Surface‐enhanced Raman spectra of individual multiwalled carbon nanotubes with small innermost diameters

The Raman spectra of individual multiwalled carbon nanotubes (MWCNTs) with the innermost diameters of 0.6–0.9 nm are studied by surface‐enhanced Raman scattering. The influences of small innermost diameters to Raman features are investigated. A clear and relatively sharp Raman peak appears at 1510 cm⁻¹ when the innermost diameter is close to 0.6 nm. Lorentzian fits of G band indicate that its splitting is affected by the small innermost diameter of MWCNT. Moreover, the splitting of 2iTO mode is also observed at 2800–3000 cm⁻¹. Copyright © 2012 John Wiley & Sons, Ltd.     

Characterisation of carbonaceous materials using Raman spectroscopy: a comparison of carbon nanotube filters,single‐ and multi‐walled nanotubes,graphitised porous carbon and graphite

Multi‐walled carbon nanotube (MWCNT) filters have been recently synthesised which have specific molecular filtering capabilities and good mechanical strength. Optical and scanning electron microscopy (SEM) reveals the formation of highly aligned arrays of bundles of carbon nanotubes having lengths up to 500 µm. The Raman spectra of this material along with four other carbonaceous materials, commercially available single‐walled carbon nanotubes (SWCNTs) and MWCNTs, graphitised porous carbon (Carbotrap) and graphite have been recorded using two‐excitation wavelengths, 532 and 785 nm, and analysed for band positions and shape with special emphasis paid to the D‐, G‐ and G′‐bands. A major difference between the different MWCNT varieties analysed is that G‐bands in the MWCNT filters exhibit almost no dispersion, whereas the other MWCNTs show a noticeable dispersive behaviour with a change in the excitation wavelength. Spectral features similar to those of the MWCNT filter varieties were observed for the Carbotrap material. From the line shape analysis, the intensity ratio, I_D/I_G, of the more ordered MWCNT filter material using the integral G‐band turns out to be two times lower than that of the less ordered MWCNT filter product at both excitation wavelengths. This parameter can, therefore, be used as a measure of the degree of MWCNT alignment in filter varieties, which is well supported also by our SEM study. Copyright © 2008 John Wiley & Sons, Ltd.     

Identification of two Ag‐2,2′:6′,2″‐terpyridine surface species on Ag nanoparticle surfaces by excitation wavelength dependence of SERS spectra and factor analysis: evidence for chemical mechanism contribution to SERS of Ag(0)–tpy

Measurement and interpretation of the excitation wavelength dependence of surface‐enhanced Raman scattering (SERS) spectra of molecules chemisorbed on plasmonic, e.g. Ag nanoparticle (NP) surfaces, are of principal importance for revealing the charge transfer (CT) mechanism contribution to the overall SERS enhancement. SERS spectra, their excitation wavelength dependence in the 445–780‐nm range and factor analysis (FA) were used for the identification of two Ag‐2,2′:6′,2″‐terpyridine (tpy) surface species, denoted Ag⁺–tpy and Ag(0)–tpy, on Ag NPs in systems with unmodified and/or purposefully modified Ag NPs originating from hydroxylamine hydrochloride‐reduced hydrosols. Ag⁺–tpy is a spectral analogue of [Ag(tpy)]⁺ complex cation, and its SERS shows virtually no excitation wavelength dependence. By contrast, SERS of Ag(0)–tpy surface complex generated upon chloride‐induced compact aggregate formation and/or in strongly reducing ambient shows a pronounced excitation wavelength dependence attributed to a CT resonance (the chemical mechanism) contribution to the overall SERS enhancement. Both the resonance (λ_exc = 532 nm) and off‐resonance (λ_exc = 780 nm) pure‐component spectra of Ag(0)–tpy obtained by FA are largely similar to surface‐enhanced resonance Raman scattering (λ_exc = 532 nm in resonance with singlet metal to ligand CT (¹ MLCT) transition) and SERS (λ_exc = 780 nm) spectra of [Fe(tpy)₂]²⁺ complex dication. Copyright © 2014 John Wiley & Sons, Ltd.     

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles for strained‐silicon surface enhanced Raman spectroscopy

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles deposited onto strained‐silicon layers grown on graded Si_1−xGe_x virtual substrates are utilized for selective amplification of the Si–Si vibration mode of strained silicon via surface‐enhanced Raman scattering spectroscopy. This solution‐based technique allows rapid, highly sensitive and accurate characterization of strained silicon whose Raman signal would usually be overshadowed by the underlying bulk SiGe Raman spectra. The analysis was performed on strained silicon samples of thickness 9, 17.5 and 42 nm using a 488 nm Ar⁺ micro‐Raman excitation source. The quantitative determination of strained‐silicon enhancement factors was also made. Copyright © 2011 John Wiley & Sons, Ltd.     

