocrystals embedded in glass

Raman scattering on a series of glass composite samples containing CdTe_1-xSe_x and CdS_1-xSe_x nanocrystals with radii in the range [2nm, 12.5nm] is reported. By properly considering the size dependence of strain and confinement effects, the chemical composition and the lattice contraction is assessed. The polarization analysis of the scattering indicates that the Fröhlich electron-phonon interaction increases at decreasing the nanocrystal size.     

Quantum confinement in CdSxSe1−x spherical nanocrystals in a fluorophosphate glass matrix

Differential (wavelength-modulated) absorption of sulfoselenide solid-solution nanocrystals has been studied in a glassy fluorophosphate matrix near the fundamental absorption edge at 360–620 nm. The observed oscillations in the absorption are attributed to size quantization of electrons and holes under strong quantum-confinement conditions. The sulfur content in the mixed semiconductor has been refined from Raman scattering spectra in CdS_xSe_1?x samples with x=0.30, and the nanocrystal size (R?30 Å) has been derived from low-frequency Raman scattering spectra. These data were used to calculate the energies of electron-hole transitions in nanocrystals of mixed composition, and their subsequent comparison with experiment. The calculations were found to be in a good agreement with the observed experimental absorption spectrum for nanocrystals about 45 Å in size. The applicability of band-structure simulation for a nonspherical nanocrystal grown in a fluorophosphate glass matrix is discussed.     

Thermal conductivity of GexSb(As)ySe100‐x‐y glasses measured by Raman scattering spectra

We systematically measured thermal conductivity of Ge_xSb(As)₁₀Se_90−x, Ge_xSb₁₅Se_85−x, and Ge_xSb(As)₂₀Se_80−x chalcogenide glasses by measuring their Stokes and anti‐Stokes Raman scattering spectra and estimating the temperature raised by laser irradiation via the ratio of Stoke and anti‐Stokes scattering cross‐section. We aimed at demonstrating the viability of Raman scattering method for thermal conductivity measurements, and understanding the role of chemical composition in determining thermal conductivity of the chalcogenide glasses. We found that, while the values of the thermal conductivity measured in the paper are in a range from ~0.078 to 1.120 Wm^‐1K^‐1 that are in agreement with those reported data in the literatures, thermal conductivity increases before it reaches a maximum at the glass with chemically stoichiometric composition, and then decreases with increasing Ge content. We ascribed the threshold behavior of the thermal conductivity to the demixing of the structural units like GeSe₂, As₂Se₃ and Sb₂Se₃ from the main glass network. The present study demonstrated that Raman scattering method is simple and easy to measure thermal conductivity of the material. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectral dependence of the optical absorption temperature coefficient of CdS1−xSex nanocrystallites embedded in a silicate glass

The absorption temperature coefficient of CdS_1−xSe_x nanocrystallites embedded in a silicate glass has been studied in the temperature range above room temperature at different technological regimes and sizes of nanocrystals. To understand the optical properties of silicate glasses with semiconductor nanocrystallites, especially that at the initial stage of their formation, it is necessary to include the structural changes occurring in the nanocrystals during the heat treatment.     

Temperature Dependence of the Transmission Spectra of Silicate Glasses Containing CdS<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Semiconducting Nanocrystals

The transmission spectra of silicate glasses containing CdS_{1 − x} Se _x semiconducting nanocrystals of various sizes are investigated in the temperature range 20–300°C. It is shown that for explaining optical properties of these materials, not only the nanocrystal sizes, but also the structural changes occurring in nanocrystals during their formation must be taken into account.     

Formation and optical properties of CdSSe semiconductor nanocrystals in the silicate glass matrix

Technological conditions providing the formation of CdS _x Se_1−x semiconductor crystal grains with sizes ranging from 2 to 8 nm in a silicate glass matrix have been determined. As the temperature of forming annealing increases, the size of crystal grains increases without changes in their crystal structure and composition. The observed short-wavelength shift of the optical absorption edge indicates that the quantum confinement affects the energy band structure of the nanocrystals. Intense luminescence of the samples is due to radiative transitions involving defects at the semiconductor nanocrystal-silicate matrix interface or intrinsic defects of nanocrystals.     

