Multiphonon resonant Raman scattering in N‐doped ZnO

Multiphonon resonant Raman scattering in N‐doped ZnO films was studied, and an enhancement of the resonant Raman scattering process as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed at room temperature. The resonant Raman scattering intensity of the 1LO phonon in N‐doped ZnO appears three times as strong as that of undoped ZnO, which mainly arises from the defect‐induced Raman scattering caused by N‐doping. The nature of the 1LO phonon at 578 cm⁻¹ is interpreted as a quasimode with mixed A₁ and E₁ symmetry because of the defects formed in the ZnO lattice. In addition, the previously neglected impurity‐induced two‐LO‐phonon scattering process was clearly observed in N‐doped ZnO. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectral probe on increased local vibrational modes and phonon lifetimes in Ho3+‐doped Bi2O3 micro‐rods

We report the appearance and enhancement in intensity of impurity related local vibrational modes in Bi₂O₃ : Ho micro‐rods along with normal modes. Pure and Ho‐doped Bi₂O₃ micro‐rods were synthesized by conventional co‐precipitation method at 60 °C. The structural and morphological studies were carried out using powder X‐ray diffraction technique and scanning electron microscopy, respectively. Raman spectroscopic studies reveal the existence of local phonon vibrational modes (LVM) due to the incorporation of Ho³⁺. Harmonic approximation method was employed to find the dopant‐related peak in the Raman spectra. Variation in full width at half maximum for LVM with increase in Ho³⁺ was also investigated. This increase in FWHM indicates the decrease in crystallinity of the doped samples. The phonon lifetime calculation carried out for each samples and the decrease in phonon lifetime with doping concentration make this material a potential candidate for optical and electronic applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Micro‐Raman scattering spectroscopy study of Li‐doped and undoped ZnO needle crystals

ZnO nanostructures have attracted great attention for possible applications in optoelectronic and spintronic devices. The electrical resistivity because of carriers can be improved by the introduction of Li ions, as Li is a possible dopant for achieving p‐type ZnO. We have carried out a comprehensive micro‐Raman scattering study of the phonons in 1% Li‐ and undoped ZnO needle crystals grown and annealed at 1073 K for 1 and 2 h under oxygen environment. Phonon mode of doped and undoped ZnO does not show any measurable shift for the doping concentration of 1%. As line width is related to point defect density, we find for both Li‐ and undoped ZnO crystals the crystallinity is improving towards the tip of the needle crystals. Copyright © 2008 John Wiley & Sons, Ltd.     

Resonant two‐magnon Raman scattering in high‐Tc cuprates

Resonance enhancement of one‐phonon, two‐phonon, and two‐magnon Raman scattering in a general, exactly solvable, multiband model is explained in a way that is in accordance with the general analytical properties of the total optical conductivity tensor. Using this approach, the charge‐transfer limit of the Emery three‐band model is examined to explain resonance enhancement of the two‐magnon Raman spectra of high‐T_c cuprates, which is found in experiments to be of 3 orders of magnitude. While previous Raman and optical conductivity analyzes of the cuprates, based on the single‐band Hubbard model, are found to be consistent with the picture where one hole per one CuO₂ unit is localized on the Cu ion, the present three‐band approach allows the study of the opposite, strong copper‐oxygen hybridization limit, which is found to be in agreement with the results of nuclear magnetic resonance (NMR) and one‐phonon Raman scattering experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

One phonon resonant Raman scattering in a quantized spherical film

We have presented a theoretical calculation of the differential cross section (DCS) for the electron Raman scattering (ERS) process associated with surface optical (SO) phonon modes in a semiconductor quantized spherical film. We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum approach. We study the selection rules for the processes. Singularities are found to be size-dependent and by varying the size of the QDs, it is possible to control the frequency shift in the Raman spectrum. A discussion of the phonon behavior for the films with large and small size is presented. The numerical results are also compared with that of experiments.     

Ultraviolet Raman scattering in ZnO nanowires: quasimode mixing and temperature effects

We use near‐resonance Raman scattering to investigate zinc oxide (ZnO) nanowires grown by chemical vapor deposition on Si substrates. We discuss the role of quasimode mixing on the wavenumber of the longitudinal optical (LO) bands, and we perform Raman measurements with different excitation powers to investigate possible laser heating effects. We find that in the Raman spectra of as‐deposited nanowires grown along the c‐axis of wurtzite, the LO bands are located slightly below the E₁(LO) mode of bulk ZnO. We perform a calculation of the expected LO wavenumber in an ensemble of randomly oriented nanowires. Our analysis shows that light refraction, together with the orientation‐dependent cross‐section of the nanowires for the incoming light, counterbalances quasimode mixing effects in the as‐grown product, giving rise to LO bands that are barely redshifted relative to the E₁(LO) mode. In the case of ZnO nanowires that have been mechanically removed (scratched) and subsequently deposited onto separate Si substrates, we observe clear laser‐induced heating. Temperature effects account well for the Raman wavenumber shifts displayed by the LO bands in the Raman spectra of the scratched nanowires. Copyright © 2010 John Wiley & Sons, Ltd.     

