Surface-enhanced Raman scattering effect of gold nanoparticle arrays: The influence of annealing temperature,excitation power and array thickness

Gold nanoparticle arrays are fabricated for surface-enhanced Raman scattering (SERS) and the effect of the annealing temperature, the thickness of nanoparticle array and the exciting power on the SERS signals are investigated. The particle distribution and particle size are dense and uniform on the glass substrate when the 10 nm gold film was annealed at 250 °C and strong SERS signals for Rhodamine 6G were achieved via a 532 nm excitation with a 10 mW power. The SERS signal at 1650 cm⁻¹ is enhanced more than 10 times as compared to that of the gold film without annealing. The strong SERS behavior of gold nanoparticle arrays may broaden the SERS applications in biomedical and analytical chemistry.     

Controlling the properties of silver nanoparticles deposited on surfaces using supercritical carbon dioxide for surface-enhanced Raman spectroscopy

Silver nanoparticles (AgNPs) have been deposited on silicon and glass surfaces via a supercritical carbon dioxide (sc-CO₂) synthesis route for application in surface-enhanced Raman spectroscopy (SERS). Arrhenius plots revealed that nucleation and growth processes in this system depend on both temperature and surface chemistry. Results also demonstrated that temperature and surface chemistry could be varied to control nanoparticle properties, such as the mean nanoparticle size, density, and surface coverage, providing two useful variables for manipulating the properties of AgNPs deposited on surfaces in this system. These data also provide scientific insight into the underlying mechanisms governing heterogeneous AgNP deposition on a substrate in a sc-CO₂ system in addition to engineering insight into the variables that can be used to manipulate AgNP characteristics. The mean particle size could be tuned over the range 20–200 nm, the interparticle distance could be tuned over the range 70 nm–1 μm, and the surface coverage could be tuned over the range 0.035–0.58. Products were analyzed by scanning electron microscopy with image analysis, transmission electron microscopy, X-ray diffraction, and SERS. The silver nanoparticle-coated substrates were successfully applied in SERS, detecting the model analyte Rhodamine 6G at a concentration of 1 μM, a three orders of magnitude improvement over SERS surfaces previously fabricated in sc-CO₂ systems. Such surfaces can find use in trace concentration analyte detection in biomedical, chemical, and environmental applications.     

Surface enhanced Raman scattering of 2-cyanopyridine adsorbed on silver colloidal particles

Surface-enhanced Raman scattering (SERS) spectra of 2-cyanopyridine (2 CP) adsorbed on silver colloidal particles have been investigated. The prominent SERS bands are observed at 556, 612, 778, 1002, 1060, 1072, 1150 and 1240 cm⁻¹. The absolute enhancement factor of the Raman signals in SERS studies has been estimated to be of the order of 10²–10⁵ for various bands. The 2CP molecules have been ascribed to adsorb on colloidal particles in standing up fashion.     

Preparation and characterisation of a stable silver colloid for SER(R)S spectroscopy

A method for the reproducible preparation of a silver colloid with strong surface‐enhanced Raman scattering (SERS) properties, good stability with a zeta potential of −55 mV and a shelf life exceeding 1 year is reported. The mean particle size is 20 nm with a narrow size distribution of 10–30 nm. The colloid is produced by the reduction of silver nitrate with hydroxylamine phosphate to give a negatively charged phosphate surface on the silver particles. This is an ultrafast room temperature reaction and with controlled rapid addition and dispersion of reagents, very reproducible batches of colloid can be prepared making it suitable for commercial applications of Surface enhanced resonance Raman scattering(SER(R)S) spectroscopy. The stability of the colloid is attributed to the extremely low solubility product (K_sp) of silver phosphate. Characterisation and stability study data for this colloid have been obtained by ultraviolet–visible spectroscopy, transmission electron microscopy, energy dispersive X‐ray spectroscopy, particle size analysis and SERS analyses using a 514 nm laser on a Raman spectrometer. A SERS method to detect and to identify riboflavin in a vitamin B complex tablet is reported to illustrate a SERS application based upon the use of this silver colloid. Copyright © 2013 John Wiley & Sons, Ltd.     

