Characterization of semiconductor core-shell nanoparticles by resonant Raman scattering and photoluminescence spectroscopy

Colloidal CdSe nanoparticles (NPs), passivated with CdS and ZnS, were characterized by resonant Raman scattering and photoluminescence (PL). The effect of the passivating shell, its volume and formation procedure on optical and vibrational spectra is discussed. Analyzing the Raman peaks due to optical phonons inside the core and those related to the core-shell interface allows some understanding of the relation between the core-shell structure and its PL properties to be achieved. In particular, a compositional intermixing at the core/shell interface of the NPs was deduced from the Raman spectra, which can noticeably affect their PL intensity.     

Phonon confinement effect on nanocrystalline LiCoO2 studied with Raman spectroscopy

A systematic investigation on nanocrystalline LiCoO₂ has been carried out using Raman spectroscopy. We synthesized nanocrystalline LiCoO₂ (ca. 20-50 nm) through a combination of rapid thermal annealing at various annealing temperatures and a sol-gel method assisted with a triblock copolymer surfactant. Powder X-ray diffraction measurements revealed the formation of LiCoO₂. The crystallite size of LiCoO₂ from the Scherrer equation strongly depended on the annealing temperature. The crystallite size was confirmed by SEM and TEM measurements. Raman shifts of the A_1g and E_g modes for nanocrystalline LiCoO₂ exhibited a broadening and a frequency shift according to the crystallite size. While the frequency shift could be ascribed to a structural strain at the surface, the broadening was due to the phonon confinement effect produced by narrow crystal boundaries.     

Synthesis and photoluminescence of CeO2:Eu phosphor powders

The crystalline structure and photoluminescence (PL) properties of europium-doped cerium dioxide synthesized by the solid-state reaction method were analyzed. CeO₂:Eu³⁺ phosphor powders exhibit the pure cubic fluorite phase up to 10 mol% doping concentration of Eu³⁺. With indirect excitation of CeO₂ host at 373 nm, the PL intensity quickly increases with increasing Eu³⁺ concentration, up to about 1 mol%, and then decreases indicating the concentration quenching. While with direct excitation (467 nm), much more stronger PL emissions, especially the electric dipole emission ⁵D₀-⁷F₂ at 612 nm, are observed and no concentration quenching occurs up to 10 mol% doping concentration of Eu³⁺. The nature of this behavior and the cause of the concentration quenching were discussed.     

General behavior of longitudinal optical phonons in cubic diatomic crystals

A general relationship for longitudinal optical (LO) phonons in diatomic cubic crystals is introduced. The analysis of spectroscopic data of diatomic cubic crystals reveals that LO frequencies correlate directly with bulk moduli in a nearest-neighbor fashion. The proportionality constant is found to be dependent only on lattice geometries. Transverse effective charges can be obtained when the Lyddane-Sachs-Teller is incorporated into the model. Our calculations are in excellent agreement with experimental values and theoretical calculations. Some interesting implications of the model are discussed.     

Raman spectroscopic and photoluminescence study of single-crystalline SnO2 nanowires

Single-crystalline SnO₂ nanowires with sizes of 4-14 nm in diameter and 100-500 nm in length were produced in a molten salt approach by using hydrothermal synthesized precursor. Structural characters of the nanowires were examined by X-ray diffraction and high-resolution electron transmission microscopy. Raman, photoluminescence and X-ray photoelectron spectra of the samples were examined under heat treatments. Three new Raman modes at 691, 514 and 358 cm⁻¹ were recorded and assigned. The former two are attributed to activation of original Raman-forbidden A_2uLO mode and the third is attributed to defects in small-sized nanowires. A strong photoluminescence is observed at about 600 nm, the temperature effects is examined and the origin of the PL process is discussed via X-ray photoelectron spectra.     

Characteristics of photoluminescence and Raman spectra of InP doped silica fiber

We fabricated a silica optical fiber doped with InP sandwiched in the core and the inner cladding layers by using the conventional modified chemical vapor deposition process. We presented the experimental X-ray analysis on the optical properties and found that compound InP was contained in the fiber core after annealing process. Broadband photoluminescence observed in InP doped fiber was well coincided with those coming from the recombination of deep levels in InP. The occurrence of temperature-dependent photoluminescence both at the lower and room temperature would be related with the localized defects and their confinement in the micro-network structure of Si-O-Si. The Raman spectra reveal that Si-O-In vibration would disorder the silica ring structures and enervate their vibrations.     

Raman and magnetic susceptibility studies of hexagonal elpasolite Cs2NaAlF6:Cr

Polarized Raman scattering spectra of distorted elpasolites Cs₂NaAlF₆ with a Cr³⁺ content of 0.1, 0.5 and 3.0 at% have been studied at both room temperature and 16 K. A shoulder located near the very intense band assigned to the AlF₆³⁻ A_1g mode indicates that the guest ion causes only small perturbations to the host lattice. Magnetic susceptibility measurements performed on the 0.1, 0.5, 3, 10 and 50 at% samples show that for particular concentrations the Cr³⁺ ions are not isolated, but participate to inter and/or intra-cluster magnetic exchange.     

