Surface-enhanced Raman spectroscopy of the growth of ultra-thin organosilicon plasma polymers on nanoporous Ag/SiO2-bilayer films

A new method for the synthesis of thin bilayer films as surface-enhanced Raman spectroscopy (SERS) active substrates was developed which is based on the combination of plasma polymerization, plasma calcination and Ag-film deposition by means of physical vapor deposition. The surface morphology of prepared substrates was characterized by field emission scanning electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. These substrates lead to high surface enhancement factors proven by the spectroscopic analysis of adsorbed Trans-1,2 bis-(4-pyridyl) ethylene molecules. By this preparation technique, SERS-active films can be deposited on any substrate. The new SERS substrates were successfully applied to study the growth of ultra-thin hexamethyldisiloxane plasma polymer films. The Raman intensity of the CH-stretching vibration was studied as a function of the film thickness. The surface enhancement decreased sharply at about 20 nm. The resulting increase in the intensity of Raman peaks for thin adsorbed plasma polymer films was observed to be a combination of the electromagnetic enhancement mechanism and the high surface area increase of the rough Ag-surface.     

Spherical Nanoparticle Arrays with Tunable Nanogaps and Their Hydrophobicity Enhanced Rapid SERS Detection by Localized Concentration of Droplet Evaporation

Periodic hexagonal spherical nanoparticle arrays are fabricated by a sacrificial colloidal monolayer template route by chemical deposition and further physical deposition. The regular network‐structured arrays are first templated by colloidal monolayers and then they are changed to novel periodic spherical nanoparticle arrays by further sputtering deposition due to multiple direction deposition and shadow effect between adjacent nanoparticles. The nanogaps between two adjacent spherical nanoparticles can be well tuned by controlling deposition time. Such periodic nanoparticle arrays with gold coatings demonstrate a very stable and high sensitive surface‐enhanced Raman scattering spectroscopy (SERS) performance. The periodic nanoparticle arrays with 10 nm gaps display much stronger SERS enhancement due to electromagnetic coupling. The chemically modified nanoparticle arrays show good hydrophobicity, which shorten process of detecting probe molecules using them as SERS‐active substrates by localized concentration of droplet evaporation and a low detection limit of 10⁻¹² m R6G can be achieved without solution wasting in a short time. The hydrophobic substrate offers a simple, convenient, and economical method to examine SERS performance by rapid concentration of solution on it and it is highly helpful to improve its practical applications in portable Raman detecting devices to detect organic molecules.     

Nanofabrication of densely packed metal-polymer arrays for surface-enhanced Raman spectrometry

A key element to improve the analytical capabilities of surface-enhanced Raman spectroscopy (SERS) resides in the performance characteristics of the SERS-active substrate. Variables such as shape, size, and homogeneous distribution of the metal nanoparticles throughout the substrate surface are important in the design of more analytically sensitive and reliable substrates. Electron-beam lithography (EBL) has emerged as a powerful tool for the systematic fabrication of substrates with periodic nanoscale features. EBL also allows the rational design of nanoscale features that are optimized to the frequency of the Raman laser source. In this work, the efficiency of EBL fabricated substrates are studied by measuring the relative SERS signals of Rhodamine 6G and 1,10-phenanthro-line adsorbed on a series of cubic, elliptical, and hexagonal nanopatterned pillars of ma-N 2403 directly coated by physical vapor deposition with 25 nm films of Ag or Au. The raw analyte SERS signals, and signals normalized to metal nanoparticle surface area or numbers of loci, are used to study the effects of nanoparticle morphology on the performance of a rapidly created, diverse collection of substrates. For the excitation wavelength used, the nanoparticle size, geometry, and orientation of the particle primary axis relative to the excitation polarization vector, and particularly the density of nanoparticles, are shown to strongly influence substrate performance. A correlation between the inverse of the magnitude of the laser backscatter passed by the spectrometer and SERS activities of the various substrate patterns is also noted and provides a simple means to evaluate possible efficient coupling of the excitation radiation to localized surface plasmons for Raman enhancement.     

