Deep UV resonance Raman spectroscopic study on electron‐phonon coupling in hexagonal III‐nitride wide bandgap semiconductors

Electron–phonon coupling (EPC) is an important issue in semiconductor physics because of its significant influence on the optical and electrical properties of semiconductors. In this work, the EPC in wide bandgap semiconductors including hexagonal BN and AlN was studied by deep UV resonance Raman spectroscopy. Up to fourth‐order LO phonons are observed in the resonance Raman spectrum of hexagonal AlN. By contrast, only the prominent emission band near the band‐edge and the Raman band attributed to E_2g mode are detected for hexagonal BN with deep UV resonance excitation. The different behavior in resonant Raman scattering between the III‐nitrides reflects their large difference in EPC. The mechanism for EPC in hexagonal BN is the short‐range deformation interaction, while that in hexagonal AlN is mainly associated with the weak long‐range Fröhlich interaction. Copyright © 2016 John Wiley & Sons, Ltd.     

Observation of low‐wavenumber out‐of‐plane optical phonon in few‐layer graphene

Few‐layer graphene grown by chemical vapor deposition has been studied by Raman and ultrafast laser spectroscopy. A low‐wavenumber Raman peak of ~120 cm⁻¹ and a phonon‐induced oscillation in the kinetic curve of electron–phonon relaxation process have been observed, respectively. The Raman peak is assigned to the low‐wavenumber out‐of‐plane optical mode in the few‐layer graphene. The phonon band shows an asymmetric shape, a consequence of so‐called Breit‐Wigner‐Fano resonance, resulting from the coupling between the low‐wavenumber phonon and electron transitions. The obtained oscillation wavenumber from the kinetic curve is consistent with the detected low‐wavenumber phonon by Raman scattering. The origin of this oscillation is attributed to the generation of coherent phonons and their interactions with photoinduced electrons. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Effect of optical phonon‐magnon interaction on the magnon softening at finite temperature

A magnon‐phonon interaction model is set up in a two‐dimensional ferromagnetic compound square‐lattice system. Using the Matsubara Green function theory we calculated the magnon dispersion curves on the main symmetric line in Brillouin zone, compared the influences of the magnetic ion optical phonon with non‐magnetic ion optical phonon on the magnetic excitation of the system and discussed the influences of various parameters on the magnon softening. The lower Debye temperature of ferromagnetic materials is, the more likely the magnon softening occurs. It turned out that the optical phonon‐magnon coupling plays an important role on the magnon softening, the longitudinal optical phonon contributes the most to the magnon softening and magnon damping. It is also found that the contribution of the non‐magnetic ion to the magnon softening and magnon damping is more significant than that of magnetic ion when the mass of the magnetic ion is less than that of the non‐magnetic ion, or the mass of magnetic ion and the non‐magnetic ion are equal.     

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.     

Raman‐induced impulsive Stokes lasing in novel SRS‐active monoclinic m‐LaVO4 crystal

Monoclinic m‐LaVO₄ vanadate with the monazite‐type structure was found to be a new favorable SRS‐active crystal. Its two‐phonon impulsive Stokes lasing has been recorded under near‐IR femtosecond pumping. Knowledge acquired about the behavior of impulsive stimulated Raman scattering in the studied crystals may be useful for the physics of coherent optical phonons and for engineering of femtosecond lasers. The fundamental results obtained here will also motivate the search for crystals able to generate multiphonon impulsive SRS. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Polarization‐sensitive CARS spectroscopy on free‐base porphyrins: coproporphyrin I tetramethyl ester

The application of polarization‐sensitive (PS) coherent anti‐Stokes Raman scattering (CARS) spectroscopy for the investigation of highly luminescent free‐base porphyrins under Q_x band resonance is discussed. For coproporphyrin I tetramethyl ester (CP‐I‐TME), PS CARS spectra involving resonances with the electronic Q_x absorption band as well as polarized spontaneous Raman spectra involving B band resonance are presented. A quantitative evaluation of the CP‐I‐TME spectra is performed and the results are compared to our previously presented data on free‐base octaethylporphine (OEP) and mesoporphyrin IX dimethyl ester (MP‐IX‐DME), which were obtained under identical excitation conditions. This comprehensive analysis reveals several spectral differences that can be attributed to the different β–substitution pattern of the porphyrin macrocycle. Additionally, the strong resonance enhancement of totally symmetric modes under Q_x band excitation is identified as a common property for OEP, CP‐I‐TME, and MP‐IX‐DME; this enhancement selectivity distinguishes the investigated substances from what is generally observed for metallo porphyrins. Copyright © 2008 John Wiley & Sons, Ltd.     

