Nanostructured Tin Oxide as a Surface‐Enhanced Raman Scattering Substrate for the Detection of Nitroaromatic Compounds

Sensing of low concentrations of two nitroaromatic compounds, 1,2‐dinitrotoluene and 2‐nitrophenol, is presented. The sensing mechanism is based on surface‐enhanced Raman scattering (SERS) using nanostructured tin oxide as the SERS‐active substrate. The SnO_x nanostructures are synthesized by a simple solgel method and doped with Ag and Au. The Raman signal of a low concentration of the analyte, otherwise extremely weak, becomes significant when the analytes are attached to these substrates. Doping of SnO_x nanopowders with Ag and Au leads to a further increase in the Raman intensities. This study demonstrates the scope of ceramic–metal nanocomposites as convenient solid‐state SERS sensors for low‐level detection.     

Controlled fabrication of silver nanoneedles array for SERS and their application in rapid detection of narcotics

Novel surface-enhanced Raman scattering (SERS) substrates with high SERS-activity are ideal for novel SERS sensors, detectors to detect illicitly sold narcotics and explosives. The key to the wider application of SERS technique is to develop plasmon resonant structure with novel geometries to enhance Raman signals and to control the periodic ordering of these structures over a large area to obtain reproducible Raman enhancement. In this work, a simple Ar(+)-ion sputtering route has been developed to fabricate silver nanoneedles arrays on silicon substrates for SERS-active substrates to detect trace-level illicitly sold narcotics. These silver nanoneedles possess a very sharp apex with an apex diameter of 15 nm and an apex angle of 20°. The SERS enhancement factor of greater than 10(10) was reproducibly achieved by the well-aligned nanoneedles arrays. Furthermore, ketamine hydrochloride molecules, one kind of illicitly sold narcotics, can be detected down to 27 ppb by using our SERS substrate within 3 s, indicating the sensitivity of our SERS substrates for trace amounts of narcotics and that SERS technology can become an important analytical technique in forensic laboratories because it can provide a rapid and nondestructive method for trace detection.     

Surface-Enhanced Raman Scattering on Silver Nanoparticles in Different Aggregation Stages

Enhancement factors of surface-enhanced Raman scattering (SERS) are compared for crystal violet attached to 15–60-nm-sized colloidal silver particles in various aggregation stages using 830 nm and 407 nm laser excitation. Enhancement factors on the order of 10⁶–10⁷ have been measured at 407 nm excitation for molecules adsorbed on spatially-isolated silver spheres exhibiting strong, sharp, single-sphere plasmon resonance at 395 nm. Extremely large SERS enhancement factors on the order of 10¹⁴ are obtained at near infrared excitation for molecules on clusters built from colloidal particles. The SERS enhancement factor is demonstrated to be independent of the size of the clusters. The increase of SERS enhancement factors by 7–8 orders of magnitude by the formation of aggregates, as well as the extremely small density of “hot sites” exhibiting this high level of enhancement, provide further strong arguments for the electromagnetic origin of the hot spots and for strongly enhanced local optical fields as a key effect in SERS at an extremely high enhancement level.     

Large-area nanogap plasmon resonator arrays for plasmonics applications

Large-area (～8000 mm(2)) Au nanogap plasmon resonator array substrates manufactured using maskless laser interference lithography (LIL) with high uniformity are presented. The periodically spaced subwavelength nanogap arrays are formed between adjacent nanopyramid (NPy) structures with precisely defined pitch and high length density (～1 km cm(-2)), and are ideally suited as scattering sites for surface enhanced Raman scattering (SERS), as well as refractive index sensing. The two-dimensional grid arrangement of NPy structures renders the excitation of the plasmon resonators minimally dependent on the incident polarization. The SERS average enhancement factor (AEF) has been characterized using over 30?000 individual measurements of benzenethiol (BT) chemisorbed on the Au NPy surfaces. From the 1(a(1)), β(CCC) + ν(CS) ring mode (1074 cm(-1)) of BT on surfaces with pitch λ(g) = 200 nm, AEF = 0.8 × 10(6) and for surfaces with λ(g) = 500 nm, AEF = 0.3 × 10(7) from over 99% of the imaged spots. Maximum AEFs > 10(8) have been measured in both cases.     

