A non‐destructive approach for doping profiles characterization by micro‐Raman spectroscopy: the case of B‐implanted Ge

B‐implanted Ge samples have been investigated by micro‐Raman spectroscopy under different excitation wavelengths, with the aim of gaining insights about the B distribution at different depths beneath the sample surface. The intensities, observed under the different excitation wavelengths, of the B–Ge Raman peak at about 545 cm⁻¹, which is due to the local vibrational mode of the substitutional B atoms in the Ge matrix, have been used to calibrate the optical absorption lengths in B‐implanted Ge. Then, by using these calibrated values, a very sharp correlation between the spectral features of the Ge–Ge Raman peak at ~300 cm⁻¹ and the content of substitutional B atoms has been derived. Accordingly, a non‐destructive approach, based on micro‐Raman spectroscopy under different excitation wavelengths, is presented to estimate, at least at the lowest depths, the carrier concentration profiles from the spectral features of the Ge–Ge Raman peak. Copyright © 2014 John Wiley & Sons, Ltd.     

Depth‐resolved in vivo micro‐Raman spectroscopy of a murine skin tumor model reveals cancer‐specific spectral biomarkers

We have developed a micro‐Raman spectrometer system for use to differentiate tumor lesions from normal skin using an in vivo animal model. A study of 494 Raman spectra from 24 mice revealed different spectral patterns at different depths and between normal and tumor‐bearing skin sites. A peak at 899 cm⁻¹ (possibly from proline or fatty acids) and one with higher intensity in the 1325–1330 cm⁻¹ range (assigned to nucleic acids) were correlated with the presence of tumors, which can potentially be used as biomarkers for skin cancer detection. Spectral diagnosis performed on the murine tumor model achieved a diagnostic sensitivity of 95.8% and specificity of 93.8%. These results encourage us to develop further the use of confocal Raman spectroscopy as a clinical tool for noninvasive human skin biochemical analysis, particularly in relation to skin cancer. Copyright © 2010 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.     

Near‐infrared Raman spectroscopy for gastric precancer diagnosis

Raman spectroscopy is a molecular vibrational spectroscopic technique that is capable of optically probing the biomolecular changes associated with neoplastic transformation. The purpose of this study was to apply near‐infrared (NIR) Raman spectroscopy for differentiating dysplasia from normal gastric mucosa tissue. A total of 65 gastric mucosa tissues (44 normal and 21 dysplasia) were obtained from 35 patients who underwent endoscopy investigation or gastrectomy operation for this study. A rapid NIR Raman system was utilized for tissue Raman spectroscopic measurements at 785‐nm laser excitation. High‐quality Raman spectra in the range of 800–1800 cm⁻¹ can be acquired from gastric mucosa tissue within 5 s. Raman spectra showed significant differences between normal and dysplastic tissue, particularly in the spectral ranges of 850–1150, 1200–1500 and 1600–1750 cm⁻¹, which contained signals related to proteins, nucleic acids and lipids. The diagnostic decision algorithm based on the combination of Raman peak intensity ratios of I₈₇₅/I₁₄₅₀ and I₁₂₀₈/I₁₆₅₅ and the logistic regression analysis yielded a diagnostic sensitivity of 90.5% and specificity of 90.9% for identification of gastric dysplasia tissue. This work demonstrates that NIR Raman spectroscopy in conjunction with intensity ratio algorithms has the potential for the noninvasive diagnosis and detection of precancer in the stomach at the molecular level. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of Al content on the structure of Al‐substituted goethite: a micro‐Raman spectroscopic study

The characterization of X‐ray diffraction, X‐ray fluorescence, and field emission scanning electron microscope were used to confirm the successful preparation of Al‐substituted goethite with different Al content. The micro‐Raman spectroscopy was utilized to investigate the effect of Al content on the goethite lattice. The results show that all the feature bands of goethite shifted to high wavenumbers after the occurrence of Al substitution for Fe in the structure of goethite. The shift of wavenumber shows a good linear relationship as a function of increasing Al content especially for the band at 299 cm⁻¹ (R² = 0.9992). The in situ Raman spectroscopy of thermally treated goethite indicated that the Al substitution not only hinders the transformation of goethite, but also retarded the crystallization of thermally formed hematite. All the results indicated that Raman spectrum displayed an excellent performance in characterizing Al‐substituted goethite, which implied the promising application in other substituted metal oxides or hydroxides. Copyright © 2013 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.     