High-density silver nanoparticle film with temperature-controllable interparticle spacing for a tunable surface enhanced Raman scattering substrate

The formation of high-density silver nanoparticles and a novel method to precisely control the spacing between nanoparticles by temperature are demonstrated for a tunable surface enhanced Raman scattering substrates. The high-density nanoparticle thin film is accomplished by self-assembling through the Langmuir-Blodgett (LB) technique on a water surface and transferring the particle monolayer to a temperature-responsive polymer membrane. The temperature-responsive polymer membrane allows producing a dynamic surface enhanced Raman scattering substrate. The plasmon peak of the silver nanoparticle film red shifts up to 110 nm with increasing temperature. The high-density particle film serves as an excellent substrate for surface-enhanced Raman spectroscopy (SERS), and the scattering signal enhancement factor can be dynamically tuned by the thermally activated SERS substrate. The SERS spectra of Rhodamine 6G on a high-density silver particle film at various temperatures is characterized to demonstrate the tunable plasmon coupling between high-density nanoparticles.     

Nanostructured surfaces and assemblies as SERS media

Metallic nanostructures attract much interest as an efficient media for surface-enhanced Raman scattering (SERS). Significant progress has been made on the synthesis of metal nanoparticles with various shapes, composition, and controlled plasmonic properties, all critical for an efficient SERS response. For practical applications, efficient strategies of assembling metal nanoparticles into organized nanostructures are paramount for the fabrication of reproducible, stable, and highly active SERS substrates. Recent progress in the synthesis of novel plasmonic nanoparticles, fabrication of highly ordered one-, two-, and three-dimensional SERS substrates, and some applications of corresponding SERS effects are discussed.     

Hierarchical 3D SERS Substrates Fabricated by Integrating Photolithographic Microstructures and Self‐Assembly of Silver Nanoparticles

Most of the surface‐enhanced Raman scattering (SERS) substrates are 2D planar systems, which limits the SERS active area to a single Cartesian plane. Here, we fabricate 3D SERS substrates with the aim to break the traditional 2D SERS active area limitation, and to extend the SERS hotspots into the third dimension along the z‐axis. Our 3D SERS substrates are tailored with increased SERS hotspots in the z‐direction from tens of nanometers to tens of micrometers, increasing the hotspots in the z‐direction by at least an order of magnitude larger than the confocal volume (～1 μm) of most Raman spectrometers. Various hierarchical 3D SERS‐active microstructures are fabricated by combining 3D laser photolithography with Langmuir‐Blodgett nanoparticle assembly. 3D laser photolithography creates microstructured platforms required to extend the SERS‐active area into 3D, and the self‐assembly of Ag nanoparticles ensures homogeneous coating of SERS‐active Ag nanoparticles over the entire microstructured platforms. Large‐area 3D Raman imaging demonstrates that homogeneous signals can be collected throughout the entire 3D SERS substrates. We vary the morphology, height, and inclination angles of the 3D microstructures, where the inclination angle is found to exhibit strong influence on the SERS signals. We also demonstrate a potential application of this hierarchical 3D SERS substrate in information tagging, storage and encryption as SERS micro‐barcodes, where multiple micro‐barcodes can be created within a single set of microstructures.     

Surface-enhanced Raman scattering of rhodamine 6G on nanowire arrays decorated with gold nanoparticles

We investigate the surface-enhanced Raman scattering (SERS) of rhodamine 6G (R6G) adsorbed on Au nanoparticles attached to InP nanowires. We find that nanowire arrays act as frameworks for effective SERS substrates with a significantly higher Raman signal sensitivity than a planar framework of Au nanoparticles adsorbed two-dimensionally on a flat surface. The SERS signal displays a clear polarization-dependent effect when the nanowires are arranged in a row. We also find that the SERS signal increases with time during continuous laser illumination. The plasmon-enhanced optical forces between Au nanoparticles may either move pairs of nanoparticles closer together or attract adsorbed molecules by moving them to the junctions of Au nanoparticle aggregates. Such effects by plasmon optical forces may cause the observed increase of the SERS signal with continuous laser illumination.     

