Correlation of size and oxygen bonding at the interface of Si nanocrystal in Si–SiO2 nanocomposite: A Raman mapping study

Raman spectroscopy/mapping is used to investigate the variation of Si phonon wavenumbers, i.e., lower wavenumber (LW ~ 495–510 cm⁻¹) and higher wavenumber (HW ~ 515–519 cm⁻¹) phonons, observed in Si–SiO₂ multilayer nanocomposite (NCp) grown using pulsed laser deposition. Sensitivity of Raman spectroscopy as a local probe to surface/interface is effectively used to show that LW and HW phonons originate at surface (Si–SiO₂ interface) and core of Si nanocrystals, respectively. The consistent picture of this understanding is developed using Raman spectroscopy monitored laser heating/annealing and cooling experiment at the site of the desired wavenumber, chosen with the help of Raman mapping. Raman spectra calculations for Si₄₁ cluster with oxygen and hydrogen termination show strong mode at 512 cm⁻¹ for oxygen terminated cluster corresponding to the vibration of surface Si atoms. This supports our attribution of LW phonons to be originating at the Si–SiO₂ surface/interface. These results along with XPS show that nature of interface (oxygen bonding) in turn depends on the size of nanocrystals and LW phonons originate at the surface of smaller Si nanocrystals. The understanding developed can conclude the ongoing debate on large variation in Si phonon wavenumbers of Si–SiO₂ NCps in the literature. Copyright © 2015 John Wiley & Sons, Ltd.     

Fabrication and surface enhanced Raman spectroscopy of single Au@SiO2 dimers linked by benzenedithiol

Metal nanoparticle dimers with controllable gap distance have attracted considerable attention because of their promising application in plasmonics. Generally, gaps with nanometer or subnanometer dimensions generate localized surface plasmon resonance (LSPR) coupling effect, thus contributing to a strong electromagnetic field for improving surface enhanced Raman scattering (SERS) effect. Here, we developed a facile approach to fabricate Au@SiO₂ dimers through the steric hindrance effect, in which the SiO₂ shell functioned as a block and a rigid dithiol molecule was employed as linker. The thickness of the SiO₂ shell played a critical role in improving the yield of dimers. The dimerization efficiency increased significantly as the shell thickness decreased to ~1 nm. When 1,4‐benzenedithiol was used as linker molecule, the yield of dimers was ~30%. Few dimers were obtained when mecaptobenzonic acid was used as linker. A thicker shell is associated with a low yield of dimer, whereas a thinner shell resulted in the formation of multimers and linear structures. The low number of linker molecules on the exposed area of monodisperse single nanoparticles and the lack of LSPR coupling effect (‘hot spots’) resulted in the disappearance of SERS signals of the linkers. The estimated SERS enhancement factor was about eight fold because of the strong coupling effect in the gap of the dimer with the distance of the dithiol molecular length. From the above results, SERS combined with SEM could be developed into powerful tools for monitoring the formation of dimers and positioning of single dimers. It may aid the control of assembly of Au nanoparticles and in probing key issues about SERS enhancements. Copyright © 2015 John Wiley & Sons, Ltd.     

Unraveling the electronic structure of transition metal dimers using resonant four‐wave mixing

The potential of two‐color resonant and degenerate four‐wave mixing spectroscopy for investigations of the complex spectra of transition metal dimers is explored. Two‐color resonant and degenerate four‐wave mixing spectroscopy scans of the well‐known A‐X and B‐X transitions in Cu₂ are reported and compared with previous experimental data obtained from standard single‐resonance techniques. The selectivity of the method is shown to enable the measurement of isotopologue pure spectra without the need for isotopically enriched metal targets. Specific subsets of the rovibronic structure are separated in a congested spectral region of overlapping transitions. The sensitivity of the method compares satisfactorily with linear spectroscopic methods such as laser‐induced fluorescence and cavity ring‐down. A new laser vaporization source for the production of transition metal dimers and clusters has been constructed. The new design aims for a high number density and maximum possible shot‐to‐shot stability. The possibilities of further applications of non‐linear four‐wave mixing spectroscopy to Cu₂ and other transition metal dimers are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

The electrochemical reduction of CO2 on a copper electrode in 1‐n‐butyl‐3‐methyl imidazolium tetrafluoroborate (BMI.BF4) monitored by surface‐enhanced Raman scattering (SERS)

The electrochemical conversion of CO₂ into value‐added products using room temperature ionic liquids as solvent/electrolyte has been proposed as an alternative to minimize the environmental effects of CO₂ emissions. A key issue in the design of electrochemical systems for the reduction of CO₂ is the in situ identification of intermediate surface species as well as reaction products. Copper electrodes, besides being used as cathodes in the electrochemical reduction of CO₂, present surface‐enhanced Raman scattering (SERS) when properly activated. In this sense, the electrochemical reduction of CO₂ over a copper electrode in the room temperature ionic liquids 1‐n‐butyl‐3‐methyl imidazolium tetrafluoroborate (BMI.BF₄) was investigated by cyclic voltammetry and by in situ SERS. The cyclic voltammetries have shown that the presence of CO₂ on the BMI.BF₄ anticipates the reduction of BMI⁺ to the corresponding carbene. Fourier‐transform‐SERS spectra excited at 1064 nm and SERS spectra excited at 632.8 nm have shown vibrational signals from adsorbed CO. These SERS results indicated that CO adsorbs on the copper surface at two different surface sites. The observation of a 2275 cm⁻¹ vibration in the SERS spectra also confirmed the presence of chemically adsorbed CO₂. Other products of CO₂ reduction in BMI.BF₄, besides CO, were identified, including BMI carbene and the BMI‐CO₂ adduct. The SERS results also suggest that the presence of a thin film of Cu₂O on the copper surface anticipates the reduction of CO₂ to CO, an important component of syngas. Copyright © 2016 John Wiley & Sons, Ltd.     

