Probing the ferroelectric phase transition in sol–gel‐derived polycrystalline bismuth ferrite thin films

Polycrystalline BiFeO₃ (BFO) thin films were successfully grown on Pt/Ti/SiO₂/Si(100) and SrTiO₃ (STO) (100) substrates using the chemical solution deposition (CSD) technique. X‐ray diffraction (XRD) patterns indicate the polycrystalline nature of the films with rhombohedrally distorted perovskite crystal structure. Differential thermal analysis (DTA) was performed on the sol–gel‐derived powder to countercheck the crystal structure, ferroelectric (FE) to paraelectric (PE) phase transition, and melting point of bismuth ferrite. We observed a significant exothermic peak at 840 °C in DTA graphs, which corresponds to an FE–PE phase transition. Raman spectroscopy studies were carried out on BFO thin films prepared on both the substrates over a wide range of temperature. The room‐temperature unpolarized Raman spectra of BFO thin films indicate the presence of 13 Raman active modes, of which five strong modes were in the low‐wavenumber region and eight weak Raman active modes above 250 cm⁻¹. We observed slight shifts in the lower wavenumbers towards lower values with increase in temperature. The temperature‐dependent Raman spectra indicate a complete disappearance of all Raman active modes at 840 °C corresponding to the FE–PE phase transitions. There is no evidence of soft mode phonons. Copyright © 2008 John Wiley & Sons, Ltd.     

Polarized Raman spectra of brushite (CaHPO4.2H2O) crystal. Investigation of the phosphate stretching modes,study of the LOTO splitting

Polarized Raman measurements were recorded on a monoclinic brushite (CaHPO₄.2H₂O) crystal in the 800–1200 cm⁻¹ spectral range, corresponding to the P O stretching modes. This study is a continuation of the investigation of the phosphate stretching modes observed in polarized infrared reflectance spectra of brushite crystal. In such ionic non‐centrosymmetric crystals, the splitting between the transverse and longitudinal components of the optic vibrations was observed in the polarized Raman spectra recorded at several scattering geometries. A″ symmetry modes of the brushite crystal were measured. Using a simple model based on the symmetry of the PO₄ group, the Raman intensities of the stretching modes are calculated and compared with experimental bands. Copyright © 2016 John Wiley & Sons, Ltd.     

Identification of oxygen vacancy types from Raman spectra of SnO2 nanocrystals

Raman spectra acquired from spherical SnO₂ nanocrystals prepared by pulsed laser ablation and hydrothermal synthesis exhibit three oxygen‐vacancy‐related Raman modes at 234, 573, and 618 cm⁻¹. The peak location and intensity vary with annealing temperature under O₂ finally approaching those of bulk materials. Density functional calculation discloses that the three Raman modes stem from subbridging, in‐plane, and bridging oxygen vacancies, respectively. Raman spectra can thus be used to discern different types of oxygen vacancies in SnO₂ nanocrystals. Copyright © 2012 John Wiley & Sons, Ltd.     

Comparative Raman spectroscopic analysis of orientation in fibers and regenerated films of Bombyx mori silk fibroin

This study is focused on the Raman spectroscopic analysis of degummed silk fibroin (SF) fibers and regenerated Bombyx mori silk fibroin films: a correlation was found between some spectral features related to the methylene deformation modes and the molecular orientation of the samples. Polarized Raman spectra on SF fibers were used to obtain the orientation distribution function of carbonyl groups along the protein backbone. The variation of the intensity ratio of 1400/1450 cm⁻¹ for the peaks attributed to the wagging and bending deformation modes of CH₂ groups with respect to the angular orientation of the fiber was measured and quantitatively correlated with the orientation distribution function of the carbonyl groups. Unpolarized Raman spectra were measured for regenerated silk fibroin films and lyophilized solutions. The variation of the intensity ratio of 1415/1455 cm⁻¹, which is related to the deformation modes of CH₂ groups in SF regenerated materials, was qualitatively related to the microstructural orientation of the samples observed by scanning electron microscopy (SEM), and to the presence of Silk I phase as suggested by the analysis of samples obtained in different casting conditions and also by the measurements on mechanically deformed films. The results obtained showed the utility of the spectroscopic intensity ratio of 1400/1450 cm⁻¹ for the rapid assessment of molecular orientation in silk fibers, which could be useful for quality and process control of regenerated silk‐based textiles. Moreover, the qualitative dependence of the intensity ratio of 1415/1455 cm⁻¹ was found to be sensitive to both the microstructural orientation and Silk I content of regenerated silk fibroin films, suggesting a possible correlation of this Raman marker of the Silk I phase with the degree of molecular order brought about by this polymorph. Copyright © 2006 John Wiley & Sons, Ltd.     

