The distributions of enhancement factors in close‐packed and nonclose‐packed surface‐enhanced Raman substrates

A method employing photochemical hole burning, previously developed to measure the distribution of Raman enhancement factors on a nanostructured substrate for surface‐enhanced Raman scattering, is used to compare the enhancement distributions of benzenethiol adsorbed on substrates optimized for 532 nm laser excitation consisting of close‐packed (CP) or nonclose‐packed (NCP) nanospheres. The ensemble‐averaged Raman enhancement factor was 2.8 times smaller for the NCP substrate. The measured distributions revealed additional information. For instance, 92% of the molecules on the CP substrate and 93.6% of the molecules on the NCP substrate had Raman enhancements below average. The minimum enhancements on both substrates were ~10⁴, but on the NCP substrate the maximum enhancement was 1.2 × 10⁸, whereas on the CP substrate the maximum was 2 × 10¹⁰. The Ag‐coated nanospheres form hemisphere‐on‐cylinder mushroom‐like structures on both lattices, but on the NCP lattice, one third of the molecules are on the flat regions between the mushrooms. The flats on the NCP lattice have enhancements of ~10⁴, showing they are part of a resonant plasmonic structure. The highest NCP enhancements of ~10⁸ are tentatively associated with regions at the bases of the mushrooms, whereas the highest CP enhancements of 2 × 10¹⁰ are tentatively associated with gaps between nanospheres where 0.0025% of the molecules reside. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering and DFT calculations studies of 3,3′‐diethylthiatri‐ carbocyanine iodide

As an infrared Raman probe, the molecule 3,3′‐diethylthiatricarbocyanine iodide (DTTC) has received much attention in the past decades due to its potential applications in Raman imaging, single‐cell detection, cancer diagnosis, and surface‐enhanced Raman scattering (SERS). In this work, ordinary Raman, SERS, and theoretical Raman spectra were investigated to estimate the DTTC suspension. More specifically, the original gold nanospheres (60 nm diameter) and gold nanorods were encoded with DTTC and stabilized with a layer of thiol–polyethylene glycol as Raman reporter; SERS data were also obtained from the samples. Hartree–Fock theory and density functional theory (DFT) calculation were applied to calculate the optimized Raman spectra of DTTC in water on the B3LYP/6‐31G level. Subsequently, the obtained experimental spectra from DTTC were carefully compared with the theoretically calculated spectra, and good agreement was obtained between the theoretical and experimental results.The bands between 500 and 3100 cm⁻¹ in the ordinary Raman and SERS spectra were assigned as well. This work will facilitate the development of ultrasensitive SERS probes for advanced biomedical imaging applications. Copyright © 2011 John Wiley & Sons, Ltd.     

Gold‐coated zinc oxide nanowire‐based substrate for surface‐enhanced Raman spectroscopy

Zinc oxide nanowires with two distinct morphologies were synthesized on silicon substrates using a simple thermal evaporation and vapor transport method in an oxidizing environment. The as‐synthesized nanowires were coated with gold to allow excitation of surface plasmons over a broad frequency range. SERS studies with near‐IR excitation at 785 nm showed significant enhancement (average enhancement > 10⁶) with excellent reproducibility to detect monolayer concentrations of 4‐methylbenzenethiol (4‐MBT) and 1,2‐benzendithiol (1,2‐BDT) probe molecules. The Raman enhancement showed a strong dependence on the gold film thickness, and the peak enhancement was observed for a ∼40‐nm‐thick film. The Raman enhancement was stronger for randomly oriented nanowires compared to aligned ones suggesting the importance of contributions from the junctions of nanowires. Copyright © 2009 John Wiley & Sons, Ltd.     

Crystal → nematic phase transition in the liquid crystalline system 1‐isothiocyanato‐4‐(trans‐4‐propylcyclohexyl) benzene (3CHBT) probed by temperature‐dependent micro‐Raman study and DFT calculations

Raman spectra of 3CHBT in unoriented form were recorded at 14 different temperature measurements in the range 25–55 °C, which covers the crystal → nematic (N) phase transition, and the Raman signatures of the phase transition were identified. The wavenumber shifts and linewidth changes of Raman marker bands with varying temperature were determined. The assignments of important vibrational modes of 3CHBT were also made using the experimentally observed Raman and infrared spectra, calculated wavenumbers, and potential energy distribution. The DFT calculations using the B3LYP method employing 6‐31G functional were performed for geometry optimization and vibrational spectra of monomer and dimer of 3CHBT. The analysis of the vibrational bands, especially the variation of their peak position as a function of temperature in two different spectral regions, 1150–1275 cm⁻¹ and 1950–2300 cm⁻¹, is discussed in detail. Both the linewidth and peak position of the ( C H ) in‐plane bending and ν(NCS) modes, which give Raman signatures of the crystal → N phase transition, are discussed in detail. The molecular dynamics of this transition has also been discussed. We propose the co‐existence of two types of dimers, one in parallel and the other in antiparallel arrangement, while going to the nematic phase. The structure of the nematic phase in bulk has also been proposed in terms of these dimers. The red shift of the ν(NCS) band and blue shift of almost all other ring modes show increased intermolecular interaction between the aromatic rings and decreased intermolecular interaction between two  NCS groups in the nematic phase. Copyright © 2009 John Wiley & Sons, Ltd.     

