Surface enhanced Raman scattering of light by ZnO nanostructures

Raman scattering (including nonresonant, resonant, and surface enhanced scattering) of light by optical and surface phonons of ZnO nanocrystals and nanorods has been investigated. It has been found that the nonresonant and resonant Raman scattering spectra of the nanostructures exhibit typical vibrational modes, E ₂(high) and A ₁(LO), respectively, which are allowed by the selection rules. The deposition of silver nanoclusters on the surface of nanostructures leads either to an abrupt increase in the intensity (by a factor of 10³) of Raman scattering of light by surface optical phonons or to the appearance of new surface modes, which indicates the observation of the phenomenon of surface enhanced Raman light scattering. It has been demonstrated that the frequencies of surface optical phonon modes of the studied nanostructures are in good agreement with the theoretical values obtained from calculations performed within the effective dielectric function model.     

Surface-Enhanced Hyper-Raman Spectroscopy

Abstract

Hyper-Raman scattering (HRS), first theoretically predicted by Decius and Rauch in 1959 [l] and experimentally demonstrated by Terhune et al. in 1965 [2], is a nonlinear optical process involving two incident photons (ω₀) and one emitted photon (ω). The emitted hyper- Raman photon frequencies are Raman-shifted relative to the second harmonic frequency (2ω₀) of the incident laser radiation [3–6]. The energy difference (2ω₀ – w) corresponds to one of the characteristicvibrational frequencies of the scattering medium or molecule. In Fig. 1 is given a schematic illustration of resonant and nonresonant HRS. The primary advantage of this nonlinear optical technique lies in its more relaxed selection rules compared with IR and Raman [7,8]. AlllR-active vibrational modes are hyper-Raman allowed, and those modes inactive in both IR and Raman (i.e., the “silent” modes) may be active in hyper-Raman scattering.     

Raman scattering by LO-phonon-plasmon coupled modes in p-type GaAs: Wave vector non conservation

Raman scattering from nearly unscreened LO-phonons in heavily doped p-GaAs has been detected in forbidden configuration resonant near the E₁ energy gap. The observed scattering is explained in terms of coupled LO-phonon-plasmon modes with large wave vectors. The required breakdown of the wave vector conservation is attributed to scattering by the ionized acceptor-impurities (Zn).     

Time-resolved hot luminescence and resonant Raman scattering: Cu2O revisited

Time-resolved resonant scattering of both one-phonon and two-phonon Raman modes at the 1s ortho-exciton state of the yellow series in Cu₂O is reported. From the time dependence of the one-phonon mode we determine the scattering rate among the triply degenerate ortho-exciton states to be 2.5 × 10⁸sec^-1. From the two-phonon modes we directly determine the exciton lifetime as a function of its kinetic energy. In both cases the resonant scattering is found to be dominated by hot luminescence.     

Binary phase shaping for selective single‐beam CARS spectroscopy and imaging of gas‐phase molecules

We report on mode‐selective single‐beam coherent anti‐Stokes Raman scattering spectroscopy of gas‐phase molecules. Binary phase shaping (BPS) is used to produce single‐mode excitation of O₂, N₂, and CO₂ vibrational modes in ambient air and gas‐phase mixtures, with high‐contrast rejection of off‐resonant Raman modes and efficient nonresonant‐background suppression. In particular, we demonstrate independent excitation of CO₂ Fermi dyads at ∼1280 and ∼1380 cm⁻¹ and apply BPS for high‐contrast imaging of CO₂ jet in ambient air. Copyright © 2010 John Wiley & Sons, Ltd.     

Resonant raman scattering at the E1 energy gap of semiconductor crystals

We present a discussion of resonant Raman scattering by optical phonons at the E₁ energy gap of group IV and groups III–V compound semiconductor crystals (e.g., Ge and InSb). For allowed scattering by TO and LO phonons, the q-dependent “double resonant” two-band calculation of the Raman tensor may display destructive interference effects when the intermediate electron-hole pairs are uncorrelated. We also discuss the Franz-Keldysh mechanism of resonant electric field induced Raman scattering by LO phonons. The double resonance terms due to this mechanism will, for large electric fields, broaden and have its largest resonance enhancement at the energy gap.     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

Directional dispersion of extraordinary phonons in layer compound InSe

The resonant Raman scattering of polar optical phonons has been measured in trigonal γ-InSe at the E'₁ exciton edge. The two-phonon scattering spectrum widely spreads over the frequency range of 50 cm^-1 with an extremely asymmetric lineshape. This spectrum has been interpreted in terms of the directional dispersion of extraordinary LO and TO phonons.     