Resonance Raman and electronic absorption study of free‐base tetraphenylporphine diacid dispersed in polymethylcyanoacrylate

We report a resonance Raman study on free‐base tetraphenylporphine (H₂TPP) and its chemically prepared diacid dispersed in polymethylcyanoacrylate (PMCA). Photoexcitation of the neutral porphine by laser light leads irreversibly to the formation of the diacid, with the π‐cation radical as intermediate species. Resonance Raman (RR) spectra of the diacid dispersed in the polymer obtained with 441.6 nm in the wavenumber region of 100–1650 cm⁻¹ are recorded. Wavenumbers with other excitation lines are also reported for the diacid species. Some bands assigned to out‐of‐plane vibrational modes and forbidden under ideal D_2h symmetry are also observed in the resonance Raman spectra of the diacid. These bands arise from the out‐of‐plane distortions, which reduce the symmetry of the molecule. These findings are supported by the electronic absorption studies of the diacid in the polymer. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman polarization studies of highly oriented organic thin films

In this work we report on the capability of polarized Raman spectroscopy to investigate the structure of thin organic films. Diindenoperylene (DIP) thin films on (1 × 1)‐rutile(110) were prepared via organic molecular beam deposition (OMBD). Raman spectra of DIP thin films showed several strong Raman modes in the wavenumber region from 1200 to 1650 cm⁻¹. The A_g mode at 1284 cm⁻¹ shows two contributions, thereby indicating the coexistence of at least two DIP film structures. Polarized Raman spectroscopy was applied to characterize the molecular orientation and the dominance of the σ‐configuration (i.e. upright standing DIP molecules) was found. Copyright © 2009 John Wiley & Sons, Ltd.     

Identification of Mn‐related Raman modes in Mn‐doped ZnO thin films

This article aims to investigate the Raman modes present in Mn‐doped ZnO thin films that are deposited using the magnetron co‐sputtering method. A broad band ranging from 500 to 590 cm⁻¹ is present in the Raman spectra of heavily Mn‐doped ZnO films. The multi‐peak‐fitting results show that this broad band may be composed of six peaks, and the peak at 528 cm⁻¹ could be a characteristic mode of Mn₂O₃. The results of this study suggest that the origin of the Raman peaks in Mn‐doped ZnO films may be due to three major types: structural disorder and morphological changes caused by the Mn dopant, Mn‐related oxides and intrinsic host‐lattice defects. Copyright © 2010 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.     

分子筛组装单质半导体碲的拉曼光谱

无机介孔材料MCM41是高有序,直孔道介孔分子筛,具有孔径约4nm的一维均匀孔道,孔壁厚约1nm,介孔体积可达40%,是一种很理想的组装材料主体。半导体碲位于第Ⅵ族,其六方相的晶格排列呈螺旋链状结构。本文采用固相合成反应方法,将单质半导体碲成功地组装在MCM41介孔分子筛中。在组装体中,单质半导体碲保持着六方相的晶体结构,其拉曼晶体振动表现出纳米晶体的结构特征。真空热处理实验表明,组装体具有良好的热稳定性。Te的六方相和所具有的独特的螺旋链状结构使Te分子很容易进入MCM41的直孔道内,同时MCM41均匀而规则的直孔道限制了Te螺旋链的随机排列,因而被组装在直孔道内的Te能螺旋链式生长,形成一维半导体纳米晶体,排列均匀,尺寸单一,具有稳定的空间构型     

Raman and infrared investigations at room temperature of the internal modes behaviour in solid nitromethane‐h3 and ‐d3 up to 45 GPa

Raman and infrared spectra of internal phonons in solid nitromethane‐h₃ and ‐d₃ were measured as a function of pressure in the range 0–40 GPa at room temperature. Experiments were performed in diamond anvil cells. The evolution of the splitting of the various modes in condition of nearly hydrostatic compression supports the maintenance of the P2₁2₁2₁ crystal structure until the material chemically transforms into an amorphous phase. The observed pressure‐induced shifts of vibrational wavenumbers are consistent with computations recently reported in the literature. Infrared and Raman spectroscopies deliver complementary information on the internal modes behaviour. The continuous evolution of the infrared band shapes suggests a weak molecular distortion during the compression process. The strong modifications that are observed in the Raman bands of the nitro group are attributed to polarization effects arising from a rearrangement of the molecules inside the unit cell in the pressure range 10–12 GPa, a consequence of a close intermolecular O…H approach. Copyright © 2007 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.     