自组装金纳米粒子及其SERS应用

利用柠檬酸钠还原法制备了粒径均匀的AuNPs,并成功实现了其在APTMS修饰的玻璃表面的自组装,得到表面增强拉曼(SERS)基底。以R6G为探针分子检验了SERS基底的活性,其具有较强的增强性能。探讨了不同粒径AuNPs对SERS基底性能的影响,结果表明SERS基底的增强因子随着粒径的增大而增强。这种自组装策略为低浓度有机污染物的探测提供了一种有效的方法。     

Realization of thermally durable close-packed 2D gold nanoparticle arrays using self-assembly and plasma etching

Realization of thermally and chemically durable, ordered gold nanostructures using bottom-up self-assembly techniques are essential for applications in a wide range of areas including catalysis, energy generation, and sensing. Herein, we describe a modular process for realizing uniform arrays of gold nanoparticles, with interparticle spacings of 2?nm and above, by using RF plasma etching to remove ligands from self-assembled arrays of ligand-coated gold nanoparticles. Both nanoscale imaging and macroscale spectroscopic characterization techniques were used to determine the optimal conditions for plasma etching, namely RF power, operating pressure, duration of treatment, and type of gas. We then studied the effect of nanoparticle size, interparticle spacing, and type of substrate on the thermal durability of plasma-treated and untreated nanoparticle arrays. Plasma-treated arrays showed enhanced chemical and thermal durability, on account of the removal of ligands. To illustrate the application potential of the developed process, robust SERS (surface-enhanced Raman scattering) substrates were formed using plasma-treated arrays of silver-coated gold nanoparticles that had a silicon wafer or photopaper as the underlying support. The measured value of the average SERS enhancement factor (2?×?10(5)) was quantitatively reproducible on both silicon and paper substrates. The silicon substrates gave quantitatively reproducible results even after thermal annealing. The paper-based SERS substrate was also used to swab and detect probe molecules deposited on a solid surface.     

Carbon nanowalls amplify the surface-enhanced Raman scattering from Ag nanoparticles

We report surface-enhanced Raman scattering (SERS) from Ag nanoparticles decorated on thin carbon nanowalls (CNWs) grown by microwave plasma chemical vapor deposition. The Ag morphology is controlled by exposing the CNWs to oxygen plasma and through the electrodeposition process by varying the number of deposition cycles. The SERS substrates are capable of detecting low concentrations of rhodamine 6G and bovine serum albumin, showing much higher Raman enhancement than ordinary planar HOPG with Ag decoration. The major factors contributing to this behavior include: high density of Ag nanoparticles, large surface area, high surface roughness, and the underlying presence of vertically oriented CNWs. The relatively simple procedure of substrate preparation and nanoparticle decoration suggests that this is a promising approach for fabricating ultrasensitive SERS substrates for biological and chemical detection at the single-molecule level, while also enabling the study of fundamental SERS phenomena.     

Polarization dependence of surface-enhanced Raman scattering in gold nanoparticle-nanowire systems

We study the polarization dependence of surface-enhanced Raman scattering (SERS) in coupled gold nanoparticle-nanowire systems. The coupling between the continuous nanowire plasmons and the localized nanoparticle plasmons results in significant field enhancements and SERS enhancements comparable to those found in nanoparticle dimer junctions. The SERS intensity is maximal when the incident light is polarized across the particle and the wire, and the enhancement is remarkably insensitive to the detailed geometrical structures of the nanoparticles.     

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.     