Naturally inspired SERS substrates fabricated by photocatalytically depositing silver nanoparticles on cicada wings

Densely stacked Ag nanoparticles with an average diameter of 199 nm were effectively deposited on TiO₂-coated cicada wings (Ag/TiO₂-coated wings) from a water-ethanol solution of AgNO₃ using ultraviolet light irradiation at room temperature. It was seen that the surfaces of bare cicada wings contained nanopillar array structures. In the optical absorption spectra of the Ag/TiO₂-coated wings, the absorption peak due to the localized surface plasmon resonance (LSPR) of Ag nanoparticles was observed at 440 nm. Strong Surface-enhanced Raman scattering (SERS) signals of Rhodamine 6G adsorbed on the Ag/TiO₂-coated wings were clearly observed using the 514.5-nm line of an Ar⁺ laser. The Ag/TiO₂-coated wings can be a promising candidate for naturally inspired SERS substrates.     

Excitation wavelength dependent surface enhanced Raman scattering of 4-aminothiophenol on gold nanorings

Detailed understanding of the underlying mechanisms of surface enhanced Raman scattering (SERS) remains challenging for different experimental conditions. We report on an excitation wavelength dependent SERS of 4-aminothiophenol molecules on gold nanorings. SERS and normal Raman spectra, combined with well-characterized surface morphology, optical spectroscopy and electromagnetic (EM) field simulations of gold nanoring substrates indicate that the EM enhancement occurs at all three excitation wavelengths (532, 633 and 785 nm) employed but at short wavelengths (532 and 633 nm) charge transfer (CT) results in additional strong enhancements of particular Raman transitions. These results pave the way to further understanding the origin of the SERS mechanism.     

Comprehensive study of polymer fiber surface modifications Part 1: high‐fluence UV‐excimer‐laser‐induced structures

Recently, there has been great interest in physico‐chemical surface treatments for modifying polymer surfaces. Ultraviolet (UV)‐excimer‐laser irradiation of polymers is of particular interest. In this study, polyamide was irradiated by a 193 nm excimer laser with a fluence above its ablation threshold (high‐fluence). Morphological changes of the resulting samples were characterized by scanning electron microscopy (SEM) and tapping mode atomic force microscopy (TM‐AFM). Chemical modifications by laser treatment were studied by X‐ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and chemical force microscopy (CFM). Topographical results indicated that ‘ripple‐like’ structures of micrometer size were formed after laser irradiation. XPS and Tof‐SIMS results showed that bond scission occurred on the polymer surface under the action of high‐fluence. Changes in surface chemical properties of the laser‐irradiated polyamide were supported by CFM experiments. Copyright © 2004 Society of Chemical Industry     

Incubation phenomena during UV‐pulse excimer laser processing of silicone elastomers

Observations of the interaction of poly(dimethylsiloxane) (PDMS) sheet (210 μm thick) with KrF excimer laser irradiation (λ = 248 nm), with low energy of 50 mJ/pulse are presented. The negative ablation or swelling of the material caused by low frequency pulse irradiation is characterized by optical microscopy, μ‐Raman spectrometry and X‐ray micro‐tomography. The appearance of defected areas in the form of cones inside the sheet and changes of material chemistry are discussed. These phenomena are considered as a precursor of the ablation occurring after passing a threshold of absorbed laser irradiation energy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44541.     