Raman study of structural disorder in ZnO nanopowders

Raman scattering spectroscopy has been used for the characterization of zinc oxide nanoparticles obtained by mechanical activation in a high‐energy vibro‐mill and planetary ball mill. Raman modes observed in spectra of nonactivated sample are assigned to Raman spectra of the ZnO monocrystal, while the spectra of mechanically activated samples point out to the structural and stoichiometric changes, depending on the milling time and the choice of equipment. Observed redshift and peak broadening of the E₂^high and E₁ (LO) first‐order Raman modes are attributed to increased disorder induced by mechanical milling, followed by the effects of phonon confinement due to correlation length decrease. The additional modes identified in Raman spectra of activated ZnO samples are related to the surface optical phonon modes, due to the intrinsic surface defects and presence of ZrO₂as extrinsic defects introduced by milling in zirconia vials. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman-spectroscopy study of PbTiO3 thin films grown on Si substrates by metalorganic chemical vapor deposition

Raman spectra have been investigated in PbTiO₃ thin films grown on Si by metalorganic chemical vapor deposition. A large grazing-angle scattering technique was taken to measure the temperature dependence of Raman spectra below room temperature. All Raman modes in the thin films are assigned and compared with those in the bulk single crystal, a newA ₁(TO) soft mode at 104 cm^–1 was recorded which satisfies the Curie-Weiss relation ² =A(T _c –T). Intensities of theA ₁(1TO) andE(1TO) modes were anomalously strengthened with increasing temperature. Raman modes for the thin films exhibit remarkable frequency downshift and upshift which is related to the effect of internal stress.     

Investigation of weak damage in Al0.25Ga0.75As/GaAs by using RBS/C and Raman spectroscopy

The weak damage induced by 0.8 MeV Si ion implantation in the Al_0.25Ga_0.75As films epitaxially grown on GaAs substrates was studied by using Rutherford backscattering spectrometry/channeling (RBS/C) and Raman spectroscopy. RBS/C spectra measured from the implanted samples showed rather low damage level induced by the ion implantation with ion dose from 1×10¹⁴ to 5×10¹⁵ cm⁻². The Raman spectra were measured on these samples. Two kinds of phonon modes, GaAs-like and AlAs-like, are observed, which indicate the existence of multiple phonon vibrational modes in the epitaxial Al_0.25Ga_0.75As films on the GaAs substrate. Compared with the unimplanted sample, the Raman photon peaks for the implanted sample shift gradually to lower energy with the increase of the implantation dose. The strains induced in the implanted layer were also evaluated from the Raman spectra. The result from high resolution double crystal X-ray diffractometry (HRXRD) also verified the evolution of the strains in the implanted layers.     

IR,Raman and SERS spectra of ethyl salicylate

The IR and Raman spectra of ethyl salicylate were recorded and analyzed. The surface enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound have been computed using the Hartree‐Fock/6‐31G* basis. The direction of charge transfer contribution to SERS has been discussed from the frontier orbital theory. The presence of methyl modes in the SERS spectrum indicates the nearness of the methyl group to the metal surface and the presence of ring vibrations and out‐of‐plane ring modes in the SERS spectrum suggests a flat orientation of the molecule on the silver surface. The first hyperpolarizability is calculated and the calculated molecular geometry has been compared with the reported similar structures. Copyright © 2009 John Wiley & Sons, Ltd.     

