Identification of pigments from the Shrine of Kaiping Diaolou by micro‐Raman spectroscopy

Shrines (or altars) are constructed in China for worshiping ancestors, Bodhisattva, and God of Wealth. In this work, pigments from the shrine of Kaiping Diaolou tower were analyzed by micro‐Raman spectroscopy, in conjunction with other analytical methods including scanning electron microscopy (SEM) with energy dispersive X‐ray spectroscopy (EDX) and X‐ray fluorescence (XRF). Paintings of the shrine were composed of 2–3 pigment layers and the total thickness was determined as about 200–300 µm by optical microscopy and SEM, indicating the fine painting skills applied in the construction of the shrine. The green pigments on the surface layer of the green fragment were identified as a mixture of lead phthalocyanine (PbPc) and cornwallite (Cu₅(AsO₄)₂(OH)₄) by XRF and micro‐Raman spectroscopy with two different excitation wavelengths (488 and 785 nm). Underneath the green layer, red and yellow ochre were found. The pigments on the surface layer of red and blue fragments were identified as hematite (Fe₂O₃) and lazurite or synthetic ultramarine [(Na₈(Al₆Si₆O₂₄)S₃)], respectively. Finally, the pigments under the two surface layers were identified by EDX and micro‐Raman spectroscopy as chromium oxide (Cr₂O₃), gypsum (CaSO₄·2H₂O) and calcite (CaCO₃). Copyright © 2011 John Wiley & Sons, Ltd.     

Densification of sol–gel silica thin films induced by hard X‐rays generated by synchrotron radiation

In this article the effects induced by exposure of sol–gel thin films to hard X‐rays have been studied. Thin films of silica and hybrid organic–inorganic silica have been prepared via dip‐coating and the materials were exposed immediately after preparation to an intense source of light of several keV generated by a synchrotron source. The samples were exposed to increasing doses and the effects of the radiation have been evaluated by Fourier transform infrared spectroscopy, spectroscopic ellipsometry and atomic force microscopy. The X‐ray beam induces a significant densification on the silica films without producing any degradation such as cracks, flaws or delamination at the interface. The densification is accompanied by a decrease in thickness and an increase in refractive index both in the pure silica and in the hybrid films. The effect on the hybrid material is to induce densification through reaction of silanol groups but also removal of the organic groups, which are covalently bonded to silicon via Si—C bonds. At the highest exposure dose the removal of the organic groups is complete and the film becomes pure silica. Hard X‐rays can be used as an efficient and direct writing tool to pattern coating layers of different types of compositions.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman spectroscopy of sol–gel derived titanium oxide thin films

Raman spectra of TiO₂ films prepared via the sol–gel process were studied by UV and visible Raman spectroscopy. The evolution of the phases of TiO₂ films during annealing was investigated, and the relative intensities of the Raman bands excited with 325 nm were found to be distinct from those of the bands excited with 514 nm. The transmittance and FTIR spectra of the films annealed at different temperatures were characterized. The crystallization process of the powders and thin films treated by different annealing methods were also studied with Raman spectroscopy. The results show that the change in the relative intensities is caused by the resonance Raman effect. The anatase to rutile transition of the powder occurs at 700 °C, while that of the thin film occurs at 800 °C. The analysis of Raman band shape (peak position and full width at half‐maximum) after conventional furnace annealing and rapid thermal annealing indicates the influence of the non‐stoichiometry and phonon confinement effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation,luminescence and structural properties of rare‐earth‐doped RbLuS2 compounds

Rare‐earth (RE = Ce, Pr, Sm, Tb) doped ternary sulfides of the general formula RbLu_0.99RE_0.01S₂ and undoped RbLuS₂ were synthesized in the form of crystalline hexagonal platelets by chemical reaction in the electric resistance furnace under the flow of hydrogen sulfide. Only a single crystalline phase of the rhombohedral lattice system (space group $ {\rm R}\bar 3{\rm m}) $ was detected by X‐ray powder diffraction. Absorption and luminescence characteristics were measured. The band edge of RbLuS₂ is found at 310 nm, and characteristic Pr³⁺, Sm³⁺ and Tb³⁺ 4f–4f emission lines in the visible spectral range are observed. A charge transfer transition in the Pr³⁺ excitation spectrum in the near UV spectral region is revealed and an efficient energy transfer from the host to the emission centers is found. The application potential for white LED or X‐ray phosphors is discussed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman spectroscopy of very small Cd1−xCoxS quantum dots grown by a novel protocol: direct observation of acoustic‐optical phonon coupling