Solvent‐dependent structural dynamics of 2(1H)‐pyridinone in light absorbing S4(ππ*) state

The B‐band resonance Raman spectra of 2(1H)‐pyridinone (NHP) in water and acetonitrile were obtained, and their intensity patterns were found to be significantly different. To explore the underlying excited state tautomeric reaction mechanisms of NHP in water and acetonitrile, the vibrational analysis was carried out for NHP, 2(1D)‐pyridinone (NDP), NHP–(H₂O)_n (n = 1, 2) clusters, and NDP–(D₂O)_n (n = 1, 2) clusters on the basis of the FT‐Raman experiments, the B3LYP/6‐311++G(d,p) computations using PCM solvent model, and the normal mode analysis. Good agreements between experimental and theoretically predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands in both the FT‐Raman and the resonance Raman spectra. The results indicated that most of the B‐band resonance Raman spectra in H₂O was assignable to the fundamental, overtones, and combination bands of about ten vibration modes of ring‐type NHP–(H₂O)₂ cluster, while most of the B‐band resonance Raman spectra in CH₃CN was assigned to the fundamental, overtones, and combination bands of about eight vibration modes of linear‐type NHP–CH₃CN. The solvent effect of the excited state enol‐keto tautomeric reaction mechanisms was explored on the basis of the significant difference in the short‐time structural dynamics of NHP in H₂O and CH₃CN. The inter‐molecular and intra‐molecular ESPT reaction mechanisms were proposed respectively to explain the Franck–Condon region structural dynamics of NHP in H₂O and CH₃CN.Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of different substrates for Raman spectroscopic imaging of eukaryotic cells

For Raman spectroscopic analyses of the cells and other biological samples, the choice of the right substrate material is very important to avoid loss of information in characteristic spectral features because of competing background signals. In the current study, Raman spectroscopy is used to characterize several potential Raman substrates. Raman vibrational bands of the substrate material are discussed. The surface topography is analyzed by atomic force microscopy, and the root mean square surface roughness values are reported. Biocompatibility of the substrates is tested with Hep G2 cells evaluating cellular morphology as well as live/dead staining. Calcium fluoride, silicon, fused silica, borofloat glass, and silicon nitride membranes support cell growth and adherence. Silicon, borofloat glass, and fused silica give rise to Raman signals in the region of interest. Calcium fluoride substrate (UV grade) is suitable for Raman spectroscopic investigation of living cells. Nickel foil is suitable substrate for Raman spectroscopic investigation but cellular adherence and viability depend on the quality of the foil. Silicon nitride membranes coated with nickel chrome is a suitable Raman substrate in closed microfluidic systems. Copyright © 2016 John Wiley & Sons, Ltd.     

Defects band enhanced by resonance Raman effect in praseodymium doped CeO2

In this work, the origin of the Raman defects band at 570 cm⁻¹ of praseodymium‐doped ceria was revisited from in situ spectra using six different exciting lines between 458 and 785 nm at low temperatures after oxidizing or reducing treatment. The observation of overtones and the fast change of relative intensity with excitation wavelength were explained by a resonance effect around 514 nm, which involved a Pr⁴⁺ containing defect stabilized at the oxidized state leading to an absorption band around 530 nm. The reduction of Pr⁴⁺ cations contained in such defects modifies the electronic properties of praseodymium doped ceria inhibiting the resonance effect. Additionally, the number of D1 defects that involved Pr³⁺ cations and oxygen vacancies increased allowing them to be distinguished. Copyright © 2016 John Wiley & Sons, Ltd.     

层合板三维-二维混合分区有限元法研究

本文提出了一种三维-二维混合分区有限元方法分析复合材料层合结构。构造了三维-二维过渡元素和三维的十七节点复合元素。本方法大大地减少了自由度,缩短了计算时间。算例表明,计算结果令人满意。本方法是可靠的并同样适用于其它结构。     

PROGRESS IN THREE-DIMENSIONALLY ORDERED SELF-ASSEMBLY OF COLLOIDAL SiO2 PARTICLES

Three-dimensionally ordered self-assembly of monodispersed colloidal SiO2 particles involving a structure with periodic alternation of refractive indices represents an advanced field of particuology, colloidal chemistry, materials science, optical physics and information science. Study on such self-assembly not only lays the foundation for the development of advanced functional materials, but also is significant in understanding the principles of nano- and micro-scele processes. Recent progress in three-dimensionally ordered self-assembly of colloidal SiO2 particles is reviewedinclusive of the authors‘‘ investigations.