Aptamer‐Assisted Assembly of Gold Nanoframe Dimers

The assembly of nanoframe dimers assisted by aptamer‐functionalized smaller spherical gold nanoparticles as prospective surface‐enhanced Raman scattering (SERS) biotraps for riboflavin, an important molecule for biological electron transfer reactions, is reported. In this approach, the aptamer‐coated gold nanoparticles designed for selective binding of riboflavin also serve as the electrostatic driver for nanoframe dimerization in dilute solutions. The gold nanoframe dimers provide unique conditions for plasmonic coupling in a hot spot with sufficient space for the binding of bulky biomolecules. The use of an aptamer allows for highly selective binding of the targeted analyte as compared with conventional organic ligands with excellent low detection limit of one micromole of riboflavin.     

Surface‐enhanced Raman scattering within silver‐nanoparticle‐decorated nanometric apertures

An analytical approach using enhanced Raman spectroscopy to record molecular vibrations and associated molecular images within nanometric apertures is presented, which can essentially rival or surpass its counterparts, i.e. fluorescence microscopy, by providing unique structure‐specific information forward to chemical identification and structure elucidation. Utilizing a precise nanolithographic technology and the following chemically electroless silver deposition procedure, we deliberately construct the large scale zero‐mode waveguide array in gold film with embossed silver nanostructures on the bottom of nanowells capable of acquiring enhanced Raman spectra with substantial sensitivity and high chemical fidelity. Two chemicals, aminothiophenol (4‐ATP) and Rhodamine 6G, respectively, are employed as molecular indicators to successfully demonstrate the capability of this analytical strategy by exhibiting high‐quality Raman spectra and 2D chemical‐specific images. With a high magnitude objective (60×), we enable to acquire Raman spectra from a single nanometric aperture and quantitatively determine a peak enhancement factor of 3.63 × 10⁵ for ATP, while 1.25 × 10⁶ to Rhodamine 6G, comparable with a regular nanoparticle‐based surface‐enhanced Raman spectroscopy‐active substrate. Overall, the compelling characteristics of this detection scheme highlight its privileges for interrogating the individual molecular behavior in extremely confined geometry and illustrating the chemical insights of trace components without any labeling reagent and extra sample preparation. Copyright © 2013 John Wiley & Sons, Ltd.     

Microstructured polymer‐based substrates with broadband absorption for surface‐enhanced Raman scattering

Large area (3 × 3 cm²) substrates for surface‐enhanced Raman scattering were fabricated by combining femtosecond laser microstructuring and soft lithography techniques. The fabrication procedure is as follows: (i) femtosecond laser machining is used to create a silicon master copy, (ii) replicates from polydimethylsiloxane are made, and (iii) a 50‐nm‐thick gold film is deposited on the surface of the replicates. The resulting substrates exhibit strongly enhanced absorption in the spectral region of 350 ∼ 1000 nm and generate enhanced Raman signal with enhancement factor of the order of 10⁷ for 10^{‐ 6} M rhodamine 6G. The main advantages of our substrates are low cost, large active area, and possibility for mass replication. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrochemically fabricated nanovolcano arrays for SERS applications

Nanovolcano arrays were fabricated by electrodepositing Ni/Cu alloys into a monolayer of self‐assembled nanospheres and then electrochemically etching the deposited alloy film. The fabricated nanovolcano arrays feature highly ordered hexagonally arranged concave nanobowls decorated with triangular nanopores at their interstices. After coated with Ag, the nanovolcano arrays serve as high‐performance substrates for surface enhancement Raman spectroscopy (SERS) measurements. The experimental study shows that the structural features of the nanovolcano arrays, including concave nanobowls, nanopores, and their long‐range orders, all contribute to the observed strong SERS enhancement in a synergetic manner, which is further confirmed by the simulation results obtained using the finite‐difference time‐domain method. Copyright © 2012 John Wiley & Sons, Ltd.     