Comparison of SERS effectiveness of copper substrates prepared by different methods: what are the values of enhancement factors?

Surface‐enhanced Raman scattering (SERS) spectroscopy is an analytical method for the detection of low amounts of analytes adsorbed on an appropriate coinage metal (Au, Ag, Cu) surface. Generally, the values of the enhancement factor are the highest on silver, lower on gold and relatively very low on copper. In this study, we have focused on the estimation of the enhancement factors of copper surface/substrates formed by different preparation procedures. The SERS activity of large electrochemically prepared substrates and colloidal systems is compared. The surface morphology of the large substrates was studied using scanning electron microscopy and atomic force microscopy. The size distribution of colloidal nanoparticles was monitored by dynamic light scattering. The values of enhancement factor are in both cases more than 10⁵ for the FT‐SERS spectra, demonstrating the fundamental role of nanostructured copper as a substrate material at the excitation wavelength (1064 nm) used. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman scattering and luminescence of yttria nanopowders and ceramics

We have studied Raman scattering in yttria nanopowders and ceramics that was excited by radiation at wavelengths of 514.5 and 632.8 nm. We show that, in undoped nanopowders and cubic phase of doped yttria ceramics, only the Raman scattering by phonons is observed, with no other Raman scattering centers having been revealed. In nanopowders of the monoclinic phase, we have observed an additional Raman line with a Raman shift of 1093 ± 4 cm^?1. If all the objects under investigation are excited by the radiation at a wavelength of 514.5 nm, their spectra exhibit four series of photoluminescence lines, two of which (at λ = 521–523 and 538–564 nm) are emitted by Er³⁺ ions, “impurity” dopants, while the other two lines (at λ = 607–635 and 644–684 nm) are emitted by intrinsic centers. Under excitation by the radiation at a wavelength of 632.8 nm, only a series of bands at λ = 644–684 nm is emitted. In addition to these photoluminescence bands, neodymium-doped ceramics show photoluminescence bands of Nd³⁺ ions. We have shown that intrinsic luminescence centers, which occur in all the examined specimens, are capable of acting as acceptors with respect to neodymium ions excited to the upper laser level.     

Fabrication of periodical Ag–Au compound nanostructure films with controllable Ag nanoparticle aggregate patterns: a study on surface‐enhanced Raman scattering

The Ag–Au compound nanostructure films with controllable patterns of Ag nanoparticle (NP) aggregates were fabricated. A strategy of two‐step synthesis was employed toward the target products. Firstly, the precursor Au NP (17 nm) films were synthesized as templates. Secondly, the Ag NPs (45 nm) were deposited on the precursor films. Three types of Ag NP aggregates were obtained including discrete Ag NPs (discrete type), necklace‐like Ag NP aggregates (necklace type), and huddle‐like Ag NP aggregates (huddle type). The surface‐enhanced Raman scattering (SERS) property was studied on these nanostructures by using the probing molecule of rhodamine 6G under the excitation laser of 514.5 nm. Interestingly, the different types of samples showed different enhancement abilities. A statistical method was employed to assess the enhancement. The relative enhancement factor for each Ag NP was estimated quantitatively under the ratio of 1 : 25 : 18 for the discrete‐type, necklace‐type, and huddle‐type samples at the given concentration of 10⁻⁸ mol/l. This research shows that the enhancement ability of each Ag NP is dependent on the aggregate morphology. Moreover, the different enhancement abilities displayed different limit detection concentrations up to 10⁻⁸, 10⁻¹¹, and 10⁻⁹ mol/l, separately. The understanding of the relationship between the defined nanostructures and the SERS enhancement is very meaningful for the design of new SERS substrates with better performance. Copyright © 2015 John Wiley & Sons, Ltd.     

High–Yield Production of Uniform Gold Nanoparticles with Sizes from 31 to 577 nm via One‐Pot Seeded Growth and Size‐Dependent SERS Property

In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl₄ into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl₄ solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.     

Low wavenumber Raman scattering of cobalt nanoparticles self‐organized in 3D superlattices far from surface plasmon resonance

We report the first observation of low wavenumber Raman scattering from cobalt nanoparticles under 514.5nm laser excitation. These 7.4nm diameter particles were self‐organized in 3D superlattices, but we assign the Raman signature to vibrations of the individual nanoparticles, according to Lamb's elastic sphere model. We estimate the relative Raman intensity to be around 500 times lower than it would be for silver nanoparticles, but our results demonstrate that surface plasmon–phonon resonance coupling is not mandatory to observe Lamb's modes in metal nanoparticles. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering studies of carbon nanotubes using Ag‐core Au‐shell nanoparticles