Formation of conical microstructures upon laser evaporation of solids

The formation and development of the large-scale periodic structures on a single crystal Si surface are studied upon its evaporation by pulsed radiation of a copper vapor laser (wavelength of 510.6 nm, pulse duration of 20 ns). The development of structures occurs at a high number of laser shots (∼10⁴) at laser fluence of 1–2 J/cm² below optical breakdown in a wide pressure range of surrounding atmosphere from 1 to 10⁵ Pa. The structures are cones with angles of 25, which grow towards the laser beam and protrude above the initial surface for 20–30 μm. It is suggested that the spatial period of the structures (10–20 μm) is determined by the capillary waves period on the molten surface. The X-ray diffractometry reveals that the modified area of the Si substrate has a polycrystalline structure and consists of Si nanoparticles with a size of 40–70 nm, depending on the pressure of surrounding gas. Similar structures are also observed on Ge and Ti. Received: 12 February 2000 / Accepted: 28 March 2000 / Published online: 20 June 2001     

应用球形和海胆状金混合SERS基底检测高环多环芳烃

合成了海胆状金银复合纳米材料,并与球形金纳米材料混合作为表面增强拉曼活性基底实现了对水中高环多环芳烃的痕量检测。对海胆状材料进行表征,粒径大小约为300～400 nm,表面有40～100 nm明显的刺状凸起。与球形金溶胶混合后并优化pH值及混合比例等参数,产生了优于球形金溶胶2～3倍的增强效果。利用此增强基底检测了危害严重的高环多环芳烃污染物——芘(四环)、苯并蒽(四环)、苯并芘(五环),得到的光谱数据反映出混合SERS基底有良好的重复性和稳定性,对测得光谱进行特征峰归属分析,固体拉曼光谱与水溶液SERS光谱有确定的对应关系,并且在低浓度范围多环芳烃特征峰峰强与其水溶液浓度有良好的线性关系。经计算,芘(四环)、苯并蒽(四环)、苯并芘(五环)的检测限分别为0.44,2.92和1.64 nmol·L-1。该研究的创新点为合成了海胆金纳米颗粒,与球形金溶胶混合后制成新型高效SERS检测基底;选用自制高效SERS基底,实现了高环PAHs痕量检测。结果表明,利用该方法制备的活性基底,可实现对水中高环多环芳烃的痕量检测,为检测水中高环多环芳烃提供了实验室依据。     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Diamine-linked array of metal (Au,Ag) nanoparticles on glass substrates for reliable surface-enhanced Raman scattering (SERS) measurements

Metal (Au, Ag) nanoparticles (M NPs) (ca. 30–40 nm) prepared by citrate reduction method were arrayed on amine-terminated glass substrates using diamine linkers with different chain lengths. 1,4-diaminobutane (C-4 diamine) produced the uniform and densely-packed array of M NPs on glass substrates at appropriate concentration ranges, whereas diamine linkers with longer chain lengths (C-8 and C-12 diamines) produced more heterogeneous and aggregated array of M NPs. When compared to Ag NPs, Au NPs demonstrated more controllable and higher packing density due to their mono-dispersed size and higher affinity to diamine linkers. Uniformly arrayed M NPs (Au, Ag) on glass substrates exhibited high enhancement factors in SERS measurements of o-chlorothiophenol probes. Au NPs arrayed substrates exhibited an approximate power-law linearity of Raman intensity with probe concentrations (from 10⁻⁷ M to 10⁻⁴ M), demonstrating more reliable SERS substrates than Ag arrayed substrates with higher SERS activity.     

表面增强拉曼光谱快速检测尿液中的尿酸

表面增强拉曼光谱是一种表面灵敏度极高的“指纹”光谱技术,检测限可达单分子级别。它可以实现痕量物质的特异性识别及快速、无损检测,广泛应用于生命科学、电化学、环境安全等领域以及人们的日常生活中。通过种子生长法成功地实现了形貌均匀、尺寸可调的球形金纳米粒子的制备,并以此作为增强基底进一步探索其粒径对尿酸拉曼谱峰强度的影响。结果表明,金纳米粒子的尺寸显著影响其拉曼增强能力。在研究范围内,随着金纳米粒子尺寸的增加,其拉曼增强能力逐渐增加。在激光波长为638 nm时,150 nm的金纳米粒子具有最优的拉曼增强能力。这使得它们可适用于尿酸溶液的快速高灵敏度分析,检测限可达0.01 mmol·L-1。进一步的研究还表明,该方法可用于痕量尿酸的定量检测。在0.01～0.5 mmol·L-1范围内,尿酸的浓度与其特征拉曼峰640 cm-1处的峰强度之间呈线性关系,线性相关系数达0.98。将该方法用于真实样品(正常人体尿液)的快速检测,发现该方法不受尿液中其他成分的干扰,可以实现人体尿液中尿酸含量的快速测定。研究结果表明,以金纳米粒子作为基底的表面增强拉曼光谱方法可方便、快速地对尿液中尿酸的含量进行分析,极大地拓展了表面增强拉曼光谱在临床上的应用与研究。     

