Facile shape-controlled synthesis of palladium nanostructures on copper for promising Surface-enhanced Raman scattering

In this letter, size-controlled Pd nanocubes, hexagonal prism and Pd dendrites nanostructures were synthesized by a simple galvanic displacement process between Pd ion and Cu. The sizes and morphology of Pd nanostructures could be controlled by simply regulating the reaction parameters, such as concentration of palladium dichloride, reaction time and types of surfactant. A possible formation mechanism of Pd nanocubes was also briefly discussed. Furtherly, Surface-enhanced Raman scattering (SERS) investigation demonstrated the nanostructures on copper foils were SERS-active by using 4-aminothiophenol (PATP) as probe molecule. We believe the unique Pd nanostructures on copper foils would be a flexible and promising SERS substrate.     

Preparation of silver nanoparticles by photo-reduction for surface-enhanced Raman scattering

A substrate for surface-enhanced Raman scattering (SERS) has been developed. Based on the surface-catalyzed reduction of Ag⁺ by citrate on the silver nanoparticles surface under light irradiation, small silver seeds on a quartz slide can be enlarged. The optical properties and characteristics of the silver films have been investigated by ultraviolet-visible spectroscopy, scan electron microscope and atomic force microscopy (AFM). The results indicate that the particle size and shape are different at different reduction time. At the first 3 h, some triangular and hexagonal nanoparticles formed; with the reduction proceeding, the shape of the silver particles became irregular and the size became larger. The silver films obtained are very suitable as SERS active substrate. The relationship between SERS intensity and the reduction time has been investigated for 1,4-bis[2-(4-pyridyl)ethenyl]-benzene molecule adsorbed on the silver film. The SERS intensity reached a maximum at 8 h reduction. The AFM measurements indicate that roughness features with an average size of 100 nm are present on the surface, which yielded the strongest SERS signal. Pyridine was used as a probe molecule to investigate the enhancement factor (EF) of the silver films. According to the formalism of Tian and co-workers, the EF of the silver films is estimated to be 3.4 × 10⁵. The silver film that can remain active for more than 50 days would seem to be suitable for various analytical applications.     

Graphene oxide-Ag nanocomposite: In situ photochemical synthesis and application as a surface-enhanced Raman scattering substrate

In the present study, a facile method is developed for the synthesis of graphene oxide-Ag nanocomposite (GOAg). The method involves the application of in situ photochemical deposition and growth processes under certain alkaline environments in the absence of chemical reductants and surfactants. Silver nanoparticles with monodisperse size are well dispersed on the surface of graphene oxide (GO). The roles of GO and NaOH in the formation of GOAg are discussed. A corresponding formation mechanism of GOAg is proposed. Fluorescence quenching and Raman enhancement are examined as well.     

Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled films of ruthenium phthalocyanine on organic monolayer-modified silver substrates

A self-assembled film of ruthenium phthalocyanine (RuPc) fabricated on a silver substrate pre-modified with a monolayer of 4-mercaptopyridine (PySH) or 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was studied by ultraviolet-visible (UV-Vis) and surface enhanced Raman scattering (SERS) spectroscopy. PySH or BPENB was used as a ligand to link RuPc since they not only modify the silver substrate, but also deliver a pyridyl group pointing out from the silver surface. Therefore, we can explore the relationship between the structure and orientation of metallophthalocyanine and the substrate modified by the two kinds of organic-monolayers with the different conjugates and molecular lengths. UV-Vis bands due to the organic-monolayer (PySH or BPENB) modified silver films shift to longer wavelengths and a new band arising from the metallophthlocyanine appears, suggesting the binding of RuPc to PySH/BPENB, as well as the interaction between the marcocycle of RuPc and the ring of PySH/BPENB. Vibrational bands arising from both the RuPc and PySH/BPENB moieties appear clearly in the SERS spectra of the RuPc-PySH/BPENB composite films, indicating that RuPc is successfully assembled on the top of PySH/BPENB film. The shifts and relative intensity changes of bands due to PySH or BPENB in the SERS spectra imply the binding of the metallophthalocyanine to the pyridyl group in the composite films. Furthermore, the comparison of the SERS spectra revealed that the orientations of PySH and BPENB in the two kinds of composite films are different; the BPENB moiety in the RuPc-BPENB composite film is more perpendicular to the silver surface compared with the PySH moiety in the RuPc-PySH composite film.     

