Co-deposition of gold nanoparticles and metalloporphyrin using the langmuir-blodgett (LB) technique for Surface-Enhanced Raman Scattering (SERS)

The synergistic effect produced by metallic nanoparticles when incorporated into different systems empowers a research field that is growing rapidly. In addition, organometallic materials are at the center of intensive research with diverse applications such as light-emitting devices, transistors, solar cells, and sensors. The Langmuir-Blodgett (LB) technique has proven to be suitable to address challenges inherent to organic devices, since the film properties can be tuned at the molecular level. Here we report a strategy to incorporate gold nanoparticles (AuNPs) into the LB film by co-deposition in order to achieve surface-enhanced Raman scattering (SERS) of the zinc(II)-protoporphyrin (IX) dimethyl ester (ZnPPIX-DME). Prior to the LB co-deposition, the properties of the Langmuir monolayer of ZnPPIX-DME at the air-water interface, containing AuNPs in the subphase, are studied through the surface-pressure versus mean molecular area (π-A) isotherms. The ZnPPIX-DME+AuNPs π-A isotherm presented a significant shift to higher molecular area, suggesting an interaction between both ZnPPIX-DME molecules and AuNPs. Those interactions are a key factor allowing the co-deposition of both AuNPs and ZnPPIX-DME molecules onto a solid substrate, thus forming the LB film. SERS of ZnPPIX-DME was successfully attained, ensuring the spatial distribution of the AuNPs. Higher enhancement factors were found at AuNP aggregates, as a result of the intense local electromagnetic field found in the metal nanoparticle aggregates. The main vibrational bands observed in the SERS spectra suggest a physical adsorption of the ZnPPIX-DME onto the surface of AuNPs. The latter is not only in agreement with the interactions pointed out by the π-A isotherms but also suggests that this interaction is kept upon LB film co-deposition.

Substrato flexível portátil para detecção e análises químicas usando fenômenos de amplificação sers e serrs por espectroscopia micro-raman e processo de obtenção do dito substrato

É descrita a invenção de um substrato flexível portátil para detecção e análises químicas usando fenômenos de amplificação sers e serrs por espectroscopia micro-raman e processo de obtenção do dito substrato. É descrita a invenção de um substrato flexível portátil para detecção e análises químicas usando fenômenos de amplificação sers (surface enhanced raman spectroscopy) e serrs (surface-enhanced resonance spectroscopy) por espectroscopia micro-raman e respectivo processo de obtenção do dito substrato que provê um substrato de borracha natural impregnando com nanopartículas de ouro.

Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.

Nanofabrication of Surface-Enhanced Raman Scattering Device by an Integrated Block-Copolymer and Nanoimprint Lithography Method

The integration of block-copolymers and nanoimprint lithography presents a novel and cost-effective approach to achieving nanoscale patterning capabilities. The authors demonstrate the fabrication of a surface-enhanced Raman scattering device using templates created by the block-copolymers nanoimprint lithography integrated method.

Bathorhodopsin structure in the room-temperature rhodopsin photosequence: picosecond time-resolved coherent anti-Stokes Raman scattering.

Structural changes in the retinal chromophore during the formation of the bathorhodopsin intermediate (bathoRT) in the room-temperature rhodopsin (RhRT) photosequence (i.e., vision) are examined using picosecond time-resolved coherent anti-Stokes Raman scattering. Specifically, the retinal structure assignable to bathoRT following 8-ps excitation of RhRT is measured via vibrational Raman spectroscopy at a 200-ps time delay where the only intermediate present is bathoRT. Significant differences are observed between the C=C stretching frequencies of the retinal chromophore at low temperature where bathorhodopsin is stabilized and at room temperature where bathorhodopsin is a transient species in the RhRT photosequence. These vibrational data are discussed in terms of the formation of bathoRT, an important step in the energy storage/transduction mechanism of RhRT.

Neutron irradiation effect in two-dimensional electron gas of AlGaN/GaN heterostructures

AlGaN/GaN heterostructures have been irradiated by neutrons with different influences and characterized by means of temperature-dependent Hall measurements and Micro-Raman scattering techniques. It is found that the carrier mobility of two-dimensional electron gas (2DEG) is very sensitive to neutrons. At a low influence of 6.13 x 10(15) cm(-2), the carrier mobility drops sharply, while the sheet carrier density remains the same as that of an unirradiated sample. Moreover, even for a fluence of up to 3.66 x 10(16) cm(-2), the sheet carrier density shows only a slight drop. We attribute the degradation of the figure-of-merit (product of n(s) x mu) of 2DEG to the defects induced by neutron irradiation. Raman measurements show that neutron irradiation does not yield obvious change to the strain state of AlGaN/GaN heterostructures, which proves that degradation of sheet carrier density has no relation to strain relaxation in the present study. The increase of the product of n(s) x mu of 2DEG during rapid thermal annealing processes at relatively high temperature has been attributed to the activation of Ge-Ga transmuted from Ga and the recovery of displaced defects.