Electric field modulated Raman scattering in CdS

We have observed electric field modulated Raman scattering by A₁ LO phonons in CdS. The field induced scattering is observed with a geometry in which Raman scattering by A₁ LO phonons is normally allowed. The interference of the field induced and allowed terms in the transition susceptibility leads to a modulated Raman scattering intensity proportional to the applied field. This is contrasted with data previously reported on field induced Raman scattering by E₁ LO phonons in a configuration in which the Raman scattering is normally forbidden and in which there is no interference between linear wavevector dependent and field induced terms in the transition susceptibility. Electric field effects on Raman scattering by TO phonons and by 2 LO phonons is also discussed.     

Raman and infrared spectra of CdIn2S4 and ZnIn2S4

Four one-phonon Raman lines have been found in CdIn₂S₄ (ZnIn₂S₄) spinels at 92 (72) cm^-1, 186 (184) cm^-1, 246 (253) cm^-1, and 367 (372) cm^-1 for incident photon energies well below the energy gap E_G ～ 2.4 (2.2) eV at 300 K. For photon energies close to E_G, the 367 cm^-1 mode underwent a resonant enhancement in CdIn₂S₄ and four infrared active but Raman forbidden F_1u modes appeared in the CdIn₂S₄ and ZnIn₂S₄ Raman spectra: TO modes at 226 (221) cm^-1 and 309 (312) cm^-1, and LO modes at 274 (272) cm^-1 and 340 (342) cm^-1.     

Raman spectra of GaAs-AlxGa1-xAs superlattices

Systematic theoretical studies of Raman spectra of GaAs-Al_xGa_1-xAs superlattices are presented. The electronic states are described by an envelope-function method and the phonon modes are described in a microscopic rigid-ion model. Both resonant and nonresonant Raman scattering processes are considered. For resonant Raman scattering, the effects of discrete exciton states plus the continuum and the valence-band mixing are included via a k-space sampling method. Both the Fröhlich and deformation-potential mechanisms for electron-phonon coupling are considered. These two mechanisms are responsible for principal features in the z(x, x)z̄ and z(x, y)z̄ geometries, respectively. We find that the effects of exciton continuum states are quite important and the resonant Raman spectra so obtained are in much better agreement with experiment compared to those without including the exciton continuum states.     

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.     

Disorder‐induced Raman scattering effects in one‐dimensional ZnO nanostructures by incorporation and anisotropic distribution of Dy and Li codopants

In Dy³⁺ and Li⁺ codoped ZnO nanowires, the additives accumulate preferentially in {0001} planes, resulting in serious breakdown of the translational symmetry in ab plane and modification of the phonon oscillation field. Not only acoustic overtones, silent optical modes, surface optical (SO) phonon modes, and multi‐phonon processes can be effectively observed in the nonresonant Raman scattering (RS) and the Fourier‐transform infrared (FTIR) spectra, but the quasi‐LO and TO modes of mixed A₁ and E₁ symmetry also show a noticeable red shift from E₁ symmetry (in ab plane) to A₁ symmetry (along c axis). The presence of dislocations and internal strain at the surface layer rich in additives, coming from the segregation of additives, forms a quasi‐bilayer system, resulting in the appearance and enhancement of SO phonon modes in RS and FTIR spectra. The Fano interference, originating from the interaction between the discrete scattering from phonons and the continuum scattering from laser‐induced electrons in the doped nanostructures, leads to typical asymmetric lineshapes on the lower wavenumber sides. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman scattering studies on manganese ion-implanted GaN

This paper reports that the Raman spectra have been recorded on the metal-organic chemical vapour deposition epitaxially grown GaN before and after the Mn ions implanted. Several Raman defect modes have emerged from the implanted samples. The structures around 182 cm^-1 modes are attributed to the disorder-activated Raman scattering, whereas the 361 cm^-1 and 660 cm^-1 peaks are assigned to nitrogen vacancy-related defect scattering. One additional peak at 280 cm^-1 is attributed to the vibrational mode of gallium vacancy-related defects and/or to disorder activated Raman scattering. A Raman-scattering study of lattice recovery is also presented by rapid thermal annealing at different temperatures between 700 °C and 1050 °C on Mn implanted GaN epilayers. The behaviour of peak-shape change and full width at half maximum (FWHM) of the A₁(LO) (733 cm^-1) and E^H₂ (566 cm^-1) Raman modes are explained on the basis of implantation-induced lattice damage in GaN epilayers.     

