Electromagnetic coupling in near-field scattering by small homogeneous and heterogeneous nanoaggregates

Progress in near-field optical spectroscopy research on metal nanoparticles demands a better understanding of the role played by particle-particle interactions and a deeper insight of the influence of the incident field wavelength. This is particularly true for scanning near-field optical microscopy (SNOM), where the mechanism by which some components of the evanescent illuminating field are transformed into propagating field components that carry information about the sample is at the core of the image formation and where the role played by the interactions between sample and tip remains a still open problem. In this perspective, we investigate numerically the optical behavior of small aggregates of spherical nanoparticles, taking into account the electromagnetic coupling between all particles and the apertureless tip. The tip is modeled as a sphere made of different materials characterized by appropriate dielectric functions. We find that the tip material affects both qualitatively and quantitatively the SNOM images; more important, from the analysis of the calculated scattering cross section, the resonance plasmon location of the whole (aggregate + tip) system undergoes detectable changes, if the tip is constituted of the same material of the sample, as the tip is situated in different positions. This modification of the plasmon frequencies induces a nontrivial variation of the near-field intensity as a function of the tip position and the resulting SNOM image can be distorted with respect to the actual shape of the sample. No simple arguments can be used to relate the value of the local field on the tip surface to the scattering cross section value; depending on the tip material, the comparison between these two measurements can help to clarify the role of basic interactions in the scattering mechanism.     

Dense two-dimensional silver single and double nanoparticle arrays with plasmonic response in wide spectral range

We report the properties of plasmons in dense planar arrays of silver single and double nanostructures with various geometries fabricated by electron beam lithography (EBL) as a function of their size and spacing. We demonstrate a strong plasmon coupling mechanism due to near-field dipolar interactions between adjacent nanostructures, which produces a major red shift of the localized surface plasmon resonance (LSPR) in silver nanoparticles and leads to strong maximum electric field enhancements in a broad spectral range. The extinction spectra and maximum electric field enhancements are theoretically modeled by using the finite element method. Our modeling revealed that strong averaged electric field enhancements of up to 60 in visible range and up to 40 in mid-infrared result from hybridization of multipolar resonances in such dense nanostructures; these are important for applications in surface enhanced spectroscopies.     

Cantilever tip near-field surface-enhanced Raman imaging of tris(bipyridine)ruthenium(II) on silver nanoparticles-coated substrates

The near-field surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) images of tris(bipyridine)ruthenium(II) adsorbed on a silver nanoparticles-coated substrate were obtained with a scanning near-field optical microscope (SNOM, or near-field scanning optical microscopy, NSOM) using a cantilever tip. In comparison with the most widely used fiber tip for SNOM, the cantilever tip has higher optical throughput and better thermal stability, making it more suitable for detecting the extremely low Raman signal in the near-field spectroscopic investigations. Our preliminary results show that the near-field SERS with the higher spatial resolution can provide richer fingerprint information than the far-field SERS. A comparison of the two types of images shows that there are more SERS than SEF hot spots, and the two types of hot spots do not overlap. More surprisingly, the near-field SERS spectra differ from the far-field SERS spectra obtained on the same sample in the band frequency and relative intensities of some major Raman bands, and some IR-active bands were observed with the near-field mode. These results are explained mainly by the electric field gradient effect and heterogeneous polarization character that operate only in the near-field SERS.     

Role of Nanocavity Plasmons in Tunneling Electron Induced Light Emission on and near a Molecule

By using a microscopic quantum model, we study theoretically different roles of nanocavity plasmons in scanning tunneling microscope (STM) induced light emission upon selective initial excitation of molecules or plasmons. The time evolution and spectroscopic properties of the emission from the coupled plasmon-molecule system in each case are studied using time-dependent quantum mater equations. When the STM tip is placed on the molecule to ensure direct carrier injection induced molecular excitation, the major role of the plasmons is to enhance the molecular emission via increasing its radiative decay rate, resulting in sharp molecule-specific emission peaks. On the other hand, when the STM tip is located in close proximity to the edge of the molecule but without direct carrier injection into the molecule, the role of the plasmon-molecule coupling is to cause destructive interferences between the two quantum objects, leading to the occurrence of Fano dips around the energy of the molecular exciton in the plasmonic emission spectra.     

