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.     

Investigation of thermostability and phonon–phonon interactions in Mo6S3I6 nanowires by Raman scattering spectroscopy

Detailed Raman scattering measurements were performed on molybdenum–sulfur–iodine nanowires (Mo₆S₃I₆). At room temperature, 21 well‐resolved Raman modes were experimentally observed for the first time in this new compound. The phase stability and vibrational properties of the nanowires were investigated by different temperature treatments. High‐temperature Raman spectra showed that the phase separation of Mo₆S₃I₆ nanowires took place between 573 and 673 K, followed by appearance of a new mode at 819 cm⁻¹ characteristic of the MoO₃ phase. Low‐temperature Raman scattering spectra showed a significant difference in phonon–phonon interactions between internal and external Raman modes of Mo₆S₃I₆ nanowires. These interesting vibrational properties can give new insights for improved material preparation and achievement of higher conductivity and other functional properties of these otherwise interesting materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Micro‐Raman study of orbiton–phonon coupling in YbVO3

First‐order and multiphonon Raman active excitations are studied in YbVO₃ as a function of temperature in the orthorhombic and monoclinic phases. Below T ≃ 170 K, a G‐type orbital ordering with a concomitant monoclinic transition occurs. They enhance the phonon polarizabilities, allowing the resolution of room‐temperature bands, and activate new excitations around 700 cm⁻¹. Below T ∼ 65 K, the 700 cm⁻¹ excitations disappear, indicating a C‐type orbital ordering and a return to the orthorhombic structure. The observed phonon combinations around 1400 cm⁻¹ with a dominant Jahn‐Teller vibration at ∼690 cm⁻¹ reflect a possible orbiton‐phonon coupling. Copyright © 2011 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.     

Resonant Raman scattering from CdTe/ZnTe self-assembled quantum dot structures

We report resonant Raman scattering results of CdTe/ZnTe self-assembled quantum dot (QD) structures. Photoluminescence spectra reveal that the band gap energies of the CdTe QDs decrease with the increase of CdTe thickness from 2.0 to 3.5 monolayers, which indicates that the size of the QDs increases. When the CdTe/ZnTe QD structures are excited by non-resonant excitation, a longitudinal optical (LO) phonon response from the ZnTe barrier material is observed at 206 cm⁻¹. In contrast, when the CdTe/ZnTe QD structures are resonantly excited near the band gap energy of the QDs, additional phonon modes emerge at 167 and 200 cm⁻¹, while the ZnTe LO phonon response completely disappears. The 167 cm⁻¹ mode corresponds to the LO phonon of the CdTe QDs. A spatially resolved Raman scattering from the cleaved edge of the QD sample reveals that the 200 cm⁻¹ mode is strongly localized at the interface between the CdTe QDs and ZnTe cap layer. This phonon mode is attributed to the interface optical (IO) phonon. The analytically calculated value of the IO phonon energy using a dielectric continuum approach, assuming a spherical dot boundary, agrees well with the experimental value.     

Experimental assessment of the phonon confinement in TiO2 anatase nanocrystallites by Raman spectroscopy

TiO₂ aerogels prepared by sol‐gel method and followed by supercritical drying have been annealed at temperatures ranging between 400 and 550 °C. The obtained TiO₂ anatase crystallites with the mean size between 6.4 and 13.9 nm, as obtained from transmission electron microscopy measurements, have been further investigated by Raman spectroscopy. It was found that the peak position and full width at half maximum (FWHM) of the TiO₂ anatase Raman bands located around 144, 398, and 638 cm⁻¹ are influenced by crystallite dimension. These spectral changes can be assigned to the combined action of several nanosize effects such as phonon confinement, phonon coupling, strain, and stoichiometry defects. Surprisingly, the best discrimination of the FWHM change with the nanocrystallite mean size was achieved for the 638 cm⁻¹ band, whereas the best discrimination for the peak position was found for the 398 cm⁻¹ band. The critical size values obtained from the peak position and FWHM evaluation were between 12.7 and 13.1 nm. Taking into consideration that only the phonon confinement and inhomogeneous strain can induce an asymmetric broadening of the Raman signal, the bands asymmetry was evaluated, and the critical size values of the nanocrystallites were determined to be between 10 and 11 nm. For a symmetric size distribution of TiO₂ anatase crystallites with dimensions between 6.4 and 13.9 nm, the obtained result indicates that the phonon confinement contribution to the overall size effects is more than 75%. No evidence about the influence of the phonon coupling and vacancies on the Raman features was observed. The comparison of the data derived from the experimental analysis with those obtained by applying the theoretical phonon confinement model indicates the necessity of developing an improved phonon confinement model. The asymmetry approach can be applied for a great variety of nanostructures, as a measure of the confinement effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure‐dependent and temperature‐dependent Raman study