Directional emission of surface-enhanced Raman scattering based on a planar-film plasmonic antenna

A planar-film plasmonic antenna for surface-enhanced Raman scattering (SERS) with good emission directivity (divergence angle < 3°) was realized on a Kretschmann prism configuration with Raman-active analytes as emitters. The simulated results of finite-difference time-domain method show the emission efficiency, the directivity and the gain of the planar-film antenna were expected to be 50%, 300 and 22 dB, respectively. Angle-resolved spectroscopy was used to characterize its properties in SERS. The experimental results show that the SERS signal of analytes was remarkably enhanced when a laser excited this planar-film plasmonic antenna at the resonance angle. Meanwhile, the radiation of SERS was concentrated in a small region in space. The planar-film antenna with high gain coefficient can be a promising light harvesting and emitting device. The good emission directivity allows high collection efficiency. This advantage opens up interesting prospects in the applications for plasmon-enhanced spectroscopy and single-phonon detections.     

Preparation of dendritic Ag/Au bimetallic nanostructures and their application in surface-enhanced Raman scattering

Dendritic Ag/Au bimetallic nanostructures have been synthesized via a multi-stage galvanic replacement reaction of Ag dendrites in a chlorauric acid (HAuCl₄) solution at room temperature. After five stages of replacement reaction, one obtains structures with protruding nanocubes; these will mature into many porous structures with a few Ag atoms that are left over dendrites. The morphological and compositional changes which evolved with reaction stages were analyzed by using scanning electron microscopy, transmission electron microscopy, UV-visible spectroscopy, selected area electron diffraction and energy-dispersive X-ray spectrometry. The replacement of Ag with Au was confirmed. A formation mechanism involving the original development of Ag dendrites into porous structures with the growth of Au nanocubes on this underlying structure as the number of reaction stages is proposed. This was confirmed by surface-enhanced Raman scattering (SERS). The dendritic Ag/Au bimetallic nanostructures could be used as efficient SERS active substrates. It was found that the SERS enhancement ability was dependent on the stage of galvanic replacement reaction.     

Silver nanoparticles deposited on anodic aluminum oxide template using magnetron sputtering for surface-enhanced Raman scattering substrate

Low-cost and highly sensitive surface-enhanced Raman scattering (SERS) substrates have been fabricated by a simple anodizing process and a magnetron sputtering deposition. The substrates, which consist of silver nanoparticles embedded on anodic aluminum oxide (AAO) templates, are investigated by a scanning electron microscope and a confocal Raman spectroscopy. The SERS activities are demonstrated by Raman scattering from adsorbed solutions of methylene blue and pyridine on the SERS substrate surface. The most optimized SERS substrate contains the silver nanoparticles, with a size distribution of 10-30 nm, deposited on the AAO template. From a calculation, the SERS enhancement factor is as high as 8.5 × 10⁷, which suggests strong potentials for direct applications in the chemical detection and analyses.     

Preparation of Ag2S–Graphene nanocomposite from a single source precursor and its surface-enhanced Raman scattering and photoluminescent activity

Ag₂S–Graphene nanocomposite was prepared via a relatively facile hydrothermal method, using a single-source molecular (silver diethyldithiocarbamate [Ag(DDTC)]) as precursor and graphene sheets as a support material. The composite was characterized by X-ray power diffraction, X-ray photoelectron spectroscopy, Field-emission scanning electron microscope, transmission electron microscopy, Fourier transform infrared, Raman spectra and fluorescence spectroscopy. The experimental results show that the Ag₂S–Graphene nanocomposite displays surface-enhanced Raman scattering (SERS) activity for graphene oxide and reveals relatively better fluorescence property compared with pure Ag₂S.     

Silver-embedded zeolite crystals as substrates for surface-enhanced Raman scattering

This paper reports the preparation of a type of Ag-embedded zeolite crystals as surface-enhanced Raman spectroscopy (SERS) substrates by chemical reduction of Ag⁺-exchanged ZSM-5. Ag⁺ ions were loaded into the zeolite framework by ion exchange. Then the exchanged-Ag⁺ ions were reduced and metallic silver clusters formed inside the zeolite channel. The resulting Ag-embedded zeolite crystals are characterized by using a number of techniques including X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm silver formed inside the crystal channel. The fabricated Ag-embedded ZSM-5 zeolite substrates displayed strong and reproducible SERS activity for different Raman probe molecules such as Tris(2,2′-bipyridyl) ruthenium(II) chloride (RuBpy) and rhodamine 6G (R6G). Since silver embedded into the zeolite channel without changing the crystal surface property, the Ag–ZSM-5 zeolite crystal can be used to prepare different SERS-active substrate (SERS-tags), in which different probe molecules may be detected. Such Ag-embedded zeolite substrate would be useful in chemical and biological sensing and in the development of SERS-based analytical devices.     