Surface characteristics of Ag‐doped Au nanoparticles probed by Raman scattering spectroscopy

We have examined the surface characteristics of Ag‐doped Au nanoparticles (below 5 mol% of Ag) by means of the surface‐enhanced Raman scattering (SERS) of 2,6‐dimethylphenylisocyanide (2,6‐DMPI) and 4‐nitrobenzenethiol (4‐NBT). When Ag was added to Au to form ∼35‐nm‐sized alloy nanoparticles, the surface plasmon resonance band was blue‐shifted linearly from 523 to 517 nm in proportion to the content of Ag up to 5%. In the SERS spectra of 2,6‐DMPI, the N‐C stretching peak also shifted almost linearly from 2184 to 2174 cm⁻¹ when the Ag content was 5 mol% or less; the peak then remained the same as that of the pure Ag film. The potential variation of the SERS spectrum of 2,6‐DMPI in an electrochemical environment, as well as the effect of organic vapor, also showed a similar tendency. From the SERS of 4‐NBT, we confirmed the occurrence of a surface‐induced photoreaction converting 4‐NBT to 4‐aminobenzenethiol, when Ag was added to Au to form alloy nanoparticles. The photoreaction induction ability also increased linearly with the Ag content, reaching a plateau level at 5 mol% of Ag. All these observations suggest that the surface content of Ag should increase almost linearly as a function of the overall mole fraction of Ag and, once the Au/Ag nanoparticles reach 5 mol% of Ag, their surfaces are fully covered with Ag, showing the same surface characteristics of pure Ag nanoparticles. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering sensing on black silicon

Reactive ion etching was used to fabricate black‐Si over the entire surface area of 4‐inch Si wafers. After 20 min of the plasma treatment, surface reflection well below 2% was achieved over the 300–1000 nm spectral range. The spikes of the black‐Si substrates were coated by gold, resulting in an island film for surface‐enhanced Raman scattering (SERS) sensing. A detection limit of 1 × 10^?6 M (at count rate > 10² s^?1 . mW^?1) was achieved for rhodamine 6G in aqueous solution when drop cast onto a ～ 100‐nm‐thick Au coating. The sensitivity increases for thicker coatings. A mixed mobile‐on‐immobile platform for SERS sensing is introduced by using dog‐bone Au nanoparticles on the Au/black‐Si substrate. The SERS intensity shows a non‐linear dependence on the solid angle (numerical aperture of excitation/collection optics) for a thick gold coating that exhibits a 10 times higher enhancement. This shows promise for augmented sensitivity in SERS applications.     

Surface enhanced Raman scattering silica substrate fast fabrication by femtosecond laser pulses

We report the fabrication of surface enhanced Raman spectroscopy (SERS) fused silica glass substrates using fast femtosecond-laser (fs-laser) scan, followed by silver chemical plating. A cross-section enhancement factor (EF) of 2.5×10⁶, evaluated by Rhodamine 6G (10⁻⁷ M solution), was obtained. The Raman mapping indicated a good uniformity over the fs-laser scanned area. The dimension and pattern of the SERS activated region can be conveniently controlled by laser 2D scanning, potentially enabling integration of SERS into a high-order optical–chemical analysis system on a glass chip.     

Single‐molecule detection of thionine on aggregated gold nanoparticles by surface enhanced Raman scattering

We report observations of single‐molecule detection of thionine and its dynamic interactions on aggregated gold nanoparticle clusters using surface enhanced Raman scattering (SERS). Spectral intensities were found to be independent of the size of Au nanoparticles studied (from 17 to 80 nm) at thionine concentration below 10⁻¹² M or at single‐molecule concentration levels. Raman line separations and, in particular, spectral fluctuations and blinking were also observed, suggesting temporal changes in single molecular motion and/or arrangements of thionine on Au nanoparticle surfaces. In contrast, by using dispersed Au nanoparticles, only ensemble SERS spectra could be observed at relatively high concentrations (> 10⁻⁸ M thionine), and spectral intensities varied with the size of Au nanoparticles. Copyright © 2007 John Wiley & Sons, Ltd.     

