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.     

Resonant Raman scattering in nanostructures with InGaAs/AlAs quantum dots

Raman scattering by optical phonons in In_xGa_{1 ? x} As/AlAs nanostructures with quantum dots has been studied experimentally for compositions corresponding to x = 0.3?1 under out-resonance conditions. Features due to scattering by GaAs-and InAs-like optical phonons in quantum dots have been detected, and the phonon frequencies have been determined as a function of the dot composition. With increasing excitation energy, a red shift is observed in the frequency of the GaAs-like phonon in quantum dots, which testifies to Raman scattering selective by the size of quantum dots. Under resonant conditions, multiphonon light scattering by optical and interface phonons is observed up to the third order, including overtones of the first-order phonons of InGaAs and AlAs materials and their combinations.     

Surface enhanced Raman scattering by CdS quantum dots

Surface enhanced Raman scattering is studied in nanostructures with CdS quantum dots formed using the Langmuir-Blodgett technology. Features due to quantum dot longitudinal optical phonons are observed in the Raman spectra of both free CdS quantum dots and such dots distributed in an organic matrix. The surface enhanced Raman scattering by nanostructures with CdS quantum dots covered by an Ag cluster film is observed experimentally. Applying Ag clusters onto the nanostructure surfaces results in a sharp (40-fold) increase in the intensity of Raman scattering by optical phonons in the quantum dots. It is shown that the dependence of surface enhanced Raman scattering on the excitation energy is resonant with a maximum at the energy corresponding to the maximum absorption coefficient of Ag clusters.     

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.     

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.     

Well width dependence of electron-phonon interaction in ZnSe/ZnSxSe1-x superlattices determined by micro-raman spectroscopy

We report a study of multiphonon resonant Raman scattering in a series of symmetric (ZnSe)_d(ZnS_1-xSe_x)_d superlattices (SL), 20Å ≤ d ≤ 150Å. In addition to confined optical phonons, the energies of interface (IF) modes with in-plane wavevectors have been assessed by means of micro-probe Raman measurements in backscattering from the SL edge. The comparison between one- and two-phonon spectra shows that the electron-phonon interaction is dominated by ZnSe-like IF phonons for d < 50Å, whereas LO₂ phonons prevail for larger well.     

Surface enhanced Raman scattering from tris (bipyridine) ruthenium (II) adsorbed on silver-modified p-GaAs

Both surface enhanced Raman scattering (SERS) and surface enhanced resonant Raman scattering (SERRS) have been observed from Ru(bpy)₃²⁺ adsorbed on p-GaAs (1 0 0) after the electrodeposition of Ag particles onto the semiconductor surface. For the enhancement factor for SERS a lower limit of 10⁴ has been determined.     

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.     

Antiresonance of Raman Scattering in CdSxSe1-x Mixed Crystals

Abstract

Resonant enhancement of the Raman scattering cross section in II - IV semiconductors has recently received much attention both theoretically and experimentally. All existing theories anticipate a monotonic increase in the scattering intensities when the scattering radiation energy approaches the direct-energy gap. Contrary to them in an early Raman study of CdS¹ a cancellation of scattering efficiencies for the two TO modes prior to the onset of the resonance was pointed out. In a latter work on pure CdS Damen et al.² found even a more pronounced “antiresonance” behavior of the nonpolar E₂ phonon at 41 cm^?1. Thus, this striking feature seems to be rather common for the Raman active modes in CdS for which no electrooptic contribution to the scattering amplitude exists. The experimental data were qualitatively explained by assuming a destructive addition between nonresonant and the weaker resonant terms in LoudoN′s expression for the first-order Raman tensor³. Consequently the cancellation energy difference /E_G - hw_L/ depends on the ratio of the resonant term to the nonresonant terms.     

Raman spectroscopy of ZnS nanostructures

We report Raman scattering results of wurtzite ZnS nanowires, nanocombs, and nanobelts. The Raman spectrum obtained from ZnS nanowires exhibits first‐order phonon modes at 272, 284, and 350 cm⁻¹, corresponding to A₁/E₁ transverse optical, E₂ transverse optical, and A₁/E₁ longitudinal optical phonons, respectively. Several multiphonon modes are also observed. The longitudinal optical phonon mode varies in wavenumber for nanocombs and nanobelts, indicating that the residual strain varies during the morphological change from ZnS nanowires to nanocombs and ultimately to nanobelts. Interestingly, a surface optical (SO) phonon mode varies in wavenumber depending on the shape and surface roughness of the ZnS nanostructures. The surface modulation wavelengths of the ZnS nanowires, nanocombs, and nanobelts are estimated using the SO phonon dispersion relations and the observed SO phonon wavenumbers. Copyright © 2012 John Wiley & Sons, Ltd.     