Chemical imaging of the surface of self-assembled polystyrene-b-poly(methyl methacrylate) diblock copolymer films using apertureless near-field IR microscopy

The nanoscale chemical composition variations of the surfaces of thin films of polystyrene- b-poly(methyl methacrylate) (PS- b-PMMA) diblock copolymers are investigated using apertureless near-field IR microscopy. The scattering of the incident infrared beam from a modulated atomic force microscopy (AFM) tip is probed using homodyne detection and demodulation at the tip oscillation frequency. An increase in the IR attenuation is observed in the PMMA-rich domains with a wavenumber dependence that is consistent with the bulk absorption spectrum. The results indicate that even though a small topography-induced artifact can be observed in the near-field images, the chemical signature of the sample is detected clearly.     

High-resolution apertureless near-field optical imaging using gold nanosphere probes

An apertureless near-field scanning optical microscope (ANSOM) that utilizes the enhanced field around a gold nanosphere, which is attached to the end of an atomic force microscope (AFM) tip, is used to image the local dielectric constant of the patterned metallic surfaces and local electric field around plasmonic nanosphere samples. A colloidal gold nanosphere (approximately 50 nm diameter) is linked to the extremity of the conventional etched-silicon probe. The scattering of laser radiation (633 or 532 nm) is modulated by the oscillating nanosphere-functionalized silicon tip, and the scattered radiation is detected. The approach curve (scattering intensity as a function of the tip-sample distance), the polarization dependence (scattering intensity as a function of the excitation polarization direction), and ANSOM image contrast confirm that the spherical nanosphere attached to the silicon tip acts as a point dipole that interacts with the sample surface via a dipole-dipole coupling, in which the dipole created by the field at the tip interacts with its own image dipole in the sample. The image obtained with the nanoparticle functionalized tip provides a dielectric map of the sample surface with a spatial resolution better than 80 nm. In addition, we show that the functionalized tip is capable of imaging the local electric field distribution above the plasmonic nanosphere samples. Overall, the result shows that high-resolution ANSOM is possible without the aid of the lightning-rod effect. With an improved tip-fabrication method, we believe that the method can provide a versatile high-resolution chemical imaging that is not available from usual forms of ANSOM.     

扫描近场光学显微镜及其在单分子探测中的应用

扫描近场光学显微镜在光学显微镜中具有独特的性能,其突破衍射光限制,具有单分子探测灵敏度,且在研究时不损伤生物样品。文中简要介绍了扫描近场光学显微镜的原理,详述近年来扫描近场光学显微镜在单分子探测中的应用,介绍了扫描近场光学显微镜结合量子点对单分子探测的进展,并对单分子探测的前景做了展望。     

Distinguishing Enantiomers by Tip‐Enhanced Raman Scattering: Chemically Modified Silver Tip with an Asymmetric Atomic Arrangement

Discrimination between enantiomers is achieved by tip‐enhanced Raman scattering (TERS) using a silver tip that is chemically modified by an achiral para‐mercaptopyridine (pMPY) probe molecule. Differences in the relative intensities of the pMPY spectra were monitored for three pairs of enantiomers containing hydroxy (?OH) and/or amino (?NH₂) groups. The N: or N⁺?H functionality of the pMPY‐modified tip participates in hydrogen‐bond interactions with a particular molecular orientation of each chiral isomer. The asymmetric arrangement of silver atoms at the apex of the tip induces an asymmetric electric field, which causes the tip to become a chiral center. Differences in the charge‐transfer (CT) states of the metal‐achiral probe system in conjunction with the asymmetric electric field produce different enhancements in the Raman signals of the two enantiomers. The near‐field effect of the asymmetric electric field, which depends on the number of analyte functional groups capable of hydrogen‐bond formation, improves the degree of discrimination.     

Non‐optical bimorph‐based force sensor for scanning near‐field optical microscopy of biological materials: characteristics,design and applications

A non‐optical force sensor that allows operation both in lateral (shear) and in vertical (tapping) force detection modes has been introduced for dynamic tip–sample distance regulation in scanning near‐field optical microscopy (SNOM) of biological samples. The sensor is based on a rectangular bimorph cantilever consisting of two thin piezoceramic layers bonded to a brass centre shim. One of the piezo layers serves as the probe dither and another as the responder of the sensed forces. The sensor is driven with a home‐made Q‐control electronics so that its sensitivity and bandwidth can be adjusted. The dynamics, characteristics and design considerations of the sensor are theoretically and experimentally discussed. Driving the bimorph cantilever at its eigenfrequency with appropriate force feedback allows one to obtain a quality factor (Q‐factor) up to 10³ in water, suitable for different sample softness and imaging environments. The high sensitivity of the sensor is demonstrated both by shear force and by tapping mode imaging of soft biological samples in their natural state. Near‐field optical resolution of better than 100 nm on red blood cells in water has been obtained. The experimental results suggest that this SNOM sensor would be a promising set‐up for biological applications. Copyright © 2007 John Wiley & Sons, Ltd.     