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.     

Al‐for‐Fe substitution in hematite: the effect of low Al concentrations in the Raman spectrum of Fe2O3

Five different mixed Al‐hematites with an aluminium molar content varying from 0 to 10% were investigated by micro‐Raman spectroscopy to study the effect of Al‐for‐Fe substitution on the hematite lattice. A red shift of hematite vibrational wavenumbers and a line broadening were observed; also a shoulder located near 430 cm⁻¹ and a broad band at 670 cm⁻¹ developed. The variation of the spectral features is discussed in terms of a local disorder correlated to the insertion of Al³⁺ ions into the Fe(O)₆ octahedra constituting hematite structure. A multivariate analysis was also carried out on the spectral data to distinguish between the doped samples analysed. Copyright © 2007 John Wiley & Sons, Ltd.     

OctTES/TEOS system for hybrid coatings: real‐time monitoring of the hydrolysis and condensation by Raman spectroscopy

The hybrid organic–inorganic system Tetra‐ethyl‐ortho‐silicate functionalized with Octyl‐triethoxy‐silane, studied as protective coating for the preservation of historical glasses from the environmental weathering agents, has been characterized by Raman spectroscopy by monitoring the sol‐gel reactions over time through characteristic features in the spectrum. In particular, for the hydrolysis reaction the disappearance of the 653 cm⁻¹ (Si‐O symmetric breathing) and 810 cm⁻¹ (CH₂ rocking in Si‐alkoxides) peaks and the growth of the 710 cm⁻¹ band, because of hydrolyzed alkyl‐silane, and of the 881 cm⁻¹ peak (ethanol C–C symmetric stretching) have been checked. Moreover, the condensation reaction can be tracked by the disappearance of the two main peaks of the alcohols at 816 and 881 cm⁻¹, going along with the growth of the broad band between 250 and 500 cm⁻¹ (Si–O–Si symmetric bending) and of the feature at 840 cm⁻¹ (Si–O–Si stretching). At the end of the condensation process the Raman spectrum still displays spectral bands unique to the alkyl chain in Octyl‐triethoxy‐silane, in the 1330–1450 cm⁻¹ and 2725–3000 cm⁻¹ ranges. Copyright © 2016 John Wiley & Sons, Ltd.     

A pigment (CuS) identified by micro‐Raman spectroscopy on a Chinese funerary lacquer ware of West Han Dynasty

A blue pigment was identified by micro‐Raman spectroscopy, X‐ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) and X‐ray diffraction (XRD). The test sample, a funerary lacquer tray, belongs to West Han Dynasty (206 BC–AD 8) of China and was decorated with faint blue patterns. The result from Raman spectroscopy showed that the faint blue is covellite (CuS) due to the presence of a characteristic peak at 474.5 cm⁻¹, which further was confirmed by XRF, SEM–EDX and XRD. This research indicated that CuS had been used as a blue pigment to decorate lacquer wares from the West Han Dynasty in China. Copyright © 2009 John Wiley & Sons, Ltd.     