We revisit the assignment of Raman phonons of rare‐earth titanates by performing Raman measurements on single crystals of O¹⁸ isotope‐rich spin ice and nonmagnetic pyrochlores and compare the results with their O¹⁶ counterparts. We show that the low‐wavenumber Raman modes below 250 cm⁻¹ are not due to oxygen vibrations. A mode near 200 cm⁻¹, commonly assigned as F_2g phonon, which shows highly anomalous temperature dependence, is now assigned to a disorder‐induced Raman active mode involving Ti⁴⁺ vibrations. Moreover, we address here the origin of the ‘new’ Raman mode, observed below T_C ~ 110 K in Dy₂Ti₂O₇, through a simultaneous pressure‐dependent and temperature‐dependent Raman study. Our study confirms the ‘new’ mode to be a phonon mode. We find that dT_C/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up to ~8 GPa. We find that pressure suppresses the anomalous temperature dependence. The role of the inherent vacant sites present in the pyrochlore structure in the anomalous temperature dependence is also discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural modifications of GaN after cerium implantation

Among the family of rare earth (RE) dopants, the doping of first member Ce into GaN is the least studied system. This article reports structure properties of Ce‐doped GaN realized by technique of ion implantation. Ce ions were implanted into metal organic chemical vapor deposition grown n‐ and p‐GaN/sapphire thin films at doses 3 × 10¹⁴ and 2 × 10¹⁵ cm⁻². X‐ray diffraction scans and Raman scattering measurements exhibited expansion of lattice in the implanted portion of the samples. First order Raman scattering spectra show appearance of several disorder‐activated Raman scattering modes in addition to typical GaN features. A dose‐dependent decrease in intensity of E₂ mode was observed in Raman the spectra of the implanted samples. Ultraviolet Raman spectra of implanted samples show complete quenching of photoluminescence emission and appearance of multiple A₁(LO) phonon scattering modes up to fifth order. Moreover, a decrease in intensity and an increase in line width of LO modes as a function of wavenumber were observed for implanted samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural studies and Raman spectroscopy of forbidden zone boundary phonons in Ni‐doped ZnO ceramics

We present X‐ray diffraction and Raman spectroscopy studies of Ni‐doped ZnO (Zn_1−xNi_xO, x = 0.0, 0.03, 0.06, and 0.10) ceramics prepared by solid‐state reaction technique. The presence of the secondary phase along with the wurtzite phase is observed in Ni‐doped ZnO samples. The E₂(low) optical phonon mode is seen to be shifted to a lower wavenumber with Ni incorporation in ZnO and is explained on the basis of force‐constant variation of ZnO bond with Ni incorporation. A zone boundary phonon is observed in Ni‐doped samples at ∼130 cm⁻¹ which is normally forbidden in the first‐order Raman scattering of ZnO. Antiferromagnetic ordering between Ni atoms via spin‐orbit mechanism at low temperatures (100 K) is held responsible for the observed zone boundary phonon. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of pressure on the Raman spectra of synthetic diamonds with boron impurity

The raman scattering technique is used for studying diamonds with a 0.04–0.1 at % boron impurity under a pressure up to 3 GPa in a chamber with sapphire anvils. The Raman frequency increases linearly with pressure for all samples with pressure coefficients of 2.947 cm^?1/GPa for pure diamond and 3.01 cm^?1/GPa for boron-doped samples. The Raman linewidths remain unchanged for pure diamond and for diamond with a boron concentration of about 0.04 at % and decrease linearly upon an increase in pressure for samples with a boron concentration of about 0.1 at %. The Raman spectra with a line profile corresponding to the Fano resonance do not change qualitatively up to a pressure of 3 GPa. In diamond samples with a boron impurity exceeding 0.1 at %, the boron concentration in the surface layer can be substantially higher than at the center of the sample.     