Raman study of BiFeO3 with different excitation wavelengths

Raman spectra of bismuth ferrite (BiFeO₃) over the frequency range of 100-1500 cm⁻¹ have been systematically investigated with different excitation wavelengths. The intensities of the two-phonon modes are enhanced obviously under the excitation of 532 nm wavelength. This is attributed to the resonant behavior when incident laser energy closes to the intrinsic bandgap of BiFeO₃. The Raman spectra of BiFeO₃ excited at 532 nm were measured over the temperature range from 77 to 678 K. Besides the abnormal changes of the peak position and the linewidth of the A₁ mode at 139 cm⁻¹, the prominent frequency shift, the line broadening and the decrease of the intensity for the two-phonon mode at 1250 cm⁻¹ were observed as the temperature increased to Néel temperature (T_N). All these results indicate the existence of strong spin-phonon coupling in BiFeO₃.     

Effect of isotope substitution and doping on the Raman spectrum of galena (PbS)

The Raman spectrum of natural PbS has been shown to exhibit features related to the IR-active (Raman forbidden) LO phonons and to allowed scattering by two phonons. In order to confirm the vibrational nature of these features, and their peculiar temperature dependence, we compare here the spectra obtained for natural samples (i.e. mineral as well as synthetic with the natural isotopic abundance) with those measured for crystals prepared from highly enriched ³⁴S. The observed isotopic shifts confirm the vibrational nature of the structures mentioned above. We have also measured the spectra of synthetic samples of PbS annealed at several different pressures of sulphur. Because of their non-stoichiometric sulphur content they have carrier concentrations (either electrons or holes) in the 1×10¹⁷-3×10¹⁸ carriers/cm³ range (as determined from their IR reflection spectra). The measured spectra, as well as their temperature dependence, do not depend on the bulk carrier concentration, a fact that must result from surface pinning of the Fermi level within the fundamental energy gap.We finally discuss the apparent paradox of why the IR spectra reveal coupled LO-phonon-plasmon modes whereas the Raman spectra exhibit the bare LO-phonons.     

Confocal Raman spectroscopic mapping studies on a single CuO nanowire

In this study we are able, using a copper grid substrate, to successfully grow separate nanowires with a high level of crystallinity, for a length of up to 10 μm. They were synthesized under various temperatures. We compare and contrast three types of geometries (micron-, nano-scale, and tip-like single CuO nanowires), to identify their potential for monitoring the size effects of quantum confinements. The confocal Raman spectrometry results confirm the expected outcome, that reducing of the diameter of a cylindrical cross-section of a single nanowire results in Raman frequency downshifts. The results can be explained by the bond polarizability model. The applicability of investigating the size effects of the quantum confinement of the tip-like geometry of a single nanowire without any preparation for different sizes of nanoparticles is possible because the detection is relatively straightforward and the reproduced Raman signals can be observed.     

Spectral analysis of Pr-, Sm- and Dy-doped transparent GeO2-BaO-TiO2 glass ceramics

In this paper, we present the photoluminescence properties of Pr³⁺-, Sm³⁺- and Dy³⁺-doped germanate glasses and glass ceramics. From the X-ray diffraction measurement, the host glass structure was determined. These glasses have shown strong absorption bands in the near-infrared (NIR) region. Compared to Pr³⁺-, Sm³⁺- and Dy³⁺-doped glasses, their respective glass ceramics have shown stronger emissions due to the Ba₂TiGe₂O₈ crystalline phase. For Pr³⁺-doped glass and glass ceramic, emission bands centered at 530 nm (³P₀→³H₅), 614 nm (³P₀→³H₆), 647 nm (³P₀→³F₂) and 686 nm (³P₀→³F₃) have been observed with 485 nm (³H₄→³P₀) excitation wavelength. Of them, 647 nm (³P₀→³F₂) has shown bright red emission. Emission bands of ⁴G_5/2→⁶H_5/2 (565 nm), ⁴G_5/2→⁶H_7/2 (602 nm) and ⁴G_5/2→⁶H_9/2 (648 nm) for the Sm³⁺:glass and glass ceramic, with excitation at ⁶H_5/2→⁴F_7/2 (405 nm) have been recorded. Of them, ⁴G_5/2→⁶H_7/2 (602 nm) has shown a bright orange emission. With regard to the Dy³⁺:glass and glass ceramic, a bright fluorescent yellow emission at 577 nm (⁴F_9/2→⁶H_13/2) has been observed, apart from ⁴F_9/2→⁶H_11/2 (667 nm) emission transition with an excitation at 454 nm (⁶H_15/2→⁴I_15/2) wavelength. The stimulated emission cross-sections of all the emission bands of Pr³⁺, Sm³⁺ and Dy³⁺:glasses and glass ceramics have been computed based on their measured full-width at half-maxima (FWHM, Δλ) and lifetimes (τ_m).     