Lipid organization and stratum corneum thickness determined in vivo in human skin analyzing lipid–keratin peak (2820–3030 cm−1) using confocal Raman microscopy

While the intercellular lipid structure of the stratum corneum (SC) plays an important role in the skin barrier function, the depth‐dependent profile of the intercellular lipids contributes decisively to deepen the understanding of the skin barrier function, drug penetration, development of skin diseases and their medication. The depth‐dependent profile of the lipids' chemico‐physical properties, such as the solid–fluid phase transition and the order–disorder transition, can exclusively be measured in human skin in vivo by means of confocal Raman microscopy. In the present paper, the lipid–keratin peak (2820–3030 cm⁻¹) was investigated. The lipid‐related Raman peaks centered at 2850 cm⁻¹ and 2880 cm⁻¹ were deconvoluted using Gaussian functions and investigated for their depth‐dependent shape and positional changes. Different fitting procedures show that even an additional Gaussian function cannot be used to fully characterize the lipid's polymethylene chains around 2880 cm⁻¹, which justifies the introduction of the sharpness of the peak centered near 2880 cm⁻¹. The results show that the 2880 cm⁻¹ peak sharpness might be used for determining the SC thickness. The concentration of the lipids with long‐chain carbon backbone (free fatty acids and ceramides) semi‐quantitatively decreases from 10 µm to 20 µm (SC thickness is 19.8 µm). The maximum position and broadness of the Gaussian peak centered at 2850 cm⁻¹ show that near the surface and in the deeper layers of the SC, the state of the lipids is more fluid and disordered compared to the medium layers of the SC. Copyright © 2016 John Wiley & Sons, Ltd.     

Micro‐Raman depth profiling of silicon amorphization induced by high‐energy ion channeling implantation

In this work, we study the silicon amorphization dependence on the crystal depth induced by 6‐MeV Al²⁺ ions implanted in the <110> and randomly oriented silicon crystal channels, which was not directly experimentally accessible in the previous similar high‐energy ion–crystal implantation cases. Accordingly, the micro‐Raman spectroscopy scanning measurements along the crystal transversal cross section of the ion implanted region were performed. The ion fluence was 10¹⁷ particles/cm². The scanning steps were 0.2 and 0.3 µm, for the channeling and random ion implantations, respectively. The obtained results are compared with the corresponding Rutherford backscattering spectra of 1.2‐MeV protons in the random and channeling orientations measured during the channeling implantation. Additionally, scanning electron microscope picture was taken on the transversal cross section of the implanted region in the channeling implantation case. We show here that the obtained silicon amorphization maxima are in excellent agreement with the corresponding estimated maxima of the aluminum concentration in silicon. This clearly indicates that the used specific micro‐Raman spectroscopy scanning technique can be successfully applied for the depth profiling of the crystal amorphization induced by high‐energy ion implantation. Copyright © 2013 John Wiley & Sons, Ltd.     

Single‐beam coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO2 via phase and polarization shaping of a broadband continuum

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO₂ is demonstrated using a single femtosecond (fs) laser beam. A shaped ultrashort laser pulse with a transform‐limited temporal width of ∼7 fs and spectral bandwidth of ∼225 nm (∼3500 cm⁻¹) is employed for simultaneous excitation of the CO₂ Fermi dyads at ∼1285 and ∼1388 cm⁻¹. CARS signal intensities for the two Raman transitions and their ratio as a function of pressure are presented. The signal‐to‐noise ratio of the single beam–generated CO₂ CARS signal is sufficient to perform concentration measurements at a rate of 1 kHz. The implications of these experiments for measuring CO₂ concentrations and rapid pressure fluctuations in hypersonic and detonation‐based chemically reacting flows are also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopy and characterisation of α‐gallium oxyhydroxide and β‐gallium oxide nanorods