On the curve of the density of phonon states for cubic boron nitride (from the results of photoluminescence measurements)

The fine structure of the phonon wing associated with the zero-phonon line (ZPL) of the BN1 center in the cubic boron nitride is analyzed in comparison with the structure of the phonon wing of the luminescence center at 3.188 eV in diamond, the second-order Raman scattering spectrum, and the theoretically calculated densities of phonon states of the c-BN compound. Taking into account the similarity of the structures of the phonon wings in the spectra of the above centers and the previously made assumptions that the structure of the phonon wing of the center at 3.188 eV is due to the specific features in the density of phonon states of diamond, it is assumed that, in the observed density of phonon states of cubic boron nitride, the critical points are represented by the specific features of the structure of the phonon wing associated with the zero-phonon line (at 3.294 eV) of the BN1 luminescence center. In turn, these latter specific features coincide accurate to within 5–10cm^?1 with the theoretically calculated lattice vibrations of the c-BN compound and the experimental data obtained from the second-order Raman spectra.     

Temperature‐dependent,micro‐Raman spectroscopic study of barium titanate nanoparticles

A comparative, temperature‐dependent (80–500 K at 5 K intervals), micro‐Raman spectroscopic study of 300 and 50 nm diameter ceramic BaTiO₃ nanoparticles was carried out with the purpose of elucidating the nanoparticle size effect on the temperature dependence of the polar and non‐polar phonons. A method for calibrating Raman intensities, along with an iterative spectral fitting algorithm, is proposed for concurrent Raman band position and intensity analysis, increasing the analytical abilities of single temperature point Raman spectroscopy. The 300 nm particles exhibit all three phase transitions, whereas the 50 nm particles do not show evidence of these phase transitions in the same temperature range. The Curie temperature appears to be a phonon converging point, irrespective of the phonon symmetry. An attempt was made to qualitatively relate the temperature‐dependent Raman spectra to complimentary non‐spectroscopic methods, such as heat capacity and X‐ray diffraction studies. The study proves that the temperature‐dependent behavior of the polar phonon, 265 cm⁻¹, can be utilized as a sensitive phase transition probe. Copyright © 2014 John Wiley & Sons, Ltd.     

Nature of some features in Raman spectra of hydroxyapatite‐containing materials

A very broad vibrational band ranging from 1000 up to 4000 cm⁻¹ and two relatively sharp bands at 5000 and 5027 cm⁻¹ are found in the Raman scattering spectrum of hydroxyapatite‐containing films obtained by gas detonation spray method. We developed a theoretical model that interprets the broad band as a result of strong interaction between the high‐frequency hydrogen bond vibrations and lattice phonons. Both sharp bands around 5000 cm⁻¹ are assigned to the overtones of v‐OH vibrations. Copyright © 2016 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.     

Resonance Raman study of He+ ion implanted nanostructured ZnS

ZnS nanocrytsals of size ∼2.5 nm were prepared by chemical precipitation technique. Pressed pellets of nanostructured ZnS were implanted with He⁺ ions at doses of 5 × 10¹⁴, 1 × 10¹⁵ and 5 × 10¹⁵ ions/cm². Raman spectra of both unimplanted and He⁺ ion implanted samples were recorded with ultraviolet (UV) excitation. LO, 2LO, 2TO, (LO + TA) and (2TO − TA) modes of ZnS were observed in the resonance Raman spectra of the unimplanted nanostructured ZnS samples. In addition, a surface mode was observed at 294 cm⁻¹. With the implantation of He⁺ ions, the 2TO mode disappeared and 2LO mode became prominent and this observation was attributed to the decrease in band gap of ZnS nanocrytsals due to ion implantation. The exciton–LO phonon coupling strength was determined from the intensity ratio of 2LO to LO modes and it was observed that the exciton–LO phonon coupling strength increases with increase in implantation dose. In the present work, we report for the first time the observation of 2TO mode in the resonance Raman spectrum of nanostructured ZnS and also the modification of exciton–LO phonon coupling strength of semiconductor nanoparticles by ion implantation. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopic study of ceramic Sr2Bi4Ti5O18

Raman spectra of ceramic Sr2Bi4Ti5O18 （SBTi5） are reported to consist of four different Raman bands. Temperature-dependent spectra reveal the relationship between the lattice vibration and the material＇s structure. There appears a relatively large change in structure of the material at about 273K, The anharmonic potential of the material has a great influence on its phonon mode full width at half maximum （FWHM）, which can be expressed by a function of temperature. Theoretical fittings of the FWHMs for the two modes at around 312 cm^-1 and 464cm^-1 indicate that the latter phonon mode is more anharmonic than the former one.     