Large-area high-performance SERS substrates with deep controllable sub-10-nm gap structure fabricated by depositing Au film on the cicada wing

Noble metal nanogap structure supports strong surface-enhanced Raman scattering (SERS) which can be used to detect single molecules. However, the lack of reproducible fabrication techniques with nanometer-level control over the gap size has limited practical applications. In this letter, by depositing the Au film onto the cicada wing, we engineer the ordered array of nanopillar structures on the wing to form large-area high-performance SERS substrates. Through the control of the thickness of the Au film deposited onto the cicada wing, the gap sizes between neighboring nanopillars are fine defined. SERS substrates with sub-10-nm gap sizes are obtained, which have the highest average Raman enhancement factor (EF) larger than 2 × 10⁸, about 40 times as large as that of commercial Klarite® substrates. The cicada wings used as templates are natural and environment-friendly. The depositing method is low cost and high throughput so that our large-area high-performance SERS substrates have great advantage for chemical/biological sensing applications.     

Fabrication of nanowire network AAO and its application in SERS

In this paper, nanowire network anodized aluminum oxide (AAO) was fabricated by just adding a simple film-eroding process after the production of porous AAO. After depositing 50 nm of Au onto the surface, nanowire network AAO can be used as ultrasensitive and high reproducibility surface-enhanced Raman scattering (SERS) substrate. The average Raman enhancement factor of the nanowire network AAO SERS substrate can reach 5.93 × 10⁶, which is about 14% larger than that of commercial Klarite® substrates. Simultaneously, the relative standard deviations in the SERS intensities are limited to approximately 7%. All of the results indicate that our large-area low-cost high-performance nanowire structure AAO SERS substrates have a great advantage in chemical/biological sensing applications.     

Fast and efficient manufacturing method of one‐ and two‐dimensional polyethylene terephthalate transmission diffraction gratings by direct laser interference patterning

One‐ and two‐dimensional diffraction gratings were fabricated on commercial polyethylene terephthalate (PET) film by two beam direct laser interference patterning (DLIP) method using a pulse laser (10 ns) with a wavelength of 266 nm. The relative diffraction efficiency of the structured specimens (at 633 nm) in transmission mode was measured and correlated with the topological characteristics of the structured PET substrates. The obtained diffraction gratings made by DLIP show better or similar diffraction efficiencies when compared with the reported efficiency of gratings made by other methods (up to 42.5% for 1 μm arrays), and can be fabricated on large areas in very short processing times (up to 18 cm²/s). POLYM. ENG. SCI., 52:1903–1908, 2012. © 2012 Society of Plastics Engineers     

Femtosecond‐laser‐assisted wet chemical etching of polymer materials

Polymers are modified by femtosecond‐(fs)‐IR‐laser irradiation under various process parameters. Several sorts of thermoplastic polymer are employed: polymethylmethacrylate (PMMA), fluorinated PMMA, poly‐N‐methyl methacrylimide (PMMI), polystyrol, polycarbonate, polyimide, and polyethylene. After the fs‐laser‐induced modification process, the irradiated area is developed by an aqueous solution of a solvent agent (n‐hexane, benzene, and methylisobutylketone). The surface topography of the fs‐laser‐irradiated area is characterized by stylus‐profilometry before and after the development procedure. Some preliminary explanations are given about the solution mechanism of the fs‐laser‐irradiated polymer region. The experimental results are relevant for the fabrication of three‐dimensional (3D)‐structures in the volume of a transparent polymer material by fs‐laser irradiation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1229–1238, 2006     

Gold nanoparticle‐functionalized thread as a substrate for SERS study of analytes both bound and unbound to gold

The potential of thread for use as a substrate for inexpensive, disposable diagnostics for surface‐enhanced Raman scattering (SERS) spectroscopy has been showed in this study. Gold‐nanoparticle coated thread can be embedded into fabrics to detect chemical or biological analytes in military and medical applications through SERS. Using this inexpensive and widely available material enables reduction in the volumes of nanoparticle solution required compared to alternatives. By testing multiple analytes, it was observed that molecular structure played a significant role in SERS signal amplification, and hence, the technique is limited to the detection of a small number of analytes possessing highly polarizable structures. Although direct chemical bonding between analyte molecules and nanoparticles gives the strongest signal enhancement, it remains possible to easily discern signals generated by analytes not directly bound, provided they possess suitable structure. Amplification of SERS signal by controlling the aggregation state of the gold nanoparticles to increase the number of SERS hotspots was observed. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1598–1605, 2014     