Vibrational spectroscopy of SiC thin films deposited by excimer laser ablation

A large number of thin SiC films, prepared at different conditions by KrF excimer laser ablation of solid SiC targets and deposition onto Si substrates (some onto quartz glass (QG) and yttrium-stabilized zirconia (YSZ)) were characterized by infrared and Raman spectroscopy. The films consisted of nano- and microcrystalline SiC and contained nanocrystalline carbon in the case of QG or YSZ substrates. Raman spectra of nanocrystalline SiC (grains <30 nm) reflect the phonon density-of-state function of SiC by broad scattering effects at 220–600 and 650–950 cm⁻¹. Medium-size crystallites are represented by a relatively narrow asymmetric band at 790 cm⁻¹ and crystallites >200 nm by an additional asymmetric band at 960 cm⁻¹. Small satellite bands at 760 and 940 cm⁻¹, attributed to SiC surface layers, were resolved in some well-ordered samples. Optical modelling was needed to interpret the IR spectra. SiC films could be represented by an effective medium model containing a SiC host phase and embedded particles with free charge carriers. The crystalline order of SiC films can be estimated from the parameters of the SiC oscillators. Received: 5 October 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

Highly efficient silver particle layers on glass substrate synthesized by the sonochemical method for surface enhanced Raman spectroscopy purposes

A fast method for preparing of silver particle layers on glass substrates with high application potential for using in surface enhanced Raman spectroscopy (SERS) is introduced. Silver particle layers deposited on glass cover slips were generated in one-step process by reduction of silver nitrate using several reducing agents (ethylene glycol, glycerol, maltose, lactose and glucose) under ultrasonic irradiation. This technique allows the formation of homogeneous layers of silver particles with sizes from 80 nm up to several hundred nanometers depending on the nature of the used reducing agent. Additionally, the presented method is not susceptible to impurities on the substrate surface and it does not need any additives to capture or stabilize the silver particles on the glass surface. The characteristics of prepared silver layers on glass substrate by the above mentioned sonochemical approach was compared with chemically prepared ones. The prepared layers were tested as substrates for SERS using adenine as a model analyte. The factor of Raman signal enhancement reached up to 5·10⁵. On the contrary, the chemically prepared silver layers does not exhibit almost any pronounced Raman signal enhancement. Presented sonochemical approach for preparation of silver particle layers is fast, simple, robust, and is better suited for reproducible fabrication functional SERS substrates than chemical one.     

A hybrid substrate for surface‐enhanced Raman scattering spectroscopy: coupling metal nanoparticles to strong localised fields on a micro‐structured surface

Electromagnetic coupling between localised plasmons on metal nanoparticles and the strong localised fields on a micro‐structured surface is demonstrated as a means to increase the enhancement factor in surface‐enhanced Raman scattering (SERS) spectroscopy. Au nanoparticles of diameter 20 nm were deposited on a micro‐structured Au surface consisting of a periodic array of square‐based pyramidal pits (Klarite). The spectra of 4‐aminothiophenol (4‐ATP) were compared before and after deposition of Au nanoparticles on the micro‐structured surface. The addition of Au nanoparticles is shown to provide significantly higher signal intensities, with improvements of the order of ∼10³ per molecule compared with spectra obtained from the micro‐structured substrate alone. This hybrid approach offers promise for combining nanoparticles with micro‐ and nano‐structured surfaces in order to design SERS substrates with higher sensitivities. Copyright © 2011 John Wiley & Sons, Ltd.     