Raman spectroscopy complemented by infrared spectroscopy was used to characterise both gallium oxyhydroxide (α‐GaO(OH)) and gallium oxide (β‐Ga₂O₃) nanorods synthesised with and without the surfactants using a soft chemical methodology at low temperatures. Nano‐ to micro‐sized gallium oxyhydroxide and gallium oxide materials were characterised and analysed by both X‐ray diffraction and Raman spectroscopy. Rod‐like GaO(OH) crystals with average length of ∼2.5 µm and width of 1.5 µm were obtained. Upon thermally treating gallium oxyhydroxide GaO(OH) to 900 °C, β‐Ga₂O₃ was synthesised retaining the initial GaO(OH) morphology. Raman spectroscopy has been used to study the structure of nanorods of GaO(OH) and Ga₂O₃ crystals. Raman spectroscopy shows bands characteristic of GaO(OH) at 950 and ∼1000 cm⁻¹ attributed to Ga OH deformation modes. Bands at 261, 275, 433 and 522 cm⁻¹ are assigned to vibrational modes involving Ga OH units. Bands observed at 320, 346, 418 and 472 cm⁻¹ are assigned to the deformation modes of Ga₂O₆ octahedra. Two sharp infrared bands at 2948 and 2916 cm⁻¹ are attributed to the GaO(OH) symmetric stretching vibrations. Raman spectroscopy of Ga₂O₃ provides bands at 630, 656 and 767 cm⁻¹ which are assigned to the bending and stretching of GaO₄ units. Raman bands at 417 and 475 cm⁻¹ are attributed to the symmetric stretching modes of GaO₂ units. The Raman bands at 319 and 347 cm⁻¹ are assigned to the bending modes of GaO₂ units. Copyright © 2008 John Wiley & Sons, Ltd.     

Germanium – the superior dopant in n‐type GaN

We present an experimental study about the influence of Si and Ge doping in GaN with focus on the occurring strain levels and overall crystalline quality. Extremely high quality samples were examined by means of Raman spectroscopy, demonstrating effective, n‐type doping concentrations up to the 5 × 10¹⁹ cm^–3 regime. By studying the full width at half maximum (FWHM) of the E₂(high) Raman mode with rising doping concentration, Ge is approved as the by far superior dopant if compared to Si. Even elevated nominal Ge concentrations yield corresponding FWHM values of just 3 cm^–1, a most competitive value even for bare bulk GaN samples. At the same time, the biaxial, compressive stress that is introduced by such high Ge doping amounts to just 0.2 GPa, in clear contrast to the particular case of silicon. Here, even moderate doping levels lead to tensile stress up to 1 GPa and consequently to a serious degeneration of the overall crystal quality as approved by our Raman analysis. Additionally, the examined high doping concentrations enable the observation of longitudinal optical phonon plasmon (LPP) modes in the Raman spectra, which serve as a direct tool for the determination of the effective doping concentration. A careful analysis of the LPP coupling at cryogenic and room temperature yields within the error interval identical free carrier concentrations in all germanium doped samples, pointing towards an energetically shallow nature of the dopant. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Micro‐Raman and IR study of the compressive behaviour of poly(paraphenylene benzobisoxazole) (PBO) fibres in a diamond‐anvil cell

The micro/nano structural evolution of PBO (poly(paraphenylenebenzobisoxazole), commercial name Zylon) fibres has been studied by Raman and IR spectroscopy in a diamond‐anvil cell, up to ∼15 GPa. Different modes were considered in the 900–1700 cm⁻¹ (Raman) and 800–3300 cm⁻¹ (IR) spectral range. The material behaviour appears more similar to that of a densely packed inorganic structure than to the behaviour previously observed for polyamide fibres, and is related to the compact arrangement of the rigid heterocyclic rings. Wavenumber shift starts with increase in pressure and a transition between the two regimes was revealed at ∼2–2.5 GPa, and it was assigned to the loss of order between neighbouring PBO chains. A good correlation is observed between the macroscopic mechanical properties and the nanomechanics at the chemical bond scale. Copyright © 2006 John Wiley & Sons, Ltd.     