High-density metallic nanogaps fabricated on solid substrates used for surface enhanced Raman scattering

The Raman signal of adsorbed molecules can be significantly enhanced by utilizing metallic structures with high-density Raman hot spots used as surface enhanced Raman scattering (SERS) substrates. In this work, we develop a simple, convenient and tunable method to fabricate high-density Ag or Au nanogaps on Si wafers. These nanogaps can serve as Raman hot spots, leading to dramatic enhancement of the Raman signal. The high-density nanogaps can be formed by repeating the electroless deposition of Ag NPs (or Au NPs) and coating of p-aminothiophenol (PATP, a Raman probe) on the deposited Ag NPs (or Au NPs) through the self-assembly process. After removal of PATP by O(2) plasma, the as-fabricated SERS substrate can be reused for the detection of other molecules.     

Synthesis and photoinduced surface‐relief grating of well‐defined azo‐containing polymethacrylates via atom transfer radical polymerization

A well‐defined photoresponsive polymethacrylate containing azo chromophores, poly[6‐(4‐phenylazophenoxy)hexylmethacrylate] [Poly(PPHM)], was prepared with azo‐based monofunctional and difunctional initiators via atom transfer radical polymerization in the presence of CuCl/1,1,4,7,10,10‐hexamethyltriethylenetetramine. The polymerizations with first‐order kinetics were well controlled with theoretical expected molecular weight and narrow molecular weight distributions in two initiation systems. The UV absorption intensities of the poly (PPHM)s increased with increasing molecular weight of the poly(PPHM)s in all cases. The 80‐nm surface‐relief gratings with 2.7% efficient diffraction formed on the poly (PPHM) film surface were obtained with a linearly polarized krypton laser with 10 min of irradiation at a recording beam intensity of 188 mW/cm² with a wavelength of 413.1 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Functional hybrid nickel nanostructures as recyclable SERS substrates: detection of explosives and biowarfare agents

We present the synthesis of highly anisotropic nickel nanowires (NWs) and large area, free-standing carpets extending over cm(2) area by simple solution phase chemistry. The materials can be post-synthetically manipulated to produce hybrid tubes, wires, and carpets by galvanic exchange reactions with Au(3+), Ag(+), Pt(2+), and Pd(2+). All of these structures, especially the hybrid carpets and tubes, have been prepared in bulk and are surface enhanced Raman scattering (SERS) active substrates. Molecules of relevance such as dipicolinic acid (constituting 5-15% of the dry weight of bacterial spores of Bacillus anthracis), dinitrotoluene, hexahydro-1,3,5-triazine (RDX), and trinitrotoluene at nanomolar concentrations have been detected. An enhancement factor of ～10(10) was observed for the Ni-Au nanocarpet. The reusability of the Ni-Au nanocarpet for SERS applications was tested 5 times without affecting the sensitivity. The reusability and sensitivity over large area have been demonstrated by Raman microscopy. Our method provides an easy and cost effective way to produce recyclable, large area, SERS active substrates with high sensitivity and reproducibility which can overcome the limitation of one-time use of traditional SERS substrates.     