Release of ultrafine particles from three simulated building processes

Building activities are recognised to produce coarse particulate matter but less is known about the release of airborne ultrafine particles (UFPs; those below 100 nm in diameter). For the first time, this study has investigated the release of particles in the 5–560 nm range from three simulated building activities: the crushing of concrete cubes, the demolition of old concrete slabs, and the recycling of concrete debris. A fast response differential mobility spectrometer (Cambustion DMS50) was used to measure particle number concentrations (PNC) and size distributions (PNDs) at a sampling frequency of 10 Hz in a confined laboratory room providing controlled environment and near–steady background PNCs. The sampling point was intentionally kept close to the test samples so that the release of new UFPs during these simulated processes can be quantified. Tri–modal particle size distributions were recorded for all cases, demonstrating different peak diameters in fresh nuclei (<10 nm), nucleation (10–30 nm) and accumulation (30–300 nm) modes for individual activities. The measured background size distributions showed modal peaks at about 13 and 49 nm with average background PNCs ~1.47 × 10⁴ cm⁻³. These background modal peaks shifted towards the larger sizes during the work periods (i.e. actual experiments) and the total PNCs increased between 2 and 17 times over the background PNCs for different activities. After adjusting for background concentrations, the net release of PNCs during cube crushing, slab demolition, and ‘dry’ and ‘wet’ recycling events were measured as ~0.77, 19.1, 22.7 and 1.76 (×10⁴) cm⁻³, respectively. The PNDs were converted into particle mass concentrations (PMCs). While majority of new PNC release was below 100 nm (i.e. UFPs), the bulk of new PMC emissions were constituted by the particles over 100 nm; ~95, 79, 73 and 90% of total PNCs, and ~71, 92, 93 and 91% of total PMCs, for cube crushing, slab demolition, dry recycling and wet recycling, respectively. The results of this study firmly elucidate the release of UFPs and raise a need for further detailed studies and designing health and safety related exposure guidelines for laboratory workplaces and operational building sites.     

Fabrication and applications of ultraflexible nanostructures using dielectric heating-assisted nanoimprint on PVC films

We developed dielectric heating-assisted nanoimprint method for rapid fabrication of ultraflexible nanostructures. Using spin-coating polyvinyl-chloride (PVC) film on the glass slide, the dielectric heating on PVC film helped the pattern transfer from the mold to PVC film in few seconds. Various kinds of nanostructures were successfully made on PVC films with about 20-μm thickness. We demonstrated the applications of ultraflexible metallic nanostructures for bending measurement using surface plasmon resonance (SPR) and surface enhanced Raman scattering (SERS) on the curved surfaces. For measuring bending angles using SPR on capped nanowire arrays, the minimum detection angle was 2.4 × 10⁻³ degree under 0.02 nm wavelength resolution. For SERS measurement, the nanorod arrays on a curved substrate can increase SERS signals for two times as compared to planar SERS substrate.     

Pulsed electron-beam melting of a copper — steel 316 system: Evolution of the chemical composition,microstructure, and properties

The surface topography, chemical composition, microstructure, nanohardness, and tribological characteristics of a Cu (film, 512 nm)-stainless steel 316 (substrate) system subjected to pulsed melting by a low-energy (20–30 keV), high-current electron beam (2–3 μs, 2–10 J/cm²) were investigated. The film was deposited by sputtering a Cu target in the plasma of a microwave discharge in argon. To prevent local exfoliation of the film due to cratering, the substrate was multiply pre-irradiated with 8–10 J/cm². On single irradiation, the bulk of the film survived, and a diffusion layer containing the film and substrate components was formed at the interface. The thickness of this layer was 120–170 nm irrespective of the energy density. The diffusion layer consisted of subgrains of γ-Fe solid solution and nanosized particles of copper. In the surface layer of thickness 0.5–1 μm, which included the copper film quenched from melt and the diffusion layer, the nanohardness and the wear resistance nonmonotonicly varied with energy density, reaching, respectively, a maximum and a minimum in the range 4.3–6.3 J/cm². As the number of pulsed melting cycles was increased to five in the same energy density range, there occurred mixing of the film-substrate system and a surface layer of thickness ∼2 μm was formed which contained ∼20 at. % copper. Displacement of the excess copper during crystallization resulted in the formation of two-phase nanocrystal interlayers separating the γ-phase grains. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 6–13, December, 2005.     

Semi-quantitative Surface Enhanced Raman Scattering Spectroscopic Creatinine Measurement in Human Urine Samples

This paper presents the development of a semi-quantitative method of measuring the creatinine biomolecule in human urine by the surface enhanced Raman scattering (SERS) technique. Creatinine is one of the major components of urine and can be used to represent the metabolic and renal function of the human body. The Raman signal of creatinine is enhanced by 50 nm Au nanoparticles. Raman spectra between 1400 and 1500 cm^?1 were analyzed to obtain the relationship between the SERS band area and creatinine concentration. The square of the correlation coefficient is 0.99 in artificial urine over the creatinine range 38.4–153.6 mg/dl. In a human urine experiment, a good linear correlation is observed over the creatinine concentration range 2.56–6.4 mg/dl. The square of correlation coefficient is 0.96.