Wavelength‐dependent amplitude of Teflon Raman lines

Raman and other spectroscopy systems operating in the deep ultraviolet (DUV) spectral region below 250 nm lack scattering standards. Such standards are particularly important for experiments that use multiwavelength excitation and/or when results are compared across different experiment platforms. Teflon has been used as an external standard in the visible and near‐IR spectral regions and has been suggested for use in the ultraviolet (UV). Comparison of the relative amplitudes of prominent Teflon Raman lines indicates a significant effect on line ratios when the excitation wavelength is below 250 nm. This dependence on excitation wavelength has been commented on previously and attributed to pre‐resonance effects, but no detailed examination had been undertaken to date. We present the results of a study of Teflon Raman line ratios obtained from closely spaced excitation wavelengths in the DUV from 210 to 320 nm. The 731 cm⁻¹ line is identified as well suited for a standard. Electronic transition energies associated with resonance of principal Teflon Raman lines are obtained. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic studies of ZnSe/GaAs interfaces

ZnSe/semi‐insulating GaAs interfaces were studied by observing photogenerated plasmon–LO (PPL) coupled modes by nonresonant micro‐Raman spectroscopy. The effect of the carriers generated by the focused laser beam was investigated for a series of different thicknesses of ZnSe epitaxial layers. The PPL mode in GaAs was observed in the micro‐Raman spectra for all samples, but with different magnitude. The plasma is believed to be an electron gas as a result of the negative nature of the interfacial region that contains predominantly hole traps. The free carrier concentration is estimated to be > 10¹⁸ cm⁻³ and their lifetime ∼0.1 ns. This relatively long lifetime suggests that the ZnSe/GaAs interface has to be of high structural quality leading to a low recombination velocity. ZnSe/GaAs heterostructures of less crystalline quality (as determined by resonant Raman measurements) shows the effect of photogenerated carriers only to lesser extent. Copyright © 2007 John Wiley & Sons, Ltd.     

Naturally irradiated fluorite as a historic violet pigment: Raman spectroscopic and X‐ray diffraction study

Naturally irradiated violet fluorite, a cubic CaF₂ mineral, is a rare historic pigment. Its documented usage in Europe stretches from ca. 1450 to ca. 1550. The intensely coloured violetish black naturally irradiated fluorite is commonly called antozonite, which is only vaguely defined based on its dark colour and specific odour emanated during grinding. In the published literature, there have been some discrepancies about its Raman spectrum. Therefore, sixteen samples of antozonite were analysed by Raman (micro‐)spectroscopy using five different excitation laser wavelengths (445, 532, 633, 780 and 1064 nm), which revealed specific bands located below 500 cm⁻¹ probably related to radiation‐caused defects. Their intensity increased with increasing violet colour saturation, thus providing a specification for antozonite's definition. Spectra excited at 445 and 780 nm contained also numerous broad bands above 500 cm⁻¹, which seem to be caused by the presence of rare earth elements. The structural damage of antozonite samples has been assessed by X‐ray diffraction and related to their lightness using analysis of image histograms. The obtained results have been applied in the analysis of micro‐samples of a Late Gothic altarpiece located in an Italian Court in UNESCO city Kutná Hora, Czech Republic, which contained exceptionally large grains of deep violet fluorite identified as antozonite. Copyright © 2015 John Wiley & Sons, Ltd.     

Hexagonal germanium formed via a pressure‐induced phase transformation of amorphous germanium under controlled nanoindentation

We have studied the stable end phase formed in amorphous germanium (a‐Ge) films that have been subjected to a pressure‐induced phase transformation under indentation loading using a large (20 µm) spherical indenter. After indentation the samples have been annealed at room temperature to remove any residual unstable R8 and BC8 phases. Raman spectroscopy indicates a single broad peak centred around 292 cm^–1 and we have used first principles density functional perturbation theory calculations and simulated Raman spectra for nano‐crystalline diamond cubic germanium (DC‐Ge) to help identification of the final phase as hexagonal diamond germanium (HEX‐Ge). Transmission electron microscopy and selected area diffraction analysis confirmed the presence of a dominant HEX‐Ge end phase. These results help explain significant inconsistencies in the literature relating to indentation‐induced phase transitions in DC‐ and a‐Ge. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)