Glass‐embedded Cd_1−xCo_xS quantum dots (QDs) with mean radius of R ≈ 1.70 nm were successfully synthesized by a novel protocol on the basis of the melting‐nucleation synthesis route and herein investigated by several experimental techniques. Incorporation of Co²⁺ ions into the QD lattice was evidenced by X‐ray diffraction and magnetic force microscopy results. Optical absorption features with irregular spacing in the ligand field region confirmed that the majority of the incorporated Co²⁺ ions are under influence of a low‐symmetry crystal field located near to the Cd_1−xCo_xS QD surface. Electron paramagnetic resonance data confirmed the presence of Co²⁺ ions in a highly inhomogeneous crystal field environment identified at the interface between the hosting glass matrix (amorphous) and the crystalline QD. The acoustic‐optical phonon coupling in the Cd_1−xCo_xS QDs (x ≠ 0.000) was directly observed by Raman measurements, which have shown a high‐frequency shoulder of the longitudinal optical phonon peak. This effect is tuned by the size‐dependent sp‐d exchange interaction due to the magnetic doping, causing variations in the coupling between electrons and longitudinal optical phonon. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

Synthesis and Raman investigation of sol–gel‐derived relaxor ferroelectric thin films

Pb(Fe_2/3W_1/3)O₃ (PFW) thin films were deposited on platinized silicon substrate by a chemical solution deposition technique. Room‐temperature X‐ray diffraction (XRD) revealed a pure cubic crystal structure of the investigated material. The microstructure indicated good homogeneity and density of the thin films. A Raman spectroscopic study was carried out on PFW to study the polar nano‐regions in the temperature range 85–300 K. The Raman spectra showed a change in the peak intensity and a shift towards the lower wavenumber side with temperature. The Raman spectra also revealed the transition from the relaxor to the paraelectric state of PFW. There was no evidence of a soft mode in the low‐temperature region, in contrast to the normal ferroelectric behavior. The polar nano‐regions tend to grow and join at low temperatures (∼85 K), which become smaller with increase in temperature. The presence of strong Raman spectra in the cubic phase of the material is due to the presence of distributed Fm3m(Z = 2) symmetry nano‐ordered regions in the Pm3m(Z = 1) cubic phase. Copyright © 2007 John Wiley & Sons, Ltd.     

Tuning the phase transition of ZnO thin films through lithography: an integrated bottom‐up and top‐down processing

An innovative approach towards the physico‐chemical tailoring of zinc oxide thin films is reported. The films have been deposited by liquid phase using the sol–gel method and then exposed to hard X‐rays, provided by a synchrotron storage ring, for lithography. The use of surfactant and chelating agents in the sol allows easy‐to‐pattern films made by an organic–inorganic matrix to be deposited. The exposure to hard X‐rays strongly affects the nucleation and growth of crystalline ZnO, triggering the formation of two intermediate phases before obtaining a wurtzite‐like structure. At the same time, X‐ray lithography allows for a fast patterning of the coatings enabling microfabrication for sensing and arrays technology.     

Microfocus X‐ray scattering and micro‐Raman spectroscopy: Transcrystallinity in isotactic polypropylene

Microfocus X‐ray scattering and micro Raman spectroscopy have been applied to study the β‐transcrystalline morphology in isotactic polypropylene. The transformation from the α‐ to the β‐form through the so‐called bifurcation of growth mechanism has been investigated with high spatial resolution. We found that the mixed α–β region does not present spatial correlation along the shearing direction, implying that there is no cooperative crystallization from the different β‐nucleation centres. In addition, a strong change in the lamellar orientation of the α‐form thin layer that induces the growth of the β‐crystallites has been observed for the first time. Finally, changes in the relative intensities of some selected Raman bands allowed the observation of the α–β transformation process at the molecular level.