Imaging Nanometre‐Sized Hot Spots on Smooth Au Films with High‐Resolution Tip‐Enhanced Luminescence and Raman Near‐Field Optical Microscopy

A novel near‐field optical microscope based on a parabolic mirror is used for recording high‐resolution tip‐enhanced photoluminescence (PL) and Raman images with unprecedented sensitivity and contrast. The measurements reveal small islands on the Au surface with dimensions of only a few nanometres with locally enhanced Au PL. These islands appear as nanometre‐sized hot spots in tip‐enhanced Raman microscopy when benzotriazole molecules adsorbed on the Au surface serve as local sensors for the optical field. The spectra show that localized plasmons are the cause of both the locally enhanced Au PL and enhanced Raman scattering. This finding suggests that the dispersive background in the surface‐enhanced Raman spectra can be explained simply by the enhanced Au PL in the gap. Furthermore, our results show that the surface flatness must be better than 1 nm, to provide an optically homogeneous substrate for near‐field enhanced PL and Raman spectroscopy.     

Distinguishing Enantiomers by Tip-Enhanced Raman Scattering: Chemically Modified Silver Tip with an Asymmetric Atomic Arrangement

Discrimination between enantiomers is achieved by tip-enhanced Raman scattering (TERS) using a silver tip that is chemically modified by an achiral para-mercaptopyridine (pMPY) probe molecule. Differences in the relative intensities of the pMPY spectra were monitored for three pairs of enantiomers containing hydroxy (−OH) and/or amino (−NH₂) groups. The N: or N⁺−H functionality of the pMPY-modified tip participates in hydrogen-bond interactions with a particular molecular orientation of each chiral isomer. The asymmetric arrangement of silver atoms at the apex of the tip induces an asymmetric electric field, which causes the tip to become a chiral center. Differences in the charge-transfer (CT) states of the metal-achiral probe system in conjunction with the asymmetric electric field produce different enhancements in the Raman signals of the two enantiomers. The near-field effect of the asymmetric electric field, which depends on the number of analyte functional groups capable of hydrogen-bond formation, improves the degree of discrimination.     

Scanning Near-Field Optical Microscopy and Spectroscopy as a Tool for Chemical Analysis

Research into the nanometer-scale region is currently of relevance in many branches of modern science and engineering, such as in microelectronics, supramolecular chemistry, and in a biological context. A great deal of attention is given to the design of molecular devices, usually towards understanding the function of existing "molecular machines". Central to this task are powerful diagnostic tools capable of recording chemical information with spatial resolution in the nanometer range. While elemental analysis of surfaces with a lateral resolution of a few dozen nanometers is almost routine, analysis of molecular species with a resolution of <1 μm is very difficult. Scanning-tunneling and atomic-force microscopies usually do not give any chemical information. By combining scanning near-field optical microscopy (SNOM)-the "optical member" of the family of scanning-probe microscopies-with optical spectroscopy, it is possible to obtain molecular information from sample areas as little as 50 nm in diameter. In SNOM, a light source is scanned above the object of interest at a distance of a few nanometers. In the optical near field, the illuminated area is not subject to the Abbé diffraction limit, but merely by the size of the illuminating source. High quality SNOM probes can be reproducibly prepared by a chemical-etching method. These etched probes have an optical transmission up to 1000-fold higher than commercial (pulled) SNOM tips and can withstand higher laser power. This last advantage allows not only high resolution optical imaging, but also localized spectroscopic investigations of surfaces and even optical "nanosampling" by pulsed-laser ablation. The ablated material can be transported over a considerable distance, which opens the possibility for its subsequent analysis with a complementary, highly sensitive analytical method, such as mass spectrometry.     

Plasmon hybridization in nanoshells with a nonconcentric core

We apply the plasmon hybridization method to a nanoshell with a nonconcentric (offset) core and investigate how the energy and excitation cross section of the plasmon modes depend on the offset distance D of the inner core from the nanoshell center. A two-center spherical coordinate system is used for mathematical convenience. It is shown that the presence of an offset core shifts the plasmon energies and makes higher multipolar nanoshell plasmons dipole active and visible in the optical spectrum. The dependence of the plasmon shifts on D is weak for small offsets but strong for large offsets. The polarization dependence of the optical absorption spectra is found to be relatively weak. The electromagnetic field enhancements are shown to be much larger than on a concentric nanoshell. The results agree very well with results from finite difference time domain simulations.     