Birth of room‐temperature magnons and Raman line enhancement in ZnO nanostructures containing cobalt oxide

Cobalt (Co) addition and thermal annealing induced structural and vibrational properties of ZnO nanostructures were analysed. X‐ray diffraction pattern reveals that the nanostructures are in hexagonal wurtzite type and the formation of Co₃O₄. The Co ion induced morphology changes have been studied by high‐resolution scanning electron microscope images and energy dispersive spectroscopy measurements confirm the presence of Co ions. CoO‐related magnon excitation bands are emerged at room temperature for the Co‐added samples. There are no changes in the band positions of the Raman spectra of pure and Co‐added materials. Annealed sample exhibits the suppression of magnon bands and formation of Co₃O₄: ZnO composites. Raman line width and the electron phonon coupling constant are decreased with respect to the annealing temperature. The formation of Co₃O₄ : ZnO composite phases have further confirmed by infrared spectra. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

How does the substrate affect the Raman and excited state spectra of a carbon nanotube?

We study the optical properties of a single, semiconducting single-walled carbon nanotube (CNT) that is partially suspended across a trench and partially supported by a SiO₂-substrate. By tuning the laser excitation energy across the E ₃₃ excitonic resonance of the suspended CNT segment, the scattering intensities of the principal Raman transitions, the radial breathing mode (RBM), the D mode and the G mode show strong resonance enhancement of up to three orders of magnitude. In the supported part of the CNT, despite a loss of Raman scattering intensity of up to two orders of magnitude, we recover the E ₃₃ excitonic resonance suffering a substrate-induced red shift of 50 meV. The peak intensity ratio between G band and D band is highly sensitive to the presence of the substrate and varies by one order of magnitude, demonstrating the much higher defect density in the supported CNT segments. By comparing the E ₃₃ resonance spectra measured by Raman excitation spectroscopy and photoluminescence (PL) excitation spectroscopy in the suspended CNT segment, we observe that the peak energy in the PL excitation spectrum is red-shifted by 40 meV. This shift is associated with the energy difference between the localized exciton dominating the PL excitation spectrum and the free exciton giving rise to the Raman excitation spectrum. High-resolution Raman spectra reveal substrate-induced symmetry breaking, as evidenced by the appearance of additional peaks in the strongly broadened Raman G band. Laser-induced line shifts of RBM and G band measured on the suspended CNT segment are both linear as a function of the laser excitation power. Stokes/anti-Stokes measurements, however, reveal an increase of the G phonon population while the RBM phonon population is rather independent of the laser excitation power.     

Metal‐nanoparticle‐coating‐induced enhancement and weakening of resonant Raman scattering in ZnO: effect of surface electric field

Effects of Ag and Ti nanoparticle coatings on resonant Raman scattering in various ZnO thin films are presented. The longitudinal optical (LO) phonons, irrespective of the ZnO quality, exhibit an enhancement and a weakening by the Ag and Ti nanoparticle coatings, respectively. The enhancement (weakening) is always accompanied by a reduced (an increased) intensity ratio of the second to first‐order LO phonons, which can be associated with changes in the electron‐phonon coupling strength in the probed area of ZnO. Angle‐resolved X‐ray photoelectron spectroscopy provides evidence for the bending of the surface energy bands and their changes induced by the metal coatings. The effect of metal nanoparticle coatings on the Raman scattering of ZnO is thus attributed to the changes in the surface electric field. Copyright © 2011 John Wiley & Sons, Ltd.     

From anti‐Stokes photoluminescence to resonant Raman scattering in GaN single crystals and GaN‐based heterostructures

The progress on anti‐Stokes photoluminescence and Stokes and anti‐Stokes Raman scattering in GaN single crystals and GaN/AlN heterostructures is reviewed. Anti‐Stokes photoluminescence investigated in the past was primarily attributed to two‐photon absorption, three‐photon absorption, and phonon‐assisted absorption. On the other hand, anti‐Stokes Raman scattering was used to determine electron‐phonon scattering time and decay time constant for longitudinal‐optical phonons. In a typical high electron mobility transistor based on GaN/AlN heterostructures, strong resonances were reached for first‐order and second‐order Raman scattering processes. Therefore, both Stokes and anti‐Stokes Raman intensities were dramatically enhanced. The feasibility of laser cooling of a nitride structure has been demonstrated. Anti‐Stokes photoluminescence and Raman scattering have potential applications in upconversion lasers and laser cooling of nitride ultrafast electronic and optoelectronic devices.     