SERS enhancement of gold nanospheres of defined size

Monodisperse, citrate‐stabilized gold nanoparticles of sizes ranging from 15 to 40 nm were synthesized and characterized by small angle X‐ray scattering and UV‐vis experiments. Identical surface properties of nanoparticles of different sizes to avoid variation in the chemical surface‐enhanced Raman scattering (SERS) enhancement, as well as selection of experimental conditions so that no aggregation took place, enabled the investigation of enhancement of individual nanospheres. Enhancement factors (EFs) for SERS were determined using the dye crystal violet (CV). EFs for individual gold nanospheres ranged from 10² to 10³, in agreement with theoretical predictions. An increase of the EFs of individual spheres with size can be correlated to changes in the extinction spectra of nanoparticle solutions. This confirms that the increase in enhancement with increasing size results from an increase in electromagnetic enhancement. Beyond this dependence of EFs of isolated gold spheres on their size, EFs were shown to vary with analyte concentration as a result of analyte‐induced aggregation. This has implications for the application of nanoparticle solutions as SERS substrates in quantitative analytical tasks. Copyright © 2011 John Wiley & Sons, Ltd.     

Induced SERS activity in Ag@SiO2/Ag core‐shell nanosphere arrays with tunable interior insulator

In this work, we demonstrated a bottom‐up growth of Ag@SiO₂/Ag core‐shell nanosphere arrays with tunable SiO₂ interior insulator and the optimized surface‐enhanced Raman scattering (SERS) substrate based on a nanostructure performed with both high sensitivity and large‐area uniformity. Their morphological, structural, and optical properties were characterized, and the induced SERS activities were investigated theoretically by the FDTD simulation and experimentally using analyte molecules. An ultrathin SiO₂ shell with tunable thickness can be synthesized pinhole‐free by a chemical vapor deposition, working as an interior insulator between the Ag core and Ag out‐layer coating. A detection limit as low as 10⁻¹² M and an enhancement factor up to 3 × 10⁷ were obtained, and the SERS signal was highly reproducible with small standard deviation. The method opened up a way to create a new class of SERS activity sensor with high‐density ‘hot spots’, and it may play an important role in device design and the corresponding biological and food safety monitoring applications. Copyright © 2016 John Wiley & Sons, Ltd.     

A facile high‐performance SERS substrate based on broadband near‐perfect optical absorption

Plasmonic systems based on metal nanoparticles on a metal film with high optical absorption have generated great interests for surface‐enhanced Raman scattering (SERS). In this study, we prepare a broadband‐visible light absorber consisting Au nanotriangles on the surface of a continuous optically opaque gold film separated with a dielectric SiO₂ layer, which is a typical metal‐insulator‐metal (MIM) system, and demonstrate it as an efficient SERS substrate. The MIM nanostructure, prepared using nanosphere lithography with a very large area, shows a broadband with absorption exceeding 90% in the wavelength regime of 630–920 nm. We observe an average SERS enhancement factor (EF) as large as 4.9 × 10⁶ with a 22‐fold increase compared to a single layer of Au nanotriangles directly on a quartz substrate. A maximum SERS EF can be achieved by optimizing the thicknesses of the dielectric layer to control the optical absorption. Owing to the simple, productive, and inexpensive fabrication technique, our MIM nanostructure could be a potential candidate for SERS applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Concentration‐ and temperature‐dependent conformation change of cyclohexyl isocyanide on gold nanoparticle surfaces

The conformational changes of cyclohexyl isocyanide (CHNC) on gold nanoparticle surfaces were investigated by means of concentration‐ and temperature‐dependent surface‐enhanced Raman scattering (SERS). The equatorial chair conformer appeared to be dominant at high‐bulk concentrations or low temperatures, whereas both the equatorial and axial chair conformers of CHNC were found to exist at low‐bulk concentrations or high temperatures as in the previous reports of cyclohexanethiol (CHT). Depending on concentrations and temperatures, the spectral changes of the NC stretching vibration on gold nanoparticles appeared to be more conspicuous than those of the cyclohexyl ring modes. A density functional theory (DFT) calculation was performed at the level of B3LYP/6‐31G + + (d,p) to compare the energetic stability of the various conformers of CHT and CHNC. The energy differences between the equatorial and axial chair conformers were predicted to be smaller for CHNC than for CHT by ∼3 kJ mol⁻¹ from the DFT calculation. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman spectroscopy on novel black silicon‐based nanostructured surfaces