Distance dependence of the Surface Enhanced Raman Scattering effect observed in amorphous TiO2 on nanostructured gold

Plasmon resonance of gold nanoparticles is responsible of the electromagnetic (EM) Surface Enhanced Raman Scattering (SERS) effect. Interaction of an amorphous matrix with a SERS substrate was studied. Thin films with different thickness of amorphous TiO₂ coated on a Klarite® substrate show a 100 times enhancement of the Raman signal. Distance dependence of the SERS interaction was shown to be less than 60 nm.     

Plasmonic properties of gold nanoparticles separated from a gold mirror by an ultrathin oxide

That a nanoparticle (NP) (for example of gold) residing above a gold mirror is almost as effective a surface enhanced Raman scattering (SERS) substrate (when illuminated with light of the correct polarization and wavelength) as two closely coupled gold nanoparticles has been known for some time. The NP-overmirror (NPOM) configuration has the valuable advantage that it is amenable to top-down fabrication. We have fabricated a series of Au-NPOM substrates with varying but thin atomic layer-deposited oxide spacer and measured the SERS enhancement as a function of spacer thickness and angle of incidence (AOI). These were compared with high-quality finite-difference time-domain calculations, which reproduce the observed spacer thickness and AOI dependences faithfully. The SERS intensity is expected to be strongly affected by the AOI on account for the fact that the hot spot formed in the space between the NP and the mirror is most efficiently excited with an electromagnetic field component that is normal to the surface of the mirror. Intriguingly we find that the SERS intensity maximizes at ~60° and show that this is due to the coherent superposition of the incident and the reflected field components. The observed SERS intensity is also shown to be very sensitive to the dielectric constant of the oxide spacer layer with the most intense signals obtained when using a low dielectric constant oxide layer (SiO(2)).     

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.     

Non-lithographic SERS substrates: tailoring surface chemistry for Au nanoparticle cluster assembly

Near‐field plasmonic coupling and local field enhancement in metal nanoarchitectures, such as arrangements of nanoparticle clusters, have application in many technologies from medical diagnostics, solar cells, to sensors. Although nanoparticle‐based cluster assemblies have exhibited signal enhancements in surface‐enhanced Raman scattering (SERS) sensors, it is challenging to achieve high reproducibility in SERS response using low‐cost fabrication methods. Here an innovative method is developed for fabricating self‐organized clusters of metal nanoparticles on diblock copolymer thin films as SERS‐active structures. Monodisperse, colloidal gold nanoparticles are attached via a crosslinking reaction on self‐organized chemically functionalized poly(methyl methacrylate) domains on polystyrene‐block‐poly(methyl methacrylate) templates. Thereby nanoparticle clusters with sub‐10‐nanometer interparticle spacing are achieved. Varying the molar concentration of functional chemical groups and crosslinking agent during the assembly process is found to affect the agglomeration of Au nanoparticles into clusters. Samples with a high surface coverage of nanoparticle cluster assemblies yield relative enhancement factors on the order of 10⁹ while simultaneously producing uniform signal enhancements in point‐to‐point measurements across each sample. High enhancement factors are associated with the narrow gap between nanoparticles assembled in clusters in full‐wave electromagnetic simulations. Reusability for small‐molecule detection is also demonstrated. Thus it is shown that the combination of high signal enhancement and reproducibility is achievable using a completely non‐lithographic fabrication process, thereby producing SERS substrates having high performance at low cost.     

Surface-enhanced Raman scattering dendritic substrates fabricated by deposition of gold and silver on silicon

This paper reports a study on the preparation of gold nanoparticles and silver dendrites on silicon substrates by immersion plating. Firstly, gold was deposited onto silicon wafer from HF aqueous solution containing HAuCl4. Then, the silicon wafer deposited gold was dipped into HF aqueous solution of AgNO3 to form silver coating gold film. Scanning electron microscopy reveals a uniform gold film consisted of gold nanoparticles and rough silver coating gold film containing uniform dendritic structures on silicon surface. By SERS (surface-enhanced Raman scattering) measurements, the fabricated gold and silver coating gold substrates activity toward SERS is assessed. The SERS spectra of crystal violet on the fabricated substrates reflect the different SERS activities on gold nanoparticles film and silver coating gold dendrites film. Compared with pure gold film on silicon, the film of silver coating gold dendrites film significantly increased the SERS intensity. As the fabrication process is very simple, cost-effective and reproducible, and the fabricated silver coating gold substrate is of excellent enhancement ability, spatial uniformity and good stability.     