Resonant Raman scattering of CdCr2Se4

The scattering cross section of the Raman-active phonons at 156 cm^?1 (Eg) and 169 cm^?1 (F2g) in the ferromagnetic semiconductor CdCr₂Se₄ (T_c=130 K) has been measured as a function of incident photon energy between 1.55 and 2.81 eV, both in the ferromagnetic and paramagnetic phases. The resonance curve peaks sharply near 2 eV and shows a broadening for temperatures below the Curie point. The relative line intensities change significantly with photon energy. The results show that the concept of spin-dependent Raman scattering in the ferromagnetic spinels has to be revised in terms of exchange-splitting-induced resonant Raman scattering.     

Resonant Raman scattering from FeS2 (pyrite)

We have observed resonant Raman scattering from the A_g mode of FeS₂ (pyrite) for incident laser energies between 2.41 and 2.73 eV, these energies being well above the fundamental gap at 0.9 eV. In contrast to the behavior of the A_g mode intensity, the E_g and T_g modes do not show resonant behavior. A simple two band model which predicts the Raman cross section proportional to |?χ/?ω|² is found to be inadequate to describe the observed intensity variation with the incident laser energy.     

Polaritons and optical phonon assignment in orthorhombic HCOOLi·H2O crystal by Raman scattering measurement

Optical phonon modes of orthorhombic HCOOLi·H₂O crystal are investigated by laser Raman scattering technique. An A₁ mode polariton with energy between 1250 cm^-1 and 1343 cm^-1 is observed by near-forward Raman scattering using Ar laser.     

Raman study of structural disorder in ZnO nanopowders

Raman scattering spectroscopy has been used for the characterization of zinc oxide nanoparticles obtained by mechanical activation in a high‐energy vibro‐mill and planetary ball mill. Raman modes observed in spectra of nonactivated sample are assigned to Raman spectra of the ZnO monocrystal, while the spectra of mechanically activated samples point out to the structural and stoichiometric changes, depending on the milling time and the choice of equipment. Observed redshift and peak broadening of the E₂^high and E₁ (LO) first‐order Raman modes are attributed to increased disorder induced by mechanical milling, followed by the effects of phonon confinement due to correlation length decrease. The additional modes identified in Raman spectra of activated ZnO samples are related to the surface optical phonon modes, due to the intrinsic surface defects and presence of ZrO₂as extrinsic defects introduced by milling in zirconia vials. Copyright © 2009 John Wiley & Sons, Ltd.     

Exciton-phonon interaction in mixed silver halides: Resonant Raman scattering vs photoluminescence

An investigation of resonant Raman scattering in mixed crystals of AgBr:Cl at 1.8 K shows that the zero-phonon and LO phonon-assisted exciton luminescence excited in the free indirect exciton absorption, exhibits an anomalous dependence on the exciton photon energy E_L. Close to the exciton gap, the bands show a Raman-like behaviour with their peaks at constant energetic distance from E_L. As E_L is tuned further into the absorption, the bands gradually develop into normal photoluminescence. The effect is explained by taking into account exciton relaxation via scattering by long-wavelength acoustic phonons, a process which is strongly energy dependent. In addition, resonant Raman scattering observed for excitation in the zero-phonon absorption suggests study for the first time of the mode behaviour of certain off-zone center phonons in this system.     

Infrared lattice vibration spectra of tetragonal ZnP2

Infrared reflectivity spectra of tetragonal ZnP₂ are measured in the frequency range from 40 to 600 cm^-1 for both polarization directions E ⊥ c and E 6 c. The parameters of 9 E modes and 4 A₂ modes are determined by a dispersion analysis of the spectra. Three additional A₂ modes are detected by infrared transmission measurements. The results obtained are compared with previous Raman scattering and two-phonon combination mode spectra.