Two different black silicon nanostructured surfaces modified with thin gold layers were tested for analytical signal enhancement with Surface‐Enhanced Raman Spectroscopy (SERS). The relationship between the thicknesses of the gold layers and the analytical signal enhancement was studied. Also, effects of Ti and Ti/Pt adhesion layers underneath the gold layers on the analytical signal enhancement were tested. An enhancement factor of 7.6 × 10⁷ with the excitation laser 785 nm was achieved for the tested analyte, Rhodamine 6G, and non‐resonance SER spectra were recorded in a 5 s acquisition mode. Such an enhancement enables to achieve a detection limit down to 2.4 pg of Rhodamine 6G on a black silicon‐based nanosurface coated with a 400‐nm‐thin layer of gold. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering‐based approach for DNA detection at low concentrations via polyvinyl alcohol‐protected silver grasslike patterns

A simple method is demonstrated to detect DNA at low concentrations on the basis of surface‐enhanced Raman scattering (SERS) via polyvinyl alcohol‐protected silver grasslike patterns (PVA‐Ag GPs) grown on the surface of the common Al substrate. By the SERS measurements of sodium citrate and thymine, the PVA‐Ag GPs are shown to be an excellent SERS substrate with good activity, stability and reproducibility. With the use of the tested molecule of thymine, the enhancement factor of the PVA‐Ag GPs is up to ~1.4 × 10⁸. The PVA‐Ag GPs are also shown to be an excellent SERS substrate with good biocompatibility for DNA detection, and the detection limit is down to ~10⁻⁵ mg/g. Meanwhile, the assignations of the Raman bands and the adsorption behaviors of the DNA molecules are also analyzed. In this work, the geometry optimization and the wavenumber analysis of adenine–Ag and guanine–Ag complexes for the ground states are performed using density functional theory, B3LYP functional and the LanL2DZ basis set. The transition energies and the oscillator strengths of adenine–Ag and guanine–Ag for the lowest six singlet excited states were calculated by using the time‐dependent density functional theory method with the same functional and basis set. The results show that the charge transfer in the adenine–Ag and guanine–Ag complexes should be the chemical factor for the SERS of the DNA molecules. Lastly, this method may be employed in large‐scale preparation of substrates that have been widely applied in the Raman analysis of DNA because the fabrication process is simple and inexpensive. Copyright © 2011 John Wiley & Sons, Ltd.     

Temperature‐depending Raman line‐shift of silicon carbide

Silicon carbide (SiC) is often used for electronic devices operating at elevated temperatures. Spectroscopic temperature measurements are of high interest for device monitoring because confocal Raman microscopy provides a very high spatial resolution. To this end, calibration data are needed that relate Raman line‐shift and temperature. The shift of the phonon wavenumbers of single crystal SiC was investigated by Raman spectroscopy in the temperature range from 3 to 112°C. Spectra were obtained in undoped 6H SiC as well as in undoped and nitrogen‐doped 4H SiC. All spectra were acquired with the incident laser beam oriented parallel as well as perpendicular to the c‐axis to account for the anisotropy of the phonon dispersion. Nearly all individual peak centers were shifting linearly towards smaller wavenumbers with increasing temperature. Only the peak of the longitudinal optical phonon A₁(LO) in nitrogen‐doped 4H SiC was shifting to larger wavenumbers. For all phonons, a linear dependence of the Raman peaks on both parameters, temperature and phonon frequency, was found in the given temperature range. The linearity of the temperature shift allows for precise spectroscopic temperature measurements. Temperature correction of Raman line‐shifts also provides the ability to separate thermal shifts from mechanically induced ones. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering from gold‐coated germanium oxide nanowires

We utilized bulk‐synthesized nanowires (NWs) of germanium dioxide as nanoscale structures that can be coated with noble metals to allow the excitation of surface plasmons over a broad frequency range. The NWs were synthesized on substrates of silicon using gold‐catalyst‐assisted vapor–liquid–solid (VLS) growth mechanism in a simple quartz tube furnace setup. The resulting NWs have diameters of ∼100–200 nm, with lengths averaging ∼10–40 µm and randomly distributed on the substrate. The NWs are subsequently coated with thin films of gold, which provide a surface‐plasmon‐active surface. Surface‐enhanced Raman scattering (SERS) studies with near‐infrared (NIR) excitation at 785 nm show significant enhancement (average enhancement > 10⁶) with good uniformity to detect submonolayer concentrations of 4‐methylbenzenethiol (4‐MBT), trans‐1,2‐bis(4‐pyridyl)ethylene (BPE), and 1,2‐benzendithiol (1,2‐BDT) probe molecules. We also observed an intense, broad continuum in the Raman spectrum of NWs after metal coating, which tended to diminish with the analyte monolayer formation. Copyright © 2008 John Wiley & Sons, Ltd.     