     

Structural,thermal and optical study of nanocrystalline silicon produced by ball milling

The ball milling process was used to obtain nanocrystalline cubic silicon. Between 5 and 10 h of milling, amorphous silicon was also formed. The differential scanning calorimetry (DSC) spectrum of a powder milled for 10 h showed that the amorphous–crystalline phase transition occurs at about 450 °C. According to Raman spectroscopy and X‐ray diffraction results, volume fractions of the crystalline, interfacial and amorphous phases were about 30, 39 and 31%, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman characterization of the structural evolution in amorphous and partially nanocrystalline hydrogenated silicon thin films prepared by PECVD

Hydrogenated silicon (Si:H) thin films were obtained by plasma‐enhanced chemical vapor deposition (PECVD). Raman spectroscopy was used to investigate the structural evolution in phosphor‐doped n‐type amorphous hydrogenated silicon thin films, which were prepared under different substrate temperatures and gas pressures. Meanwhile, the effect of nitrogen doping on the structure of P‐doped thin films was also investigated by Raman spectroscopy. Moreover, the transition from the amorphous state to the nanocrystalline state of undoped Si:H films deposited through low argon dilution was studied by Raman spectroscopy, X‐ray diffraction, and transmission electron microscopy. The results show that Raman spectroscopy can sensitively detect the structural evolution in hydrogenated silicon thin films deposited under different conditions in a PECVD system. Copyright © 2010 John Wiley & Sons, Ltd.     

A Raman spectroscopic study of teeth affected with molar–incisor hypomineralisation

Raman spectroscopy was used to chemically map lesions associated with molar–incisor hypomineralisation in human teeth. Three teeth with hypomineralised lesions of differing severity, described as white, yellow or brown, were mapped using integral ratios of major component bands (hydroxyapatite, amide I and b‐type carbonate) and principal component analysis scores values. These lesions were found to contain depleted levels of mineral (hydroxyapatite) compared with those of healthy enamel. Principal component analysis also highlighted changes in the phosphate structure and variations in various organic constituents. These variations were consistent with increased disorder in the mineral component of the hypomineralised tooth lesions. Scanning electron microscopy–energy dispersive X‐ray spectroscopy supported the findings based on Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

Semipolar (11\bar 2\bar 2) ZnO thin films grown on LaAlO3‐buffered LSAT (112) single crystals by pulsed laser deposition

Semipolar (11\bar 2 \bar 2) ZnO was successfully grown on (112) LaAlO₃/(LaAlO₃)_0.29(Sr₂AlTaO₆)_0.35 substrate by pulsed laser deposition. The epitaxial relationship is [11\bar 23]_{\rm ZnO} // [11\bar 1]_{\rm LAO/LSAT} with the polar axis of [000\bar 1]_{\rm ZnO} pointing to the surface. For ZnO films with thickness of 1.6 μm, the threading dislocation density is ～1 × 10⁹ cm^–2, and the density of basal stacking faults is below 1 × 10⁴ cm^–1. The (11\bar 2 \bar 2) ZnO exhibits strong D⁰X emissions with a FWHM of 9 meV and very few green–yellow emissions in the low‐temperature (10 K) and room‐temperature photoluminescence spectra, respectively.

     

Radiation damage to protein specimens from electron beam imaging and diffraction: a mini‐review of anti‐damage approaches,with special reference to synchrotron X‐ray crystallography

Recent research progress using X‐ray cryo‐crystallography with the photon beams from third‐generation synchrotron sources has resulted in recognition that this intense radiation commonly damages protein samples even when they are held at 100 K. Other structural biologists examining thin protein crystals or single particle specimens encounter similar radiation damage problems during electron diffraction and imaging, but have developed some effective countermeasures. The aim of this concise review is to examine whether analogous approaches can be utilized to alleviate the X‐ray radiation damage problem in synchrotron macromolecular crystallography. The critical discussion of this question is preceded by presentation of background material on modern technical procedures with electron beam instruments using 300–400 kV accelerating voltage, low‐dose exposures for data recording, and protection of protein specimens by cryogenic cooling; these practical approaches to dealing with electron radiation damage currently permit best resolution levels of 6 Å (0.6 nm) for single particle specimens, and of 1.9 Å for two‐dimensional membrane protein crystals. Final determination of the potential effectiveness and practical value of using such new or unconventional ideas will necessitate showing, by experimental testing, that these produce significantly improved protection of three‐dimensional protein crystals during synchrotron X‐ray diffraction.     