High‐pressure Raman spectra of deuterated L‐alanine crystal

Raman spectra of deuterated L ‐alanine have been obtained at high‐pressure conditions. A phase transition at ∼1.5 GPa associated with the splitting of some internal modes and increase of the wavenumber of the external modes was observed. Similarly to the hydrogenated L ‐alanine crystal, this first transition was related to a symmetry change. Moreover, further modifications of the Raman spectra were observed at 4.4 GPa, which may be associated to conformational changes of the molecule. To give further support to such a hypothesis, neutron powder diffraction measurements were performed. Information about the cell parameter at atmospheric pressure gave valuable information about the N D distances, shedding light on the behavior of the torsional vibration of ND₃⁺. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopy of hydrogen arsenate group (AsO3OH)2− in solid‐state compounds: cobalt‐containing zinc arsenate mineral,koritnigite (Zn,Co)(AsO3OH)·H2O

Raman spectra of two well‐defined types of koritnigite crystals from the Jáchymov ore district, Czech Republic, were recorded and interpreted. No substantial differences were observed between both crystal types. The observed Raman bands were attributed to the (AsO₃OH)²⁻ stretching and bending vibrations as well as stretching and bending vibrations of water molecules and hydroxyl ions. The non‐interpreted Raman spectra of koritnigite from the RRUFF database and the published infrared spectra of cobaltkoritnigite were used for comparison. The O H···O hydrogen bond lengths in the crystal structure of koritnigite were inferred from the Raman spectra and compared with those derived from the X‐ray single‐crystal refinement. The presence of (AsO₃OH)²⁻ units in the crystal structure of koritnigite was proved from the Raman spectra, which supports the conclusions of the X‐ray structure analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Organic cyclic difluoramino‐nitramines: infrared and Raman spectroscopy of 3,3,7,7‐tetrakis(difluoramino)octahydro 1,5‐dinitro‐1,5‐diazocine (HNFX)

We present the first vibrational structure investigation of 3,3,7,7‐tetrakis(difluoramino)octahydro‐1,5‐dinitro‐ 1,5‐diazocine (HNFX)—and, more generally, of a member of the new class of gem‐bis(difluoramino)‐substituted heterocyclic nitramine energetic materials—using combined theoretical and experimental approaches. Optimized molecular structure and vibrational spectra of the Ci… symmetry conformer constituting the HNFX crystal were computed using density functional theory methods. Fourier transform infrared and Raman spectra of HNFX crystalline samples were also collected at ambient temperature and pressure. The average deviation of calculated structural parameters from X‐ray diffraction data is ∼1% at the B3LYP/6‐311 + + G(d,p) level of theory, suggesting the absence of significant molecular distortion induced by the crystal field. Very good agreement was found between simulated and measured spectra, allowing reliable assignment of the fundamental normal modes of vibration of the HNFX crystal. Detailed analysis of the normal modes of the C–(NF₂)₂ and N–NO₂ moieties was performed due to their critical importance in the initial steps of the molecular homolytic fragmentation process. Copyright © 2009 John Wiley & Sons, Ltd.     

Photoluminescence and Raman spectra of the ordered vacancy compound CuGa5Se8

We studied the photoluminescence (PL) and Raman properties of the ordered defect compound CuGa₅Se₈. Twelve peaks were detected from the room-temperature Raman spectra with the A₁ mode around 160 cm⁻¹. Due to the stress in the polycrystalline thin film the corresponding frequencies of the Raman modes of a CuGa₅Se₈ single crystal were slightly shifted. One broad asymmetric PL band at 1.788 and 1.765 eV was observed at 10 K in the PL spectra of CuGa₅Se₈ single crystal and polycrystalline layer, respectively. The temperature and laser power dependencies of the PL spectra were also studied. The shape and properties of the PL band assure the presence of potential fluctuations and the analyses of the PL data suggest that the emission is due to band-to-tail (BT) or band-to-impurity (BI) recombination.     

Raman spectroscopic study of the uranyl titanate mineral euxenite (Y,Ca,U,Ce,Th) (Nb,Ta,Ti)2O6

Raman spectra of the uranyl titanate mineral euxenite were analysed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. The observed bands are attributed to the Ti O and (UO₂)²⁺ stretching and bending vibrations, as well as lattice vibrations of rare‐earth ions. The Raman bands of euxenite are in harmony with those of the uranyl oxyhydroxides. The mineral euxenite is metamict as is evidenced by the intensity of the U O stretching and bending modes, which are of lower intensity than expected, and with bands that are significantly broader. Copyright © 2010 John Wiley & Sons, Ltd.