Cross‐section and selection rules in surface‐enhanced hyper Raman scattering

The expression for the surface‐enhanced hyper Raman scattering (SEHRS) cross‐section of symmetrical molecules within the framework of the dipole–quadrupole theory is presented. It is formed by contributions that depend on various dipole and quadrupole moments. The enhancement coefficients for the quadrupole enhancement mechanism in some limited cases can reach a value 10³⁰. It is demonstrated that the contributions follow some selection rules. Qualitative classification of the contributions based on the enhancement degree is given. It is demonstrated that the SEHR spectra of pyrazine and pyridine can be explained by the presented theory. Copyright © 2011 John Wiley & Sons, Ltd.     

Defects in crystals studied by Raman scattering

Raman studies of crystal defects are reviewed. Raman spectroscopy is a powerful technique and has been used widely for investigating disordered structures. The degree of disorder in a crystal is quantitatively evaluated in terms of the phonon correlation length. The asymmetric Raman line shapes in defective crystals such as microcrystals, ion-implanted semiconductors are well reproduced by the spatial correlation (SC) model. The effect of alloying induced-potential fluctuations on Raman scattering is also explained within the framework of the SC model. In disordered graphite, the in-plane phonon correlation length is obtained from the relative intensity ratio of the disorder induced peak. The initial lattice disordering rates and the relaxation rates of disorder are determined, using real-time Raman measurements during ion irradiation in a scale of seconds. In this way, the phonon confinement due to the local defects is observed in the kinetic manner. Localized vibrational modes of defects in crystals are also described. In particular, Raman observation of the hydrogen molecule in crystalline semiconductors is discussed in detail.     

One‐phonon resonant electron Raman scattering in a cylindrical GaAs/AlAs quantum dot

We have presented a theoretical calculation of the differential cross section for the electron Raman scattering process associated with the interface optical phonon modes in cylindrical GaAs quantum dots (QDs) with a AlAs matrix. We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum approach. The selection rules for the processes are studied. Singularities are found to be sensitively size‐dependent, and, by varying the size of the QDs, it is possible to control the frequency shift in the Raman spectra. A discussion of the phonon behavior for QDs with different size is presented. Copyright © 2013 John Wiley & Sons, Ltd.     

Halide‐ion‐assisted increase of surface‐enhanced hyper‐Raman scattering: a clear observation of the chemical effect

We show that the increase of surface‐enhanced hyper‐Raman scattering (SEHRS) intensity of organic dye molecules adsorbed on single silver (Ag) colloid aggregate in the presence of halide ions is a direct evidence of the chemical effect in the enhancement mechanism. Time‐dependent SEHRS measurements before and after adding halide ions enabled us to distinctly observe the chemical effect. The presence of the halide ions results to a more stable chemical interaction between metal and dye molecule, making it more resistant against photodegradation effects. This study can contribute in elucidating the chemical effect mechanism and aid in the development of SEHRS as a useful spectroscopic tool. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface optical phonon—assisted electron Raman scattering in a semiconductor quantum disc

We have carried out a theoretical calculation of the differential cross section for the electron Raman scattering process associated with the surface optical phonon modes in a semiconductor quantum disc.electron states are considered to be confined within a quantum disc with infinite potential barriers.The optical phonon modes we have adopted are the slab phonon modes by taking into consideration the Frohlich interaction between an electron and a phonon.The selection rules for the Raman process are given.Numerical results and a discussion are also presented for various radii and thicknesses of the disc,and different incident radiation energies.     

Non‐degenerate second‐order scattering and difference combination bands in infrared‐pump/anti‐Stokes resonance Raman‐probe experiments

Non‐degenerate second‐order scattering due to interaction of infrared and ultraviolet pulses is observed in picosecond infrared‐pump/anti‐Stokes Raman‐probe experiments under electronic resonance conditions. We detected resonance hyper‐Rayleigh scattering at the sum frequency of the pulses as well as the corresponding frequency‐down‐shifted resonance hyper‐Raman lines. Nearly coinciding resonance hyper‐Raman and one‐photon resonance Raman spectra indicate conditions of A‐term resonance Raman scattering. Second‐order scattering is distinguished from transient anti‐Stokes Raman scattering of v = 1 to v = 0 transitions and v = 1 to v′ = 1 combination transitions by taking into account their different spectral and temporal behaviour. Separating these processes is essential for a proper analysis of transient vibrational populations. Copyright © 2007 John Wiley & Sons, Ltd.     

