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.     

Temperature‐dependent Raman spectroscopy of BaTiO3 nanorods synthesized by using a template‐assisted sol–gel procedure

In the present work, multiphase polycrystalline BTO nanorods were synthesized using template‐assisted sol–gel deposition and their structural evolution was studied using thermo Raman spectroscopy, X‐ray diffractometry and high‐resolution transmission electron microscopy (HRTEM). In the BTO nanorods, the tetragonal phase was the dominant one, while both Raman and HRTEM indicated a coexistence with the high‐temperature hexagonal polymorph. This phase was stable across the whole of the investigated temperature range (from −95 °C to 200 °C). The investigated nanorods underwent a diffuse phase transition from tetragonal to cubic with respect to the temperature, whereas the final phase‐transition temperature was shifted to higher values compared to that expected for BTO. The low‐temperature orthorhombic‐to‐rhombohedral phase transition was also shifted to higher temperatures. These differences could be explained by the strain induced by the presence of hexagonal nanolamellas intergrown within the tetragonal nanocrystals. This result indicates that the temperature of the ferroelectric phase transition in polycrystalline BTO nanorods can be manipulated by introducing a stable hexagonal phase. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Micro‐Raman spectroscopic study of artificially aged natural and dyed wool

The objective of this study was to evaluate the use of micro‐Raman spectroscopy as a non‐invasive vibrational spectroscopic technique applied to the examination of wool samples, which may be applied to textile materials of cultural heritage interest. In this work, a selection of wool materials were primarily investigated in their unaged states through the utility of a natural wool reference together with selected samples dyed with different natural colorants, namely woad, weld and madder. The identification of the main modes of vibration of the wool fibre keratin was assessed in all the samples, which aided the determination of the changes within the protein structure, in particular, through the cysteine and peptide cross‐linkages brought about by the addition of the dyes that can produce effects similar to degradation. The dye too was assessed importantly to enable its identification through its characteristic scattering or fluorescence emissions on a woollen matrix, as well as to ascertain whether a uniform covering across the surface of the wool was achieved or not. Regarding the artificial degradation of the samples it was possible to observe numerous modifications within the molecular structure of the wool, in particular, within the amide I, C H bending, amide III and S‐S stretchings along with the physical photo‐yellowing of fibres given by the presence of lipids dispersed across the surface of the wool. The effects of ageing on the dyed samples were also investigated, indicating that many of the bands relative to the colorants were still present, yet so too were numerous vibrations from the wool that also indicated a certain level of stress and degradation to the underlying wool. Copyright © 2008 John Wiley & Sons, Ltd.     

Micro‐Raman analysis of GaAs Schottky barrier solar cell

Gallium arsenide (GaAs) cells have been in the race with silicon single‐crystal cells for the highest efficiency photovoltaic devices. The annealed, irradiated Schottky barrier (SB) solar cells were characterised using micro‐Raman spectroscopy at three different regions: namely, at the (1) ohmic contact region, (2) unirradiated region and (3) irradiated region. We also present a micro‐Raman study of the damage process in annealed GaAs SB solar cells bombarded by high‐energy ions. A Gaussian line shape was fitted to the Raman spectra of the longitudinal optical phonon A₁(LO), and parameters such as intensity, full width at half maximum (FWHM) and the area under the peak were obtained for the different annealing temperatures. Biaxial stress (σ), carrier concentration (n), depletion length (L_d), dislocation velocity (ν) and life time of the first‐order optical phonon (τ) of the A₁(LO) mode of the irradiated region of the samples annealed at different temperatures were calculated. Copyright © 2010 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopic study of El Gasco pumice,western Spain

A micro‐Raman spectroscopic study of pumice materials from El Gasco (Sierra de Gata, Spain) has been performed for the first time. The obtained spectra allow the precise identification of the minerals, quartz, haematite, magnetite, ilmenite, rutile and anatase, in general agreement with results obtained by complementary techniques of X‐Ray Diffraction (XRD) and Electron Microprobe. Also, fayalite and ferroan ringwoodite have been identified. The presence of high‐pressure polymorphs indicates that the pumice rocks were subjected to high‐pressure conditions quite similar to those observed in shock‐induced molten and recrystallised materials, such as some meteorites and impact‐related rocks. Copyright © 2006 John Wiley & Sons, Ltd.     

Correlation of structure and spin–phonon coupling in (La,Nd) doped BiFeO3 films

We studied the effect of structural change on the spin–phonon coupling in doped BiFeO₃ (BFO) films (Bi_0.8La_0.1Nd_0.1FeO₃) grown on SrTiO₃ (001) substrate. The temperature‐dependent Raman studies show phonon anomalies in the vicinity of magnetic ordering temperature T_N owing to the spin–phonon coupling. Doped films exhibit strong anomalies in the line widths of Raman bands around T_N revealing the presence of strong spin–lattice coupling. The modification in structure as a result of A‐site doping in BFO films plays an important role in controlling the nature of spin–phonon coupling. Copyright © 2014 John Wiley & Sons, Ltd.     