In-situ partial sintering of gold-nanoparticle sheets for SERS applications

A new, versatile substrate design for surface-enhanced Raman spectroscopy (SERS) is introduced that provides better illumination and collection efficiency than other solid substrates. It uses sheets of 5 nm diameter gold nanoparticles that are draped by drying-mediated self-assembly onto 100 nm thick silicon nitride membranes. During laser illumination, partial in-situ sintering of the nanoparticles into larger structures with tiny gaps (≈2 nm) greatly increases the SERS enhancement factor. The detection of 1 pM of p-mercaptoaniline and 1 fg of 2,4-dinitrotoluene is demonstrated. The use of self-assembled nanoparticle sheets furthermore makes it possible to perform SERS detection in situ on top of a probe solution droplet.     

Nanoparticle formation in Au thin films by electron-beam-induced dewetting

We carried out investigations on electron-beam-induced nanoparticle formation in thin (5-30?nm) Au films on smooth SiO(2)/Si substrates. When the Au films were irradiated with an electron beam, the Au films broke up into nanoparticles through the dewetting process. The dominant wavelengths of the surface (corresponding to the pitch between nanoparticles) were closely related with the thickness of the Au. We then developed a new technique for the formation of periodically arranged Au nanoparticles using a holed substrate. The nanoholes induced heterogeneous nucleation and helped to form ordered nanoparticles between the holes. Two-dimensionally, periodically arranged Au nanoparticles with a pitch of 100?nm were?obtained.     

Novel method for preparing controllable and stable silver particle films for surface-enhanced Raman scattering spectroscopy

A new surface-enhanced Raman scattering (SERS) active substrate has been developed based on our previous study. Small silver nanoparticles on a quartz slide can be enlarged by using a mixture of commercially available reagents called Silver Enhancer and Initiator. The optical properties and characteristics of the new substrate have been investigated by ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM). The results indicate that the small silver nanoparticles grow and some silver aggregates emerge on the quartz slide after the slide is immersed into the Silver Enhancer and Initiator Mixture (SEIM). The average diameter of the silver nanoparticles on the substrate becomes approximately double after the immersion into SEIM for 20 s. 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was used as a Raman probe to evaluate the enhancement ability of the new silver substrate. It has been found that the SERS intensity can be increased about 10 times by using the substrate treated by SEIM compared with that without being treated by SEIM. Interestingly enough, the SERS enhancement increases with time. This may be due to the reorganization of silver nanoparticles on the quartz surface. The new substrate can remain active for more than 90 days. The adsorption mode of BPENB on the new substrate and the dependence of the BPENB configurations on the concentration of BPENB in methanol solution have also been investigated by SERS or UV-Vis spectroscopy. The SERS spectra of a self-assembled monolayer (SAM) BPENB film adsorbed on a silver substrate treated by SEIM show that BPENB molecules are chemically absorbed through the Ag-N bond. Consequently, a nearly perpendicular orientation of BPENB on the silver surface is proposed. The SERS spectra of BPENB SAMs on the new substrates fabricated from methanol solutions with different concentrations are compared. The concentration dependence of the SERS spectra reveals that the BPENB molecules are adsorbed on the silver film as monomers when the film is prepared from the solution with a lower concentration (<4 x 10(-6) M) and as aggregates when it is prepared from the solution with a higher concentration (>1 x 10(-5) M).