Photoselective laser photo-ion microscopy with 5 nm resolution

Spectral selectivity has been attained in the method of field-ion microscopy with a spatial resolution of about 5 nm and time-of-flight determination of the photo-ion masses. Light-absorbing CdS_xSe_1−x nanocrystals in a transparent glass matrix are detected by irradiating field tips made from red light filters with copper-vapor laser radiation. The nanocrystals appeared in the photo-ion images as bright spots on a dark background. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 7, 450–454 (10 April 1998)     

MREI‐model calculations of Raman‐active modes in layered mixed crystals TiS2−xSex(0≤x≤2)

A modified random‐element isodisplacement model has been developed and used to calculate the concentration dependence of the wavenumbers of Raman‐active modes in mixed crystal system, TiS_2−xSe_x(0≤x≤2). Earlier theoretical work, based on the Jaswal model, predicted a phase transition in this system on cooling up to 125 K temperature for the composition x ≥ 1.2. But recently reported resistivity measurements did not find the existence of any phase transition for a composition x < 1.4 on cooling. Our calculations show these findings and give remarkably better fitting to Raman data. The estimated values of the force constants are found to lie generally in the range 10⁵–10⁶ amu cm⁻². Copyright © 2007 John Wiley & Sons, Ltd.     

Resonant Raman scattering in CdSxSe1−x nanocrystals: effects of phonon confinement,composition, and elastic strain

Optical phonon modes, confined in CdS_xSe_1−x nanocrystal (NC) quantum dots (≈2 nm in radius) grown in a glass matrix by the melting‐nucleation method, were studied by resonant Raman scattering (RRS) spectroscopy and theoretical modeling. The formation of nanocrystalline quantum dots (QDs) is evidenced by the observation of absorption peaks and theoretically expected resonance bands in the RRS excitation spectra. This system, a ternary alloy, offers the possibility to investigate the interplay between the effects of phonon localization by disorder and phonon confinement by the NC/matrix interface. Based on the concept of propagating optical phonons, which is accepted for two‐mode pseudo‐binary alloys in their bulk form, we extended the continuous lattice dynamics model, which has successfully been used for nearly spherical NCs of binary materials, to the present case. After determining the alloy composition for NCs (that was evaluated with only 2–3% uncertainty using the bulk longitudinal optical phonon wavenumbers) and the NC size (using atomic force microscopy and optical absorption data), the experimental RRS spectra were described rather well by this theory, including the line shape and polarization dependence of the scattering intensity. Even though the presence of a compressive strain in the NCs (introduced by the matrix) masks the expected downward shift owing to the phonons' spatial quantization, the asymmetric broadening of both Raman peaks is similar to that characteristic of NCs of pure binary materials. Although with some caution, we suggest that both CdSe‐like and CdS‐like optical phonon modes indeed are propagating within the NC size unless the alloy is considerably heterogeneous. Copyright © 2011 John Wiley & Sons, Ltd.     

Fröhlich electron-phonon interaction in CdSxSe1-xnanocrystals

We demonstrate that the polar electron-phonon coupling in CdS_xSe_1-x nanocrystals increases with decreasing crystallite size. This result is supported by the size dependence of the Huang-Rhys parameter measured by absorption and photoluminescence spectroscopy and by microprobe resonant Raman measurements which allow us to determine the size dependence of the electron-LO phonon coupling and the relative strength between Fröhlich and deformation potential Raman polarizabilities.     