Particle‐Arrayed Silver Mesocubes Synthesized via Reducing Silver Oxide Mesocrystals for Surface‐Enhanced Raman Spectroscopy

In this study, we demonstrate an easy particle‐mediated protocol using the specific structure of mesocrystal Ag₂O sacrificial templates to synthesize highly rough‐cubic Ag mesocages. To the best of our knowledge, the mesocrystal particles are reported for the first time as sacrificial templates for synthesizing metal particles. The obtained Ag mesocages show high surface‐enhanced Raman scattering (SERS) sensitivity because of the highly rough topography formed by arrays of uniform individual Ag nanoparticles. Abundant “hot spots” with greatly enhanced local electromagnetic field are promoted densely on the mesocage surface by the plenty of deep and narrow gaps and the hollow structure. The single‐particle SERS signal generated by the Ag mesocage has an enhancement factor of approximately 10⁹, which is approximately four times higher than the Ag mesocage synthesized using single‐crystal Ag₂O particle as a template. Meanwhile, this signal displays a linear dependence on the detected analyte concentration, sensitively down to 1.0 × 10^?12 m .     

Large‐area Ag nanorod array substrates for SERS: AAO template‐assisted fabrication,functionalization, and application in detection PCBs

Highly ordered arrays of thiolated β‐cyclodextrin (HS‐β‐CD) functionalized Ag‐nanorods (Ag‐NRs) with plasmonic antennae enhancement of electrical field have been achieved for encapsulation and rapid detection of polychlorinated biphenyls (PCBs). The large‐area ordered arrays of rigid Ag‐NRs supported on copper base were fabricated via porous anodic aluminum oxide (AAO) template‐assisted electrochemical deposition. The inter‐nanorod gaps between the neighboring Ag‐NRs were tuned to sub‐10 nm by thinning the pore‐wall thickness of the AAO template using diluted H₃PO₄. The nearly perfect large‐area ordered arrays of Ag‐NRs supported on copper base render these systems excellent in surface‐enhanced Raman scattering (SERS) performance with uniform electric field enhancement, as testified by the SERS spectra and Raman mappings of rhodamine 6 G. Furthermore, the Ag‐NRs were functionalized with HS‐β‐CD molecules so as to capture the apolar PCB molecules in the hydrophobic cavity of the CD. Compared to the ordinary undecorated SERS substrates, the HS‐β‐CD modified Ag‐NR arrays exhibit better capture ability and higher sensitivity in rapid detection of PCBs. Copyright © 2012 John Wiley & Sons, Ltd.     

Sub‐microsecond‐resolved multi‐speckle X‐ray photon correlation spectroscopy with a pixel array detector

Small‐angle X‐ray photon correlation spectroscopy (XPCS) measurements spanning delay times from 826 ns to 52.8 s were performed using a photon‐counting pixel array detector with a dynamic range of 0–3 (2 bits). Fine resolution and a wide dynamic range of time scales was achieved by combining two modes of operation of the detector: (i) continuous mode, where data acquisition and data readout are performed in parallel with a frame acquisition time of 19.36 µs, and (ii) burst mode, where 12 frames are acquired with frame integration times of either 2.56 µs frame^?1 or 826 ns frame^?1 followed by 3.49 ms or 1.16 ms, respectively, for readout. The applicability of the detector for performing multi‐speckle XPCS was demonstrated by measuring the Brownian dynamics of 10 nm‐radius gold and 57 nm‐radius silica colloids in water at room temperature. In addition, the capability of the detector to faithfully record one‐ and two‐photon counts was examined by comparing the statistical distribution of photon counts with expected probabilities from the negative binomial distribution. It was found that in burst mode the ratio of 2 s to 1 s is markedly smaller than predicted and that this is attributable to pixel‐response dead‐time.     

Effect of high‐energy light‐ion irradiation on SI‐GaAs and GaAs:Cr as observed by Raman spectroscopy

The structural evolutions of high‐energy (50 MeV) lithium ion (Li³⁺) irradiated undoped semi‐insulating GaAs (SI‐GaAs) and chromium‐doped SI‐GaAs (GaAs:Cr) were investigated by Raman measurements. It is shown that high‐energy Li³⁺ irradiation causes amorphization beyond a fluence of 3 × 10¹³ ions/cm² in undoped SI‐GaAs. Interestingly, the same fluence of ions does not seem to affect the crystallinity in GaAs:Cr appreciably. The effect of ion irradiation on the change in lattice ordering and anharmonicity of the phonon modes of undoped SI‐GaAs and GaAs:Cr is also compared. Copyright © 2011 John Wiley & Sons, Ltd.