利用AFM和SNOM对淋巴细胞膜表面超微结构及其光学性质的初步研究

利用原子力显微镜(Atomic Force Microscopy，AFM)对淋巴细胞表面形貌进行了形态学的初步研究，观察到了其膜表面其他显微技术所不能发现的超微结构．同时也运用扫描近场光学显微镜(Scanning Near field Optical Microscopy，SNOM)对淋巴细胞进行成像，观察了其对光的透射、吸收等光学性质，并对两种成像方法进行了比较．研究发现：淋巴细胞膜表面凹凸不平，分布着大量直径几十到几百纳米不等的小颗粒；淋巴细胞中央部位有自发荧光现象．结果表明，AFM和SNOM可作为进一步探讨淋巴细胞的结构与功能关系的有力工具．     

Tailoring plasmonic substrates for surface enhanced spectroscopies

Our understanding of how the geometry of metallic nanostructures controls the properties of their surface plasmons, based on plasmon hybridization, is useful for developing high-performance substrates for surface enhanced spectroscopies. In this tutorial review, we outline the design of metallic nanostructures tailored specifically for providing electromagnetic enhancements for surface enhanced Raman scattering (SERS). The concepts developed for nanoshell-based substrates can be generalized to other nanoparticle geometries and scaled to other spectroscopies, such as surface enhanced infrared absorption spectroscopy (SEIRA).     

Fabrication of a Biocompatible Mica/Gold Surface for Tip-Enhanced Raman Spectroscopy

Tip-enhanced Raman spectroscopy (TERS) is a promising technique for structural studies of biological systems and biomolecules, owing to its ability to provide a chemical fingerprint with sub-diffraction-limit spatial resolution. This application of TERS has thus far been limited, due to difficulties in generating high field enhancements while maintaining biocompatibility. The high sensitivity achievable through TERS arises from the excitation of a localized surface plasmon resonance in a noble metal atomic force microscope (AFM) tip, which in combination with a metallic surface can produce huge enhancements in the local optical field. However, metals have poor biocompatibility, potentially introducing difficulties in characterizing native structure and conformation in biomolecules, whereas biocompatible surfaces have weak optical field enhancements. Herein, a novel, biocompatible, highly enhancing surface is designed and fabricated based on few-monolayer mica flakes, mechanically exfoliated on a metal surface. These surfaces allow the formation of coupled plasmon enhancements for TERS imaging, while maintaining the biocompatibility and atomic flatness of the mica surface for high resolution AFM. The capability of these substrates for TERS is confirmed numerically and experimentally. We demonstrate up to five orders of magnitude improvement in TERS signals over conventional mica surfaces, expanding the sensitivity of TERS to a wide range of non-resonant biomolecules with weak Raman cross-sections. The increase in sensitivity obtained through this approach also enables the collection of nanoscale spectra with short integration times, improving hyperspectral mapping for these applications. These mica/metal surfaces therefore have the potential to revolutionize spectromicroscopy of complex, heterogeneous biological systems such as DNA and protein complexes.     

Enhancement of adsorbed dye monolayer fluorescence by a silver nanoparticle overlayer

Deposition of silver nanoparticles directly onto a Rhodamine Red monolayer covalently bound to glass is found to increase the photoluminescence by as much as 20 times depending on excitation wavelength and nanoparticle density. At the same time, the excited state lifetime is reduced by more than a factor of 2, the fluorescence spectrum is blue-shifted, and greater polarization anisotropy in the emission is observed. We attribute these effects to local enhancement of the optical fields near the molecules by interactions with silver plasmons. We approximately separate the relative contributions of increased absorption and increased emissive rate to the observed enhancement of fluorescence. A study of the spatial inhomogeneity of the effect using scanning confocal microscopy demonstrates that average enhancements at least twice as large are possible.     

扫描近场光学显微镜对纳米结构的观察

光学显微镜在人们认识微观世界的过程中一直扮演着非常重要的角色．随着认识的深入，对空间分辨率的要求也越来越高．但是众所周知，普通光学显微镜（远场情况下）的分辨率受光的衍射效应所限制，一般可表达为0．61A／N．A．（约等于A／2，A为照射光的波长，N．A．为数值孔径）     

Protein-ligand binding investigated by a single nanoparticle TERS approach

We report TERS imaging of individual 50 nm, biotin-labeled gold nanoparticles bound to a streptavidin-derivatized glass slide. Individual gold nanoparticles detected by a nanoparticle TERS tip generate Raman enhancements in both the biotin and streptavidin signals. These results indicate that nanoparticles are capable of investigating nanoscale spatial and chemical environments with non-resonant Raman enhancements.