Influence of hydrogenation on the structure and visible photoluminescence of germanium oxide thin films

Substoichiometric germanium oxide thin films were prepared by evaporation of GeO₂ powder. The as-deposited samples showed a luminescence band in the visible range. Hydrogen was used to passivate the dangling bond defects and therefore to determine the origin of photoluminescence in the germanium oxide films. Hydrogen was introduced in the films from an electron cyclotron resonance (ECR) plasma source during or after the evaporation. The films hydrogenated during evaporation contain little oxygen because of an etching mechanism. In the post-hydrogenated films, the oxygen content is higher. With the hydrogenation treatment, the oxygen dangling bonds are suppressed. It is proposed that the photoluminescence in the visible range is attributed to the structural defects.     

Synthesis of nanocrystalline magnesium nitride (Mg3N2) powder using thermal plasma

Nanocrystalline magnesium nitride (Mg₃N₂) powder was synthesized from bulk magnesium by thermal plasma at atmospheric pressure. Magnesium vapor was generated through heating the bulk magnesium by DC plasma jet and reacted with ammonia gas. Injecting position and flow rates of ammonia gas were controlled to investigate an ideal condition for Mg₃N₂ synthesis. The synthesized Mg₃N₂ was cooled and collected on the chamber wall. Characteristics of the synthesized powders for each experimental condition were analyzed by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and thermogravity analysis (TGA). In absence of NH₃, magnesium metal powder was formed. The synthesis with NH₃ injection in low temperature region resulted in a formation of crystalline magnesium nitride with trigonal morphology, whereas the mixture of magnesium metal and amorphous Mg₃N₂ was formed when NH₃ was injected in high temperature region. Also, vaporization process of magnesium was discussed.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

A comparative study of microstructure of RuO2 nanorods via Raman scattering and field emission scanning electron microscopy

Raman scattering (RS) and field emission scanning electron microscopy (FESEM) have been used to extract microstructural information of RuO₂ nanorods (NRs) and a two-phase system comprising NRs embedded in polycrystalline matrix deposited on different substrates by the metal-organic chemical vapor deposition method. The red shifts and asymmetric broadening of the Raman line shape for the NRs are analyzed by the spatial correlation model. The deduced spatial correlation length l is found to be much smaller than that of the average size L₀ estimated from the FESEM images. The Raman features for the two-phase system can be resolved into two parts: a Lorentzian line shape feature corresponding to the polycrystallite at higher frequency side and an asymmetrically broadened NRs' signature located at lower frequency end. The volume fraction of NRs in the two-phase system can be determined from the analysis. These results demonstrate the significance of RS as a structural characterization method when used in conjunction with FESEM.     

Photoluminescence and Raman studies of Xe ion-implanted diamonds: Dependence on implantation dose

We report on photoluminescence and Raman studies of Xe ion-implanted diamond. Several natural and high-purity artificial diamonds implanted within the wide dose range of 10¹⁰-5×10¹⁴ ion/cm² were studied. The room temperature luminescence of the Xe center consists of two zero phonon lines, at 813 nm (strong) and 794 nm (weak). The dose dependences of photoluminescence and Raman spectra were studied. For doses less than 10¹³ ion/cm², the luminescence intensity grows with the implantation dose linearly. The defect-induced photoluminescence quenching was observed for doses equal or more than 10¹³ ion/cm². Possible models of the Xe center will be discussed. The nature of damages induced by ion implantation at different doses was analyzed using micro-Raman spectroscopy.     

Rapid and quantitative detection of ethanol proportion in ethanol-gasoline mixtures by Raman spectroscopy

The paper reports a Raman spectral in-situ detection technique to measure the ethanol proportion in an ethanol-gasoline mixture rapidly and quantitatively. The transformed information of Raman spectra for different mixtures of gasoline and ethanol have been observed and recorded. The relative intensity ratio of two typical Raman peaks for ethanol and gasoline satisfies a linear relation with a variation in volume ratio which could be used as a quantitative measure. This method, compared with the direct intensity measurement of a Raman peak, may not only eliminate the random measurement error due to dark current, but also confirm the accurate the proportion of ethanol and gasoline.     

Photoluminescence at room temperature in polycrystalline BaxSr1−xTiO3 ceramics obtained by solid-state reaction method

Stoichiometric Ba_xSr_1−xTiO₃ ceramics (x=0.7, 0.8, and 0.9) have been prepared by solid-state reaction method. It has been observed in our experiments that the photoluminescence (PL) spectra in such samples at room temperature were centered around 800 nm; the results have been found to differ from observations in current literature. An explanation of this phenomenon was given, and the origin of such photoluminescence is ascribed to certain defects existing in these compounds, such as oxygen vacancies.