Optical properties of -doped semiconductors: Plasmon–phonon coupling and Raman spectra

Collective excitations and their coupling to optical phonons have been studied for a two-dimensional electron gas in -doped polar semiconductors within the random-phase approximation. The inelastic light scattering spectrum due to the coupled plasmon–phonon modes are calculated for the multisubband two-dimensional electron systems. Our calculation shows that, due to the high electron density in these systems, both intrasubband and intersubband plasmons are strongly coupled to the optical-phonons. On the other hand, due to the high impurity concentration, level broadening modifies the inelastic light scattering spectrum significantly.     

High P–T Raman study of transitions in relaxor multiferroic Pb(Fe0.5Nb0.5)O3

The vibrational and structural properties of Pb(Fe_0.5Nb_0.5)O₃ have been investigated using Raman spectroscopy up to 40 GPa at 300 K and from 300 to 415 K at selected pressures. The measurements reveal three phase transitions, at 5.5, 8.7, and 24 GPa at room temperature. The temperature dependences of the spectra indicate transitions at 1.5 GPa, at 335 and 365 K. The results are consistent with the appearance of an intermediate tetragonal P4mm phase between the ferroelectric R3m and paraelectric Pm‐3m phases. A P–T phase diagram is proposed that allows further insight into the magnetoelectric coupling present in this material. Copyright © 2015 John Wiley & Sons, Ltd.     

Micro‐Raman study of Zr‐substituted Bi4Ti3O12 ceramics

We have studied the lattice vibrational modes of Zr‐substituted Bi₄Ti₃O₁₂ ceramics using micro‐Raman spectroscopy. Replacement of Zr at the Ti site in the perovskite block is found from the increase in the lattice parameters as a function of Zr contents. Combined X‐ray diffraction patterns and Raman analysis suggested less than 40 mole% Zr solubility in Bi₄Ti₃O₁₂. At 40 mole% of Zr substitution or above, the unreacted monoclinic‐phase ZrO₂ is observed in the X‐ray diffraction patterns and the Raman spectra. The incorporation of Zr in Bi₄Ti₃O₁₂ reduces the soft mode wavenumber and the transition temperature. Moreover, temperature dependent studies confirmed the ferroelectric to paraelectric transition in Bi₄Ti₃O₁₂ at about 675 °C. On increasing the Zr content up to 40% on the Ti sites of Bi₄Ti₃O₁₂, a systematic decrease in the phase transition temperature from 675 to 630 °C was observed. Copyright © 2007 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopic characterization of a tunable electrochromic device for application in smart windows

An asymmetric electrochromic (EC) device based on an active EC tungsten oxide–titanium oxide (WO₃–TiO₂) layer was constructed. The EC active layer consisted predominantly of monoclinic WO₃ nanocrystallites with a minor additional component of hexagonal WO₃ and amorphous TiO₂. Detailed micro‐Raman spectroscopic studies of the intercalation and deintercalation of lithium in the EC active layer of the EC device as a function of the applied voltage were performed. Three significant structural stages occur upon intercalating Li into the WO₃–TiO₂ layer when coloration potentials of 1.0, 1.5, 2.0, and 3.0 V are applied to the EC device. In the first stage (applied potential of 1.0 V), the m‐Li_x WO₃ phase is retained. In the second stage, (applied potential of 1.5 and 2.0 V) the m‐Li_x WO₃ transforms to a tetragonal phase. In the third stage, (applied potential of 3.0 V) the Raman spectrum exhibits no spectral bands, showing that Li_x WO₃ has attained the highest‐symmetry cubic phase. This phase sequence is confirmed by the X‐ray diffraction (XRD) measurement. These phase transitions can be reversed and, upon complete deintercalation, m‐WO₃ with traces of h‐WO₃ is recovered. Optical transmission studies were performed in conjunction with Raman and XRD studies. A shift of the optical transmittance peak position from 639 to 466 nm and reduction in the width of the transmittance curve with increasing applied potential opens up the possibility of smart window applications for the nanocrystalline WO₃‐based EC device. Copyright © 2008 John Wiley & Sons, Ltd.     

Micro‐Raman investigations on inclusions of unusual habit in a commercial tanzanite gemstone

The vibrational properties of submillimetre size inclusions of unusual habit in a commercial tanzanite gemstone were investigated by confocal Raman microspectroscopy with the aim of probing both their chemical composition and crystal structure. Highly contrasted Raman spectra were recorded in confocal conditions from several inclusions incorporated at different depths, ranging between a few microns to some tens of microns beneath the gemstone surface. The observed spectral features were identified as specific markers of hematite (α‐Fe₂O₃). Their unambiguous assignment has been inferred by comparing our experimental findings with the literature data recorded either in single crystals of hematite or in other iron oxides and oxyhydroxides. Our results rule out the presence of any pseudomorphic variety of hematite in the investigated gemstone, while confocal micro‐Raman spectroscopy definitively proved itself as a very reliable, relatively costless and noninvasive tool for unambiguous identification of subsurface regions of gemstones. Copyright © 2011 John Wiley & Sons, Ltd.     