Surface optical Raman modes in GaN nanoribbons

Raman scattering studies were performed in GaN nanoribbons grown along [1 0 0]. These samples were prepared inside Na‐4 mica nanochannels by the ion‐exchange technique and subsequent annealing in NH₃ ambient. Detailed morphological and structural studies including the crystalline orientation were performed by analyzing the vibrational properties in these GaN nanoribbons. Pressure in the embedded structure was calculated from the blue shift of the E₂(high) phonon mode of GaN. Possible red shift of optical phonon modes due to the quantum confinement is also discussed. In addition to the optical phonons allowed by symmetry, two additional Raman peaks were also observed at ∼633 and 678 cm⁻¹ for these nanoribbons. Calculations for the wavenumbers of the surface optical (SO) phonon modes in GaN in Na‐4 mica yielded values close to those of the new Raman modes. The SO phonon modes were calculated in the slab (applicable to belt‐like nanoribbon) mode, as the wavenumber and intensity of these modes depend on the size and the shape of the nanostructures. The effect of surface‐modulation‐assisted electron–SO phonon scattering is suggested to be responsible for the pronounced appearance of SO phonon modes. A scaling factor is also estimated for the interacting surface potential influencing the observed SO Raman scattering intensities. Copyright © 2010 John Wiley & Sons, Ltd.     

Optical phonons in CuAlS2

The optical phonons at k=0 of CuAlS₂ have been investigated by Raman scattering, infrared reflectivity and absorption measurements from 50 to 1000 cm^-1 at T=300 K. Eleven of the thirteen expected optically active phonons have been observed and identified with respect to their symmetry types. The phonon frequencies appear in a range from 498 to 76 cm^-1 with predominant polar modes at 445 and 266 cm^-1. The dielectric dispersion for E ⊥ c and E ∥ c has been determined by Kramers-Kronig integrations.     

旋光性单轴晶体的喇曼光谱中TO和LO模的识别

本文提出一种简便识别旋光性单轴晶体喇曼光谱中横模和纵模的方法。应用90°散射几何配置x(z+Δy,xz)y,散射光的偏振方向与x轴成δ夹角。应用Loudon给出的单轴晶体极性声子的喇曼散射效率公式,计算TO和LO模的散射效率,它们依赖于喇曼张量元和δ角,其极大值分别位于δ_max^TO和δ_max^LO处,这两个角度的符号正好相反。因此,由判定δ_max的符号,可以将TO和LO模区分开来,并且从|δ_max|值可以了解喇曼张量的各向异性。 关键词：     

Zone edge phonons in CdS1−xSex

Zone edge phonons of mixed CdS_1?xSe_x have been studied by mean of infrared absorption and Raman scattering techniques. In the A point of the Brillouin zone, it has been shown that transverse acoustical phonons have a one mode behaviour, and that optical phonons have a two modes behaviour. CdS and CdSe zone center phonons can combined and give a LO(CdS) + LO(CdSe) Raman peak in addition to the 2LO(CdS) and 2LO(CdSe) peaks; this is not the case for phonons from the edge of the Brillouin-zone where no CdS + CdSe combination can take place.     

Resonant Raman study of LO + acoustic phonon modes in CdSe

In studying resonant Raman scattering in the vicinity of the A and B excitons of CdSe, we have observed three new Raman peaks. Two of the peaks have been identified as two-phonon modes consisting of a longitudinal optical (LO) phonon plus respectively a transverse acoustic (TA) and a longitudinal acoustic (LA) phonon. A theory which involves the scattering of photoexcited B excitons to the A exciton by acoustic phonons via the piezoelectric exciton-phonon interaction was found to explain quantitatively the peak positions, lineshape and resonance enhancements of the observed peaks.     

Raman and infrared spectra of ZnSiAs2

The optical phonons at k = 0 of ZnSiAs₂ have been investigated by Raman scattering and infrared reflectivity measurements at 300 K. Eleven of thirteen expected optically active phonons have been observed and identified with respect to their symmetry types. The phonon frequencies appear in the range from 415 cm^-1 to 75 cm^-1 with predominant polar modes at 400 cm^-1 (gG₅), 389 cm^-1 (Γ₄) and 242 cm^-1 (Γ₄). The dielectric dispersion for E ⊥ c and E 6 c has been determined by Kramers-Kronig integrations.     

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.     

First-order Raman scattering in cylindrical wurtzite nanowire

We have presented a theoretical study on electron resonant Raman scattering (ERRS) process associated with the bulk longitudinal optical (LO), surface optical (SO) and quasi-confined (QC) phonon modes in a free-standing wurtzite nanowire (NW). We consider the Fröhlich electron–phonon interaction in the framework of the dielectric continuum model. Numerical calculations on the GaN material reveal that differential cross-section (DCS) is sensitive to the wire size. The bulk LO and high-frequency quasi-confined (QC₊) phonons make main contributions to the DCS and the impact of the SO phonon can be negligible in the ERRS process. Moreover, scattering intensity of the bulk LO phonon is strongly enhanced as the incident photon energy approaches the energy band-gap of the GaN.     

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.     

Theory of Raman light scattering by nanocrystal acoustic vibrations

A theory of Raman scattering of light by acoustic phonons in spherical nanocrystals of zinc-blende and wurtzite semiconductors has been developed with the inclusion of the complex structure of the valence band. The deformation-potential approximation was used to describe the exciton-phonon interaction. It is shown that this approximation allows only Raman scattering processes involving spheroidal acoustic phonons with a total angular momentum F=0 or 2. The effect of phonon quantum confinement on linewidth in Raman scattering spectra and scattered polarization is analyzed. An expression for the shape of the spectral line corresponding to nonresonant scattering from F=0 phonons was obtained. Fiz. Tverd. Tela (St. Petersburg) 41, 1473–1483 (August 1999)