Layer‐dependent resonant Raman scattering of a few layer MoS2

We report resonant Raman scattering of MoS₂ layers comprising of single, bi, four and seven layers, showing a strong dependence on the layer thickness. Indirect band gap MoS₂ in bulk becomes a direct band gap semiconductor in the monolayer form. New Raman modes are seen in the spectra of single‐ and few‐layer MoS₂ samples which are absent in the bulk. The Raman mode at ~230 cm⁻¹ appears for two, four and seven layers. This mode has been attributed to the longitudinal acoustic phonon branch at the M point (LA(M)) of the Brillouin zone. The mode at ~179 cm⁻¹ shows asymmetric character for a few‐layer sample. The asymmetry is explained by the dispersion of the LA(M) branch along the Γ‐M direction. The most intense spectral region near 455 cm⁻¹ shows a layer‐dependent variation of peak positions and relative intensities. The high energy region between 510 and 645 cm⁻¹ is marked by the appearance of prominent new Raman bands, varying in intensity with layer numbers. Resonant Raman spectroscopy thus serves as a promising non invasive technique to accurately estimate the thickness of MoS₂ layers down to a few atoms thick. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman identification of lonsdaleite in Popigai impactites

Micro‐Raman spectroscopy and X‐ray diffraction method (XRD) were used to characterize impact carbonaceous rocks excavated from the Popigai crater (Siberia). The deconvolution of the first‐order Raman spectra of the rocks containing different amounts of carbon phases (diamond, lonsdaleite and graphite) allowed the identification of lonsdaleite spectrum. The most intensive band at 1292–1303 cm⁻¹ was ascribed to A_1g vibration mode of lonsdaleite, whereas the less intense band at 1219–1244 cm⁻¹ was attributed, in agreement with previously reported ab initio calculations, to E_2g vibration mode. The established correlation between the intensities of Raman and XRD peaks permits a rough estimation of lonsdaleite/diamond phase ratio in the impact rocks using micro‐Raman measurements. The second‐order Raman spectra of lonsdaleite–diamond rocks were recorded. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman investigation of defective SiC nanocrystals

Phonon confinement effect and surface optical mode in SiC nanocrystal have been investigated through Raman spectroscopy. Considering high density of stacking faults in SiC grains, the correlation length of RWL (proposed by Richter, Wang, Li to explain phonon confinement in nano silicon) model is determined as a distance between nearby stacking faults. Thus, homogeneous region becomes thin slices in cylindrical SiC grains, which redefines weighting function. Effect of anisotropy of phonon dispersion curve is also analyzed during calculation. The additional 875‐cm⁻¹ band is attributed to defects and amorphous SiC, which is confirmed by transmission electron microscopy. SiC grains are approximated as column array with grain boundary substances regarded as surrounding medium, which explains surface optical phonon mode at 915 cm⁻¹. Copyright © 2015 John Wiley & Sons, Ltd.     

Study of spin–phonon coupling in LiFe1 − xMnxPO4olivines

LiFe_{1 − x}Mn_xPO₄ olivines are promising material for improved performance of Li‐ion batteries. Spin–phonon coupling of LiFe_{1 − x}Mn_xPO₄ (x = 0, 0.3, 0.5) olivines is studied through temperature‐dependent Raman spectroscopy. Among the observed phonon modes, the external mode at ~263 cm⁻¹ is directly correlated with the motions of magnetic Fe²⁺/Mn²⁺ ions. This mode displays anomalous temperature‐dependent behavior near the Néel temperature, indicating a coupling of this mode with spin ordering. As Mn doping increases, the anomalous behavior becomes clearly weaker, indicating the spin–phonon coupling quickly decreases. Our analyses show that the quick decrease of spin–phonon coupling is due to decrease of the strength of spin–phonon coupling, but not change of spin‐ordering feature with Mn doping. Importantly, we suggest that the low electrochemical activity of LiMnPO₄ is correlated with the weak spin–phonon coupling strength, but not with the weak ferromagnetic ground state. Our work would play an important role as a guide in improving the performances of future Li‐ion batteries. Copyright © 2015 John Wiley & Sons, Ltd.