A nanoforest structure for practical surface-enhanced Raman scattering substrates

A nanoforest structure for surface-enhanced Raman scattering (SERS) active substrates is fabricated and analyzed. The detailed morphology of the resulting structure can be easily controlled by modifying the process parameters such as initial gold layer thickness and etching time. The applicability of the nanoforest substrate as a label-free SERS immunosensor is demonstrated using influenza A virus subtype H1N1. Selective binding of the H1N1 surface antigen and the anti-H1 antibody is directly detected by the SERS signal differences. Simple fabrication and high throughput with strong in-plane hot-spots imply that the nanoforest structure can be a practical sensing component of a chip-based SERS sensing system.     

Raman scattering for the size of CdSe and CdS nanocrystals and comparison with other techniques

The sizes of the ensembles of CdSe regular nanocrystals (RNCs), CdSe magic-sized nanocrystals (MSNCs), and CdS RNCs were investigated by Raman scattering. The nanocrystal ensembles were synthesized via wet-chemistry approaches. The size distribution increases from CdSe MSNCs (2.26 nm), to CdSe RNCs (3.52 nm), and to CdS RNCs (3-8 nm and 4-10 nm). The sizes derived from Raman spectra are compared with those from other characterization tools such as UV/vis spectroscopy and transmission electron microscopy (TEM). The present study suggests that Raman scattering is an alternative and reliable technique for the determination of nanocrystal size and size distribution.     

Controllable synthesis of pentagonal silver nanowires via a simple alcohol-thermal method

Pentagonal silver nanowires with diameters in range of 20-40 nm, and lengths up to ~ 10 µm were successfully synthesized via a simple and effective alcohol-thermal route. These nanowires were prepared by reducing silver nitrate in ethanol solution with dodecylamine which acted as complexing, reducing and capping agent. The molar ratio of dodecylamine to AgNO₃ played an important role in controlling aspect ratio of the products. Samples were characterized in detail by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) technologies. UV-vis absorption spectrum of the nanowires in solution has been taken to study their optical properties. Based on the analysis of the experimental results, the possible formation mechanism of nanowires was proposed as well.     

Silver nanowire layer-by-layer films as substrates for surface-enhanced Raman scattering

In this paper, the fabrication of highly stable, surface-enhanced Raman scattering (SERS) active dendrimer/silver nanowire layer-by-layer (LBL) films is reported. Ag nanowires, approximately 100 nm in diameter, were produced in solution and transferred, using the LBL technique, onto a single fifth-generation DAB-Am dendrimer layer on a glass substrate. The Ag nanowires, and the resulting LBL films were characterized using UV-visible surface plasmon absorbance, while the LBL films were further characterized by atomic force microscopy measurements and surface-enhanced Raman and resonance Raman scattering of several analytes. The dendrimer was found to effectively immobilize the Ag nanowires with increased control over spacing and aggregation of the particles. These films are shown to be excellent substrates for SERS/SERRS measurements, demonstrating significant enhancement, and trace detection capability. Several trial analytes were tested using a variety of excitation energies, and results confirmed effective enhancement of Raman signals throughout the visible range (442-785 nm) with different molecules. Analytes were deposited onto the enhancing Ag nanowire LBL films surface using both casting and Langmuir-Blodgett monolayer transferring techniques.     

Silver-coated zeolite crystal films as surface-enhanced Raman scattering substrates

Silver-coated zeolite A and zeolite NaX crystal films prepared by vacuum deposition were investigated as surface-enhanced Raman scattering (SERS) substrates. The substrates were active for the enhancement of Raman scattering from uranyl ions. A detection limit of 10(-5) M for uranyl was obtained using silver-coated zeolite A films. One advantage of these zeolite-based substrates is that the negatively charged microporous framework provides the selectivity for adsorption based on static electric charges. The SERS effects of positively charged uranyl ions and neutrally charged benzoic acid were compared. For the zeolite A substrate, there was a 100-times-greater sensitivity.     

Tunable and highly reproducible surface-enhanced Raman scattering substrates made from large-scale nanoparticle arrays based on periodically poled LiNbO3 templates

Abstract

This work describes novel surface-enhanced Raman scattering (SERS) substrates based on ferroelectric periodically poled LiNbO₃ templates. The templates comprise silver nanoparticles (AgNPs), the size and position of which are tailored by ferroelectric lithography. The substrate has uniform and large sampling areas that show SERS effective with excellent signal reproducibility, for which the fabrication protocol is advantageous in its simplicity. We demonstrate ferroelectric-based SERS substrates with particle sizes ranging from 30 to 70 nm and present tunable SERS effect from Raman active 4-mercaptopyridine molecules attached to AgNPs when excited by a laser source at 514 nm.     