Polarized Raman scattering in helimagnetic β‐MnO2

A rutile β‐MnO₂ film was grown on MgO substrate using plasma‐assisted molecular beam epitaxy (PAMBE) monitored by reflection high‐energy electron diffraction (RHEED). Polarized Raman spectra at various temperatures were obtained to investigate the influence of the helimagnetic structure on the vibrational modes of β‐MnO₂. A red shift of E_g modes indicates a gradual formation of spin angles between neighboring Mn⁴⁺ ions. The intensities of the E_g and A_1g modes with y‐polarized incidence increase remarkably below the Néel temperature. A new view as vibrational mode projection (VMP) indicates the interactions between the magnetic component of incident light and the helimagnetic structure. Copyright © 2008 John Wiley & Sons, Ltd.     

First-order Raman scattering in a free-standing GaN nanowire with ring geometry

We have investigated one phonon resonant Raman scattering in GaN nanowires (NWs) with ring geometry. We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum approach. The selection rules are studied. For the GaN NWs with small radius, results reveal that the main contribution to the differential cross-section (DCS) stems from the surface optical (SO) phonons especially from the high-frequency of SO phonons, with a minor contribution from the longitudinal optical (LO) phonons. Meanwhile, dispersions of the two branches of the SO phonon modes are obvious when the wire is thin. Moreover, compared to GaAs NWs, the GaN NWs make more contribution to the DCS in the small quantum size.     

Deep‐UV tip‐enhanced Raman scattering

We report for the first time the tip‐enhancement of resonance Raman scattering using deep ultraviolet (DUV) excitation wavelength. The tip‐enhancement was successfully demonstrated with an aluminum‐coated silicon tip that acts as a plasmonic material in DUV wavelengths. Both the crystal violet and adenine molecules, which were used as test samples, show electronic resonance at the 266‐nm excitation used in the experiments. With results demonstrated here, molecular analysis and imaging with nanoscale spatial resolution in DUV resonance Raman spectroscopy can be realized using the tip‐enhancement effect. Copyright © 2009 John Wiley & Sons, Ltd.     

N型4H-SiC低温拉曼光谱特性

利用拉曼散射技术对N型4H-SiC单晶材料进行了30～300 K温度范围的光谱测量。实验结果表明,随着温度的升高,N型4H-SiC单晶材料的拉曼峰峰位向低波数方向移动,峰宽逐渐增宽。分析认为,晶格振动随着温度的升高而随之加剧,其振动恢复力会逐渐减小,使振动频率降低;原子相对运动会随温度的升高而加剧,使得原子之间及晶胞之间的相互作用减弱,致使声学模和光学模皆出现红移现象。随着温度的升高,峰宽逐渐增宽。这是由于随着温度的升高声子数逐渐增加,增加的声子进一步增加了散射概率,从而降低了声子的平均寿命,而声子的平均寿命与峰宽成反比,因此随着温度的升高峰宽逐渐增宽。声子模强度随温度升高呈现不同规律,E₂(LA),E₂(TA),E₁(TA)和A₁(LA)声子模随着温度升高强度单调增加,而E₂(TO),E₁(TO)和A₁(LO)声子模强度出现了先增后减的明显变化,在138 K强度出现极大值。分析认为造成原因是由于当温度高于138 K时,高能量的声子分裂成多个具有更低能量的声子所致。     

Phonon–phonon interactions in Ce0.85Gd0.15O2−δ nanocrystals studied by Raman spectroscopy

Phonon–phonon interactions and phase stability of Gd‐doped ceria nanocrystals were examined over the temperature range 293–1100 K by Raman spectroscopy. The phonon confinement model (PCM) based on size, inhomogeneous strain and anharmonic effects was used to properly describe the anharmonic interactions in this system. The interplay between size and anharmonic effects influenced different phonon decay channels in nano grains than in larger grains. After the gradual cooling down to room temperature (RT), the Raman study revealed the phase separation in this system pointing to the phase instability of Ce_0.85Gd_0.15O_2−δ nanocrystals after heat treatment. The concentration of extrinsic (intrinsic) oxygen vacancies was also studied by Raman spectroscopy during the heat treatment of the Ce_0.85Gd_0.15O_2−δ nanocrystalline sample. Copyright © 2009 John Wiley & Sons, Ltd.