Study of spin–phonon coupling in LiFe1 − xMnxPO4olivines

LiFe_{1 − x}Mn_xPO₄ olivines are promising material for improved performance of Li‐ion batteries. Spin–phonon coupling of LiFe_{1 − x}Mn_xPO₄ (x = 0, 0.3, 0.5) olivines is studied through temperature‐dependent Raman spectroscopy. Among the observed phonon modes, the external mode at ~263 cm⁻¹ is directly correlated with the motions of magnetic Fe²⁺/Mn²⁺ ions. This mode displays anomalous temperature‐dependent behavior near the Néel temperature, indicating a coupling of this mode with spin ordering. As Mn doping increases, the anomalous behavior becomes clearly weaker, indicating the spin–phonon coupling quickly decreases. Our analyses show that the quick decrease of spin–phonon coupling is due to decrease of the strength of spin–phonon coupling, but not change of spin‐ordering feature with Mn doping. Importantly, we suggest that the low electrochemical activity of LiMnPO₄ is correlated with the weak spin–phonon coupling strength, but not with the weak ferromagnetic ground state. Our work would play an important role as a guide in improving the performances of future Li‐ion batteries. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural analysis of xCsCl(1−x)Ga2S3 glasses by means of DFT calculations and Raman spectroscopy

The alkali metal halide doping of gallium‐sulfide glasses yields improvements in the optical, thermal and glass forming properties. To understand these improvements, the short‐range order of xCsCl(1 − x)Ga₂S₃ glasses was probed by Raman spectroscopy. Raman spectra have been interpreted using density functional theory (DFT) harmonic frequency calculations on specific clusters of GaS₄H₄ and/or GaS₃H₃Cl tetrahedral subunits. The assignment of the observed vibrational bands confirms the main structural conclusions obtained with X‐ray and neutron diffraction experiments and gives some new insights into the gallium‐network present in the xCsCl(1 − x)Ga₂S₃ glasses. At the lowest concentration, the observed spectrum may be interpreted with small clusters such as dimers and trimers connected by corner‐sharing (CS) GaS₄H₄ tetrahedral subunits. The vibrational fingerprints of tri‐clusters with three‐fold coordinated sulfur atoms have also been identified; however, no Raman signature of chlorine‐doped subunits has been found to be caused by their insufficient intensity. For higher CsCl concentrations, distinct spectral features corresponding to chlorine‐doped clusters appear and are increasing in intensity with x. In other words, undoped and Cl‐doped tetrahedra coexist in the xCsCl(1 − x)Ga₂S₃ glasses. The added chlorine atoms induce a fragmentation of the glass network and replace the sulfur atoms in the CS tetrahedral environment. The comparison of the observed spectra with theoretical predictions and diffraction data favoured one‐fold coordinated chlorine atoms in the glass network. Copyright © 2009 John Wiley & Sons, Ltd.     

Controlled SnO2 nanocrystal growth in SiO2–SnO2 glass‐ceramic monoliths

Crack‐free (100–x) SiO₂–x SnO₂ glass‐ceramic monoliths have been prepared by the sol–gel method obtaining for the first time SnO₂ concentrations of 20% with annealing at 1100 °C. Heat‐treatment resulted in the formation and growth of SnO₂ nanocrystals within the silica matrices. Combined use of Fourier transform–Raman spectroscopy and in situ high‐temperature X‐Ray diffraction shows that SnO₂ particles begin to crystallize in the cassiterite‐type phase at 80 °C and that their average apparent size remains around 7 nm, even after annealing at 1100 °C. Nanocrystal sizes and size distributions determined by low‐wavenumber Raman are in good agreement with those obtained from transmission electron microscopy measurements. Results indicate that the formation and the growth of SnO₂ nanocrystals impose a residual porosity in the silica matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Ag–Ge–Se glasses: a vibrational spectroscopy study

Ag_x(Ge_0.25Se_0.75)_100−x glasses with x varying from 0 to 25 have been shown to exhibit a conductivity threshold around x ~8–10. In this work, the structural changes induced by introduction of Ag in Ge₂₅Se₇₅ glass have been investigated using Raman and infra‐red spectroscopies. In ambient conditions, changes are observed in position, width and intensity for vibrations assigned to Ge–Se bonds, showing that the tetrahedral network is relaxed and gains flexibility as Ag is introduced. High pressure experiments on two glasses containing 5 and 25 at.% Ag confirm that Ag‐rich (25%) glasses clearly exhibit higher compressibility than Ag‐poor (5%) glasses. Copyright © 2013 John Wiley & Sons, Ltd.     