3D nano-arrays of silver nanoparticles and graphene quantum dots with excellent surface-enhanced Raman scattering

Active surface-enhanced Raman scattering (SERS) substrates, 3D nano-arrays of Ag nanoparticles (NPs) and graphene quantum dots (GQDs), were prepared using a photochemical approach and an electrophoresis deposition technique with the formation mechanism addressed. The GQDs (ca. 6?nm average) fit into the inter-particle gaps between Ag NPs, as verified by their scanning electron microscopy and high-resolution transmission electron microscopy. This deliberately designed 3D assembly of Ag NPs and GQDs could promote the synergistic effects of both components to further enhance the SERS performances according to both electromagnetic mechanism and chemical mechanism. Preliminary experiments show that the 3D substrates exhibited strong SERS signals comparing with bare Si substrates. This work provides a promising way for 3D SERS substrates.     

Silver nanocrystal-modified silicon nanowires as substrates for surface-enhanced Raman and hyper-Raman scattering

Metal catalyzed, CVD-grown silicon nanowires decorated by chemical assembly of closely spaced Ag nanocrystals were modified with the well-known "silver mirror" reaction and investigated as substrates for surface-enhanced Raman (SERS) and hyper-Raman (SEHRS) spectroscopy. Four chromophores were examined: Rhodamine 6G, crystal violet, a cyanine dye, and a cationic donor-acceptor substituted stilbene. After soaking the substrates overnight in 10(-4) M aqueous chromophore solutions, all four chromophores gave good-quality SERS spectra in < or =60 s using <1 microW of 458-nm cw laser power, and SEHRS spectra are obtained in < or =120 s using <1 mW of mode-locked 916-nm laser power. Results from this substrate are compared with those on colloidal silver nanoparticles deposited as a film, as well as surfaces grown by the silver mirror reaction.     

Amplitude-squared and amplitude-cubed squeezing in stimulated Raman and in spontaneous Raman scattering

Coherent light coupled to a third-order nonlinear medium is responsible for spontaneous and for stimulated Raman processes. The analytical solutions up to second order in coupling constants of various field modes for spontaneous Raman and for stimulated Raman processes are utilized to obtain the amplitude-squared and amplitude-cubed squeezing of the input coherent light. The amplitude-squared and amplitude-cubed squeezing are completely ruled out for all modes for spontaneous Raman processes. For stimulated Raman processes, we observe that the squeezing for amplitude-squared and amplitude-cubed are possible for pump and for vibrational phonon modes. It is found that the percentage of higher ordered amplitude squeezing decreases with the increase of the orders. The squeezing in Stokes and in anti-Stokes modes are ruled out even for stimulated Raman processes.     

New strategy for ready application of surface-enhanced resonance Raman scattering/surface-enhanced Raman scattering to chemical analysis of organic films on dielectric substrates

Dropping of appropriately concentrated AgNO3 and NaBH4 solutions, as well as laser-ablated Ag sols, onto organic molecules results in the formation of aggregated Ag nanoparticles that can induce surface-enhanced Raman scattering (SERS) for the molecules. The addition of flocculating agents such as alkali halides can further increase the Raman signals. We demonstrate in this work that Raman spectra can be obtained even for 0.01 monolayers of R6G on Si simply by spreading silver nanoparticles and/or fabricating Ag nanoparticles and nanoaggregates at the gaps and vacant sites of R6G molecules. The application prospect of the present methodology is extremely high, not only because of its simplicity but also because of the fact that the observation of vibrational spectra is one of the most incisive methods for understanding the chemical and physical phenomena on a variety of surfaces.     

Deposition of the fractal-like gold particles onto electrospun polymethylmethacrylate fibrous mats and their application in surface-enhanced Raman scattering

The ultrafine polymethylmethacrylate fibers containing gold nanoparticles have been prepared by using the electrospinning technique. Then the continuously coarse gold films formed by fractal-like thorny gold particles were deposited on the organic eletrospun fiber surface by an electroless process. The morphology of coarse gold films was characterized by scanning electron and transmission electron microscopy. The results revealed that the morphology of the gold particles was affected not only by the amount of gold seeds embedded in the organic fibers but also by the amount of gold deposited on the fiber's surfaces. The surface-enhanced Raman scattering (SERS) effect of the fibrous mats coated with gold films was evaluated by using Rhodamine B as an adsorbate. The results indicated that this kind of fibrous mat exhibited high and reproducible SERS activity and could be developed as highly sensitive SERS substrate.