Structural and morphological study of gamma‐irradiation synthesized silver nanoparticles

Silver nanostructured particles with controlled size, shape, and morphology were achieved by gamma irradiation of aqueous solution containing AgNO_3, ploy (vinyl pyrrolidone), (PVP) or mixture of PVP and ploy (vinyl alcohol), (PVA). The reaction condition parameters such as solvent content, polymer type and irradiation dose were investigated. The physico‐chemical properties and morphological structures of the as‐prepared sliver nanostructures were characterized using UV/VIS spectroscopy, TEM, XRD, and Fourier transform infrared spectroscopy (FTIR) spectroscopy. Hexagonal and nanorods structures of sliver nanoparticles having single surface plasmon resonance peak and triangular (nanoprism) nanoparticles having different surface plasmon resonance peak were obtained. The XRD patterns of the as‐prepared silver nanostructure show four diffraction peaks at 2θ of 38.4°, 44.5°, 64.6°, and 77.6° of the face‐centered cubic structure silver nanoparticles. FTIR measurements indicated that the sliver nanoparticles were coordinated through the functional groups of PVA and/or PVP. POLYM. COMPOS., 38:2687–2694, 2017. © 2015 Society of Plastics Engineers     

Raman enhancement of rhodamine adsorbed on Ag nanoparticles self-assembled into nanowire-like arrays

ABSTRACT: This work reports on Raman scattering of rhodamine (R6G) molecules absorbed on either randomly distributed or grating-like arrays of approximately 8-nm Ag nanoparticles developed by inert gas aggregation. Optimal growth and surface-enhanced Raman scattering (SERS) parameters have been obtained for the randomly distributed nanoparticles, while effects related to the aging of the silver nanoparticles were studied. Grating-like arrays of nanoparticles have been fabricated using line arrays templates formed either by fracture-induced structuring or by standard lithographic techniques. Grating structures fabricated by both methods exhibit an enhancement of the SERS signal, in comparison to the corresponding signal from randomly distributed Ag nanoparticles, as well as a preferential enhancement in the areas of the sharp features, and a dependence on the polarization direction of the incident exciting laser beam, with respect to the orientation of the gratings structuring. The observed spectroscopic features are consistent with a line-arrangement of hot-spots due to the self- alignment of metallic nanoparticles, induced by the grating-like templates.     

表面增强拉曼散射基底的研究进展

表面增强拉曼光谱(SERS)由于其高的灵敏度、抗干扰能力强等优点,被广泛应用在表面科学、分析化学、物理学等领域,是研究表面和界面过程的重要工具,是定性鉴定化学组成相近化合物的有力手段.因此,高品质、高活性的SERS基底一直是科研工作者们追求和研究的重点.本文对SERS活性基底的发展进行了介绍,从金、银金属纳米粒子作为基底的拉曼效应的科学研究,又进一步总结了非金属纳米粒子ZnO、TiO₂、ZnS、Cu₂O、CdTe、CdS等SERS基底.今后,将贵金属与半导体纳米材料复合将是SERS基底的研究热点.SERS光谱目前可以在液相色谱分析的检测器、医学检测仪器、刑侦分析检测等众多领域得到应用.     

Effect of pulsed laser irradiation on the SiC surface

The effect of a pulsed laser irradiation (Nd:YVO₄, 1064 nm) in air on the surface morphology and chemical composition of silicon carbide and on the adhesion with an epoxy adhesive was investigated. Scanning and transmission electron microscopies, atomic force microscopy, and X‐ray photoelectron spectroscopy revealed that the laser treatment reduced the contamination level of the surface and induced the formation of a silica‐based nanostructured columnar layer on the SiC surface. The mechanism for the formation of five different microstructural regions is described in this paper. In addition, the formation of a 5‐10‐nm‐thick graphite layer between the oxide layer and SiC was observed. The joining test with Hysol^® EA9321 showed that the nanostructured columnar silica layer was completely infiltrated by the adhesive, thus leading to a significant increase in the joined specific area and a mechanical interlocking at the adhesive/substrate interface. Nevertheless, the apparent shear strength of the joined SiC samples slightly decreased after the laser processing of the surfaces from about 42 MPa for lapped SiC to about 35 MPa for laser‐nanostructured SiC. The formation of the graphite layer was found to be responsible of the poor adhesion properties of the SiC surfaces modified by the laser radiation.