Surface‐enhanced Raman scattering from carbon nanotube bundles adsorbed with plasmon‐tunable Ag‐core Au‐shell nanoparticles (Ag@Au nps) was carried out for the first time. By utilizing nanoparticles whose plasmon resonance peak (541, 642 nm) closely matches the commonly used Raman excitation sources (532, 632.81 nm), we can observe a large enhancement in the Raman signatures of carbon nanotubes. We obtain greater enhancement in the Raman signal for the above case when compared to nanotubes adsorbed with conventional Ag, Au or other ‘off resonant’ Ag@Au nps. The power‐dependent SERS experiment on single‐walled nanotubes (SWNTs) with resonant Ag@Au nps reveals a linear behavior between the G‐band intensity and the photon flux density, which is in agreement with the vibrational pumping model of SERS. The observed enhancement by resonance matching is pronounced for carbon nanotubes and may lead to insights into understanding nanotube–nanoparticle interaction. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of carbon nanotube filters and other carbonaceous materials by Raman spectroscopy—II: study on dispersion and disorder parameters

Recently, we have reported on the characterization of various carbonaceous materials including multiwalled carbon nanotube (MWCNT) filters, which have specific molecular filtering capabilities and good mechanical strength and can be produced in bulk as highly aligned arrays of bundles of CNTs. We have extended our studies using Fourier transform‐Raman spectroscopy with 1064 nm excitation wavelength and a rotating sample holder in the region 1000–2800 cm⁻¹, in addition to 532 and 785 nm, which were used for Raman excitation in our previous study. Raman spectra were analyzed for band positions and line shape with special emphasis on the D‐, G‐ and G′‐ bands. For the single‐walled species, Carbotrap and graphite spectra were also recorded with 488 nm excitation. A dispersion study has been made from the Raman data available with the different excitation wavelengths. Slight band shifts and band broadening could be observed under the two sample conditions, one with the stationary sample and the other with sample rotation. The spectral changes are related to the excessive heating caused in a stationary sample by laser irradiation. Based on our findings in this study combined with our earlier study, we can state that only a careful line shape analysis and study of intensity pattern of the D‐ and G‐Raman bands under well‐defined measurement conditions lends itself as a good measure of degree of alignment in the MWCNT bundles. Copyright © 2010 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.     

Raman Scattering Intensities of the NO2 Symmetric Stretching Vibration Band of Some Aromatic Nitrocompounds (II)

The Raman scattering intensities of the NO₂ symmetric stretching vibration band were investigated experimentally for some para and meta substituted nitrobenzenes. The excitation profiles obtained with the six excitation wavelengths from 457.9 to 514.5 nm were presented. The results were examined in terms of the Albrecht-Hutley's theory, and the electronic states involved in the preresonance Raman intensity enhancement were suggested.     

The growth of the passive film on iron in 0.05 M NaOH studied in situ by Raman micro‐spectroscopy and electrochemical polarisation. Part I: near‐resonance enhancement of the Raman spectra of iron oxide and oxyhydroxide compounds

Raman spectroscopy, in principle, is an excellent technique for the study of molecular species developed on metal surfaces during electrochemical investigations. However, the use of the more common laser wavelengths such as the 514.5‐nm line results in spectra of less than optimal intensity, particularly for iron oxide compounds. In the present work, near‐resonance enhancement of the Raman spectra was investigated for the iron oxide and iron oxyhydroxide compounds previously reported to be present in the passive film on iron, using a tuneable dye laser producing excitation wavelengths between 560 and 637 nm. These compounds were hematite (α‐Fe₂O₃), maghemite (γ‐Fe₂O₃), magnetite (Fe₃O₄), goethite (α‐FeOOH), akaganeite (β‐FeOOH), lepidocrocite (γ‐FeOOH) and feroxyhyte (δ‐FeOOH). Optimum enhancement, when compared to that with the 514.5‐nm line, was obtained for all the iron oxide and oxyhydroxide standard samples in the low wavenumber region (<1000 cm⁻¹) using an excitation wavelength of 636.4 nm. Particularly significant enhancement was obtained for lepidocrocite, hematite and goethite. Copyright © 2010 John Wiley & Sons, Ltd.     

Broad spectral photonic crystal fiber surface enhanced Raman scattering probe

A broad spectral surface enhanced Raman scattering sensor is developed using the solid core holey photonic crystal fiber with silver nanoparticles cluster. This SERS probe offers an operational excitation wavelength range overlaying visible light and near infrared light. The PCF SERS sensing is demonstrated in the detection of the 4-Mercaptobenzoic acid (10⁻⁶ M) solution with 514.5 and 785 nm excitation. In this structure of PCF sensor, the related analysis shows that leakage modes also make an important contribution in the SERS activity not only by the evanescent field way.     