Polarized Raman mapping study of the microheterogeneity in 0.67PbMg1/3 Nb2/3O3‐0.33PbTiO3 single crystal

Polarized micro‐Raman spectroscopy was carried out on the (001) face of a 0.67PbMg_1/3Nb_2/3O₃‐33%PbTiO₃ (PMN‐33%PT) single crystal. The Raman images revealed the spatial variations of the intensity of the Raman bands, suggesting that the structure in the PMN‐33%PT single crystal varied from one micro‐area to another. When changing the polarization direction of the incident light with respect to the selected crystalline axes, the intensities of the Raman modes varied periodically. According to the Raman selection rules (RSRs), the angular dependences of the Raman modes indicated that the PMN‐33%PT single crystal is in the monoclinic phase. Furthermore, the color patterns in the Raman images were associated with the coexistence of the M_A‐ and M_C‐type monoclinic phases in the PMN‐33%PT single crystal. Our results provide useful information for understanding the microheterogeneity of the relaxor PMN‐xPT single crystals with compositions near the morphotropic phase boundary region. Copyright © 2010 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.     

Rapid screening of sildenafil and tadalafil adulterated in healthcare products by Micro‐Raman spectroscopy

Sildenafil and tadalafil are inhibitors of phosphodiesterase type 5, which are frequently added into healthcare products. The objective of this study was to evaluate the possibility of using micro‐Raman spectroscopy as a non‐destructive technique to screen for sildenafil and tadalafil in adulterated healthcare products. Using a viewing microscope, the suspect area of healthcare products was selected, which had a discernable crystal form or shape from the surrounding zone. Optimization of instrumental parameters of the Raman spectrometer was chosen to reduce the background fluorescence, and the Raman spectra were collected. The spectra collected were compared with the standard Raman spectra of pure sildenafil and tadalafil. Samples with an identifiable Raman signature to that of sildenafil or tadalafil could be confirmed using liquid chromatography–mass spectrometry (LC/MS). Additionally, wavelet denoising combined with similarity calculation was used to establish an automated approach for discrimination of adulterated healthcare products. Correlation coefficient was chosen for similarity calculation based on the spectra collected and the standard Raman spectra of pure sildenafil and tadalafil. We compared ten samples, secured by administrative authorities in Shanghai, to analyse and demonstrate the capabilities of our proposed method. We established six samples containing sildenafil or tadalafil warranting analysis using LC/MS. Thus, the use of micro Raman spectroscopy provides a quick, convenient and non‐destructive method for screening adulterated chemicals in healthcare products. Raman spectroscopy combined with similarity calculation requires little training after spectra library is developed, thus showing great promise to identify the adulterated healthcare products in the future. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman phonon anomalies in Sr(Fe1-xCox)2As2

Phonon anomalies have been reported in iron-pnictide superconductors indicating a diverse interplay between different orders in the materials.Here,we report Raman scattering measurements on Sr(Fe_1-xCo_x)₂As₂(x=0 and x=0.04)single crystals in the B;symmetry with respect to a 1 Fe unit cell.Upon cooling,we observe a larger split(13 cm;)of Eg Raman phonon modes pertaining to in-plane Fe and As displacements as the crystals undergo the tetragonal-toorthorhombic structural phase transition,although a considerable split(9 cm;)has been reported in BaFe_1-xCo_x)₂As₂.Furthermore,the splitting of E;phonon modes is strongly reduced upon doping.We perform an order-parameter analysis revealing a similar doping dependence of E;phonon splitting as reported in other compounds of the 122 family,indicating these phonon anomalies widely exist in 122 iron-based superconductors and might share the same mechanisms.     

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.     

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 spectroscopy analysis of 16th century Portuguese Ferreirim Masters oil paintings

In the present work a set of eight altarpieces of the 16th century (1532–1534), attributed to the Ferreirim Masters (Gregório Lopes, Garcia Fernandes and Cristóvão de Figueiredo), from the Santo António de Ferreirim Monastery (North of Portugal), were analysed by micro‐Raman spectroscopy. For this purpose some samples were taken from the paintings to characterise its artist's ‘school’. It was found that the preparation was made with chalk and gypsum and the palette composed mainly of lamp black, azurite, lead white (mixed with other pigments), lead–tin yellow type I, goethite (the main constituent of yellow ochre), red lead (as under painting), haematite (the main constituent of red ochre) and vermilion. Indigo was detected in one sample. Some derivatives and degradation products were found mainly in the panels subjected to high temperatures during a fire occurred in 1954: a degradation product from massicot or red lead, lead carbonate (dehydrated derivative of lead white), bassanite and anhydrite (hemi‐ and dehydrated forms of gypsum). These results are compared with those of previous total reflection X‐ray fluorescence spectroscopy (TXRF) analyses. Copyright © 2009 John Wiley & Sons, Ltd.