Direct visual evidence for the chemical mechanism of surface‐enhanced resonance Raman scattering via charge transfer: (II) Binding‐site and quantum‐size effects

We describe quantum‐size and binding‐site effects on the chemical and local field enhancement mechanisms of surface‐enhanced resonance Raman scattering (SERRS), in which the pyridine molecule is adsorbed on one of the vertices of the Ag₂₀ tetrahedron. We first investigated the influence of the binding site on normal Raman scattering (NRS) and excited state properties of optical absorption spectroscopy. Second, we investigated the quantum‐size effect on the electromagnetic (EM) and chemical mechanism from 300 to 1000 nm with charge difference density. It is found that the strong absorption at around 350 nm is mainly the charge transfer (CT) excitation (CT between the molecule and the silver cluster) for large clusters, which is the direct evidence for the chemical enhancement mechanism for SERRS; for a small cluster the strong absorption around 350 nm is mainly intracluster excitation, which is the direct evidence for the EM enhancement mechanism. This conclusion is further confirmed with the general Mie theory. The plasmon peak in EM enhancement will be red‐shifted with the increase of cluster size. The influence of the binding site and quantum‐size effects on NRS, as well as chemical and EM enhancement mechanisms on SERRS, is significant. 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.     

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.     

Temperature‐depending Raman line‐shift of silicon carbide

Silicon carbide (SiC) is often used for electronic devices operating at elevated temperatures. Spectroscopic temperature measurements are of high interest for device monitoring because confocal Raman microscopy provides a very high spatial resolution. To this end, calibration data are needed that relate Raman line‐shift and temperature. The shift of the phonon wavenumbers of single crystal SiC was investigated by Raman spectroscopy in the temperature range from 3 to 112°C. Spectra were obtained in undoped 6H SiC as well as in undoped and nitrogen‐doped 4H SiC. All spectra were acquired with the incident laser beam oriented parallel as well as perpendicular to the c‐axis to account for the anisotropy of the phonon dispersion. Nearly all individual peak centers were shifting linearly towards smaller wavenumbers with increasing temperature. Only the peak of the longitudinal optical phonon A₁(LO) in nitrogen‐doped 4H SiC was shifting to larger wavenumbers. For all phonons, a linear dependence of the Raman peaks on both parameters, temperature and phonon frequency, was found in the given temperature range. The linearity of the temperature shift allows for precise spectroscopic temperature measurements. Temperature correction of Raman line‐shifts also provides the ability to separate thermal shifts from mechanically induced ones. Copyright © 2009 John Wiley & Sons, Ltd.     

Triple‐resonant two‐phonon Raman scattering in graphene

The triple‐resonant (TR) second‐order Raman scattering mechanism in graphene is re‐examined. It is shown that the magnitude of the TR contribution to the photon‐G′ mode coupling function in graphene is one order of magnitude larger than the widely accepted two‐resonant coupling. Enhancement of the order of 100 in the Raman intensity, with respect to the usual double‐resonant model, is found for the G′ band in graphene, and is expected in the related sp²‐based carbon materials, as well. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering studies of carbon nanotubes using Ag‐core Au‐shell nanoparticles

Surface‐enhanced Raman scattering from carbon nanotube bundles adsorbed with plasmon‐tunable Ag‐core Au‐shell nanoparticles (Ag@Au nps) was carried out for the first time. By utilizing nanoparticles whose plasmon resonance peak (541, 642 nm) closely matches the commonly used Raman excitation sources (532, 632.81 nm), we can observe a large enhancement in the Raman signatures of carbon nanotubes. We obtain greater enhancement in the Raman signal for the above case when compared to nanotubes adsorbed with conventional Ag, Au or other ‘off resonant’ Ag@Au nps. The power‐dependent SERS experiment on single‐walled nanotubes (SWNTs) with resonant Ag@Au nps reveals a linear behavior between the G‐band intensity and the photon flux density, which is in agreement with the vibrational pumping model of SERS. The observed enhancement by resonance matching is pronounced for carbon nanotubes and may lead to insights into understanding nanotube–nanoparticle interaction. Copyright © 2009 John Wiley & Sons, Ltd.     

Spin–orbit stiffness of the spin‐polarized electron gas

In a spin‐polarized electron gas, Coulomb interaction couples the spin and motion degrees of freedom to build propagating spin waves. The spin wave stiffness S_sw quantifies the energy cost to trigger such excitation by perturbing the kinetic energy of the electron gas (i.e. putting it in motion). Here we introduce the concept of spin–orbit stiffness, S_so, as the energy necessary to excite a spin wave with a spin polarization induced by spin–orbit coupling. This quantity governs the Coulombic enhancement of the spin–orbit field acting of the spin wave. First‐principles calculations and electronic Raman scattering experiments carried out on a model spin‐polarized electron gas, embedded in a CdMnTe quantum well, demonstrate that S_so = S_sw. Through optical gating of the structure, we demonstrate the reproducible tuning of S_so by a factor of 3, highlighting the great potential of spin–orbit control of spin waves in view of spintronics applications. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)