Columnar structures and stress relaxation in thick GaN films grown on sapphire by HVPE

Thick GaN films with high quality are directly grown on sapphire in a home-built vertical hydride vapour phase epitaxy (HVPE) reactor. The optical and structural properties of large scale columnar do-mains near the interface are studied using cathodoluminescence and micro-Raman scattering. These columnar do-mains Show a strong emission intensity due to extremely high free carrier concentration up to 2 x 10(19) cm(-3), which are related with impurities trapped in structural defects. The compressive stress in GaN Elm clearly decreases with increasing distance from interface. The quasi-continuous columnar domains play an important role in the stress relaxation for the upper high quality layer.

Microstructure characterization of transition films from amorphous to nanocrocrystalline silicon

Hydrogenated silicon (Si:H) films near the threshold of crystallinity were prepared by very high-frequency plasma-enhanced chemical vapor deposition (VHF-PECVD) using a wide range of hydrogen dilution R-H = [H-2]/[SiH4] values of 2-100. The effects of H dilution R-H on the structural properties of the films were investigated using micro-Raman scattering and Fourier transform infrared (FTIR) absorption spectroscopy. The obtained Raman spectra show that the H dilution leads to improvements in the short-range order and the medium-range order of the amorphous network and then to the morphological transition from amorphous to crystalline states. The onset of this transition locates between R-H = 30 and 40 in our case, and with further increasing R-H from 40 to 100, the nanocrystalline volume fraction increases from similar to23% to 43%, and correspondingly the crystallite size enlarges from similar to2.8 to 4.4 nm. The FTIR spectra exhibit that with R-H increasing, the relative intensities of both the SiH stretching mode component at 2100 cm(-1) and wagging mode component at 620 cm(-1) increase in the same manner. We assert that these variations in IR spectra should be associated with the formation of paracrystalline structures in the low H dilution films and nanocrystalline structures in the high H dilution films. (C) 2003 Elsevier Science B.V. All rights reserved.

Stress and its effect on optical properties of GaN epilayers grown on Si(111), 6H-SiC(0001), and c-plane sapphire

The stress states in unintentionally doped GaN epilayers grown on Si(111), 6H-SiC(0001), and c-plane sapphire, and their effects on optical properties of GaN films were investigated by means of room-temperature confocal micro-Raman scattering and photoluminescence techniques. Relatively large tensile stress exists in GaN epilayers grown on Si and 6H-SiC while a small compressive stress appears in the film grown on sapphire. The latter indicates effective strain relaxation in the GaN buffer layer inserted in the GaN/sapphire sample, while the 50-nm-thick AlN buffer adopted in the GaN/Si sample remains highly strained. The analysis shows that the thermal mismatch between the epilayers and the substrates plays a major role in determining the residual strain in the films. Finally, a linear coefficient of 21.1+/-3.2 meV/GPa characterizing the relationship between the luminescent bandgap and the biaxial stress of the GaN films is obtained. (C) 2003 American Institute of Physics.

Microstructure of a-SiOx : H

A set of a-SiOx:H (0.52 < x < 1.58) films are fabricated by plasma-enhanced-chemical-vapor-deposition (PECVD) method at the substrate temperature of 250degreesC. The microstructure and local bonding configurations of the films are investigated in detail using micro-Raman scattering, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). It is found that the films are structural inhomogeneous, with five phases of Si, Si2O:H, SiO:H, Si2O3:H and SiO2 that coexist. The phase of Si is composed of nonhydrogenated amorphous silicon (a-Si) clusters that are spatially isolated. The average size of the clusters decreases with the increasing oxygen concentration x in the films. The results indicate that the structure of the present films can be described by a multi-shell model, which suggests that a-Si cluster is surrounded in turn by the subshells Of Si2O:H, SiO:H, Si2O3:H, and SiO2.

Optical properties of nanocrystalline silicon embedded in SiO2

Nanocrystalline silicon embedded SiO2 matrix has been formed by annealing the a-SiOx films fabricated by plasma enhanced chemical vapor deposition technique. Absorption and photoluminescence spectra of, the films have been studied in conjunction with micro-Raman scattering spectra. It is found that absorption presents an exponential dependence of absorption coefficient to photon energy in the range of 1.5-3.0 eV, and a sub-band appears in the range of 1.0-1.5 eV. The exponential absorption is due to the indirect band-to-band transition of electrons in silicon nanocrystallites, while the sub-band absorption is ascribed to transitions between surfaces and/or defect states of the silicon nanocrystallites. The existence of Stokes shift between absorption and photoluminescence suggests that the phonon-assisted luminescence would he enhanced due to the quantum confinement effects.

High temperature annealing behaviors of luminescent SIOx : H films

The effects of high temperature annealing on the microstructure and optical properties of luminescent SiOx:H films have been investigated. Micro-Raman scattering and IR absorption, in combination with atomic force microscopy (AFM), provide evidence for the existence of both a-Si clusters in the as-grown a-SiOx:H and Si nanocrystals in the 1170 degrees C annealed films. The dependence of optical coefficients (alpha) on photon energy (h nu) near the absorption edge (E-g) is found to follow the square root law: (alpha h nu)(1/2) proportional to (E-g - h nu), indicating that nano-Si embedded in SiO2 is still an indirect material. A comparison of the deduced absorption edge with the PL spectra shows an obvious Stokes shift, suggesting that phonons should be involved in the optical transition process.