两种激发波长下蔬菜水果的拉曼光谱对比研究

本文通过改变不同的激光光源波长,测试分析了一系列蔬菜水果表面的拉曼谱。比较514.5nm和1064nm波长下的拉曼谱,发现514.5nm激发下许多蔬菜水果的拉曼谱均出现胡萝卜素的共振拉曼光谱,同时有很强的光荧光。更换成1064nm的近红外激光波长后,基本消除了光荧光和共振效应的影响,可用来测量蔬菜水果的有效成分,而514.5nm激发下只出现胡萝卜素的光谱,为区分蔬菜水果表面的外来物质,如农药,提供了很大的方便。     

Study of Raman spectrum of uranium using a surface‐enhanced Raman scattering technique

Raman spectroscopic investigation on weak scatterers such as metals is a challenging scientific problem. Technologically important actinide metals such as uranium and plutonium have not been investigated using Raman spectroscopy possibly due to poor signal intensities. We report the first Raman spectrum of uranium metal using a surface‐enhanced Raman scattering‐like geometry where a thin gold overlayer is deposited on uranium. Raman spectra are detected from the pits and scratches on the sample and not from the smooth polished surface. The 514.5‐ and 785‐nm laser excitations resulted in the Raman spectra of uranium metal whereas 325‐nm excitation did not give rise to such spectra. Temperature dependence of the B_3g mode at 126 cm⁻¹ is also investigated. Copyright © 2011 John Wiley & Sons, Ltd.     

Single‐molecule surface‐enhanced Raman scattering of fullerene C60

We achieved single‐molecule surface‐enhanced Raman scattering (SM‐SERS) spectra from ultralow concentrations (10⁻¹⁵ M) of fullerene C₆₀ on uniformly assembled Au nanoparticles. It was found that resonant excitation at 785 nm is a powerful tool to probe SM‐SERS in this system. The appearance of additional bands and splitting of some vibrational modes were observed because of the symmetry reduction of the adsorbed molecule and a relaxation in the surface selection rules. Time‐evolved spectral fluctuation and ‘hot spot’ dependence in the SM‐SERS spectra were demonstrated to result from the single‐molecule Raman behavior of the spherical C₆₀ on Au nanoparticles. Copyright © 2010 John Wiley & Sons, Ltd.     

具有双共振吸收峰的Au纳米粒子制备及其拉曼表征

表面增强拉曼散射(SERS)很大程度的弥补了拉曼散射强度弱的缺点,迅速成为科研工作者们的研究热点,在食品安全、环境污染、毒品以及爆炸物检测等领域应用广泛。纳米技术的发展使得目前对于SERS的研究主要集中于金属纳米颗粒基底的制备,金属纳米粒子的种类、尺寸及形貌对SERS增强和吸收峰峰位均有影响,要获得好的增强效果,需要对金属纳米结构进行工艺优化。特别是,需要结合金属纳米粒子的结构和激励光波长,以期获得更好的增强效果。为了研究SERS增强和吸收峰之间的关系,开展了具有双共振吸收峰的金属纳米粒子的研究。首先利用FDTD Solutions仿真建模,主要针对金纳米颗粒直径、金纳米棒长径比及分布状态对共振吸收峰进行仿真,得到金纳米球理论直径在50 nm左右,金纳米棒理论长径比在3.5~4.5左右时,吸收峰分别分布在532及785 nm附近,符合多波段激励光拉曼增强条件;对于激励光偏振方向,其沿金纳米棒长轴方向偏振时吸收峰位于785 nm附近,沿金纳米球短轴方向偏振时吸收峰位于532 nm附近。然后采用种子生长法,制备了可用于多种波长激励光的双吸收峰表面增强拉曼散射基底。通过改变硝酸银用量(5,10,20,30和40 μL)、盐酸用量(0.1和0.2 mL)以及其生长时间(15,17,21和23 h)等多种工艺参数来控制金纳米棒含量,得到了同时含有金纳米球及金纳米棒的双吸收共振峰金纳米粒子。最后用该样品作为基底,罗丹明6G(R6G)作为探针分子,分别测试其在532,633和785 nm激励光入射时的SERS表征,对分析物R6G最低检测浓度均达到了10-7 mol·L-1,增强因子达到了~105,满足了多波段SERS检测的需要。     

光纤共振和预共振喇曼光谱

在液芯光纤内产生共振和预共振喇曼效应,喇曼光谱强度可以大幅度提高,最高可达10⁹倍.本文介绍获得光纤(预)共振喇曼光谱的可行性、实验及实验结果.用远离吸收带的激光激发获得了α甲基吡啶预共振喇曼光谱.用小功率激光(0.8mW)、低浓度溶液(9.6×10¹²mol/L)还获得了β叶红素在CS₂中的共振喇曼光谱.