Low‐temperature synthesis and Raman scattering of Mn‐doped ZnO nanopowders

Nanocrystalline Mn‐doped zinc oxides Zn_1−xMn_xO (x = 0–0.10) were synthesized by the sol–gel technique at low temperature. The calcination temperature of the as‐prepared powder was found at 350 °C using differential thermal analysis. A thermogravimetric analysis showed that there is a mass loss in the as‐prepared powder till 350 °C and an almost constant mass till 800 °C. The X‐ray diffraction patterns of investigated nanopowders calcined at 350 °C correspond to the hexagonal ZnO structure without any foreign impurities. The average grain size of the nanocrystal that was observed around ∼25–40 nm from transmission electron microscopy matched well with the crystallite size calculated from the line shape of X‐ray diffraction. The chemical bonding structure in Zn_1−xMn_xO nanopowders was examined using X‐ray photoelectron spectroscopy techniques, which indicate substitution of Mn²⁺ ions into Zn²⁺ sites in ZnO lattice. Micro Raman spectroscopy confirmed the insertion of Mn ions in the ZnO host matrix, and similar wurtzite structure of Zn_1−xMn_xO (x < 10%) nanocrystals. Temperature‐dependent Raman spectra of the nanocrystals displayed suppression of luminescence and enhancement in full width at half maximum in pure ZnO nanocrystals with increase in temperature, which suggests an enhancement in particle size at elevated temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Phonon confinement and substitutional disorder in Cd1−xZnxS nanocrystals

1‐longitudinal optical (LO) phonons in free‐standing mixed Cd_1−xZn_xS nanocrystals, synthesized using chemical precipitation, are investigated using Raman spectroscopy. As expected for the nanocrystals, the 1‐LO modes are found to appear at slightly lower wavenumbers than those in the bulk mixed crystals and exhibit one‐mode behavior. On the other hand, the line broadening is found to be much more than that can be accounted on the basis of phonon confinement. From the detailed line‐shape analysis it turns out that the substitutional disorder in the mixed crystals contributes much more to the line broadening than the phonon confinement. The linewidth arising from these mechanisms are also extracted from the analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies on Structural,Morphological and Optical Properties of Chemically Deposited CdS<Subscript>1-x</Subscript>Se<Subscript>x</Subscript> Thin Films

The thin films of CdS_1-xSe_x were successfully deposited over glass substrates by chemical bath deposition technique. Cadmium acetate, thiourea and sodium selenosulfate were used as source materials for Cd²⁺, S^2? and Se^2? ions, while 2-mercaptoethanol was used as capping agent. The various deposition conditions such as precursor concentration, deposition temperature, pH and deposition time were optimized for the deposition of CdS_1-xSe_x thin films of good quality and the films were annealed at 200° and 300 °C. The structural, morphological, chemical and optical properties were examined by various characterization techniques and discussed in detail. The optical band gap of CdS_1-xSe_x thin film samples were estimated and found in the range from 2.11 to 1.79 eV for as-deposited and annealed thin films.     

Studies on growth and characterization of ternary CdS1−xSex alloy thin films deposited by chemical bath deposition technique

Ternary alloyed CdS_1−xSe_x thin films of variable composition ‘x’ were grown by the simple and economical chemical bath deposition technique. The as-grown thin films were characterized for structural, compositional, surface morphological, optical and electrical studies. The X-ray diffraction (XRD) patterns of the sample indicated that all the samples were polycrystalline in nature with hexagonal structure. Scanning electron microscopy (SEM) micrographs showed uniform morphology with spherical shaped grains distributed over entire glass substrate. EDAX studies confirmed that the CdS_1−xSe_x films were having approximately same stoichiometry initially as well as finally. Room temperature optical measurements showed that band gap engineering could be realized in CdS_1−xSe_x thin films via modulation in composition ‘x’. Electrical resistivity of CdS_1−xSe_x thin films for various compositions was found to be low. The broad and fine tunable band gap properties of ternary CdS_1−xSe_x thin films have potential applications in opto-electronic devices.