On the application of a single‐crystal κ‐diffractometer and a CCD area detector for studies of thin films

A multipurpose six‐axis κ‐diffractometer, together with the brilliance of the ESRF light source and a CCD area detector, has been explored for studying epitaxial relations and crystallinity in thin film systems. The geometrical flexibility of the six‐axis goniometer allows measurement of a large volume in reciprocal space, providing an in‐depth understanding of sample crystal relationships. By a set of examples of LaAlO₃ thin films deposited by the atomic layer deposition technique, the possibilities of the set‐up are presented. A fast panoramic scan provides determination of the crystal orientation matrices, prior to more thorough inspection of single Bragg nodes. Such information, in addition to a broadening analysis of families of single reflections, is shown to correlate well with the crystallinity, crystallite size, strain and epitaxial relationships in the thin films. The proposed set‐up offers fast and easy sample mounting and alignment, along with crucial information on key features of the thin film structures.     

In situ synchrotron X‐ray diffraction analysis of deformation behaviour in Ti–Ni‐based thin films

Deformation mechanisms of as‐deposited and post‐annealed Ti_50.2Ni_49.6, Ti_50.3Ni_46.2Cu_3.5 and Ti_48.5Ni_40.8Cu_7.5 thin films were investigated using the in situ synchrotron X‐ray diffraction technique. Results showed that initial crystalline phases determined the deformation mechanisms of all the films during tensile loading. For the films dominated by monoclinic martensites (B19′), tensile stress induced the detwinning of 〈011〉 type‐II twins and resulted in the preferred orientations of (002)_B19′ parallel to the loading direction (∥ LD) and (020)_B19′ perpendicular to the LD (⊥ LD). For the films dominated by austenite (B2), the austenite directly transformed into martensitic variants (B19′) with preferred orientations of (002)_B19′ ∥ LD and (020)_B19′ ⊥ LD. For the Ti_50.3Ni_46.2Cu_3.5 and Ti_48.1Ni_40.8Cu_7.5 films, martensitic transformation temperatures decreased apparently after post‐annealing because of the large thermal stress generated in the films due to the large differences in thermal expansion coefficients between the film and substrate.     

Raman spectroscopic investigation of lanthana‐doped neodymium‐yttria transparent ceramics

Transparent ceramics of the formula (Nd_0.01La_xY_0.99−x)₂O₃ (x = 0, 0.05, 0.10) were made with nanopowders and sintered in H₂ atmosphere. The Raman spectra of Ln₂O₃ (Ln = Y, La, Nd) powders and (Nd_0.01La_xY_0.99−x)₂O₃ ceramics were investigated. The results show that both La₂O₃ and Nd₂O₃ powders are of hexagonal structure, and all (Nd_0.01La_xY_0.99−x)₂O₃ ceramics exhibit the same cubic Y₂O₃ crystal structure. Their lattice parameters were refined by the Rietveld method. The full‐widths at half‐maximum of Raman peaks increase with the increase in La₂O₃ content in transparent (Nd_0.01Y_0.99)₂O₃ ceramics, while their intensities decrease. At the same time, All Raman peaks shift to lower wavenumbers, and the phonon energy is slightly reduced. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectroscopic and structural investigations of α‐, β‐, and γ‐AlH3 phases

With its reputation as a high‐energy density fuel, aluminum hydride (AlH₃) has received renewed attention as a material that is particularly suitable, not only for hydrogen storage but also for rocket propulsion. While the various phases of AlH₃ have been investigated theoretically, there is a shortage of experimental studies corroborating the theoretical findings. In response to this, we present here an investigation of these compounds based primarily on two research areas in which there is the greatest scarcity of information in the literature, namely Raman and infrared (IR) absorption analysis. To the authors' knowledge, this is the first report of experimental far‐IR absorption results on these compounds. Two different samples prepared by broadly similar ethereal reactions of AlCl₃ with LiAlH₄ were analyzed. Both Raman and IR absorption measurements indicate that one sample is purely γ‐AlH₃ and that the other is a mixture of α‐, β‐, and γ‐AlH₃ phases. X‐ray diffraction confirms the spectroscopic findings, most notably for the β‐AlH₃ phase, for which optical spectroscopic data are reported here for the first time. Copyright © 2010 John Wiley & Sons, Ltd.