Tip-enhanced Raman mapping with top-illumination AFM

Tip-enhanced Raman mapping is a powerful, emerging technique that offers rich chemical information and high spatial resolution. Currently, most of the successes in tip-enhanced Raman scattering (TERS) measurements are based on the inverted configuration where tips and laser are approaching the sample from opposite sides. This results in the limitation of measurement for transparent samples only. Several approaches have been developed to obtain tip-enhanced Raman mapping in reflection mode, many of which involve certain customisations of the system. We have demonstrated in this work that it is also possible to obtain TERS nano-images using an upright microscope (top-illumination) with a gold-coated Si atomic force microscope (AFM) cantilever without significant modification to the existing integrated AFM/Raman system. A TERS image of a single-walled carbon nanotube has been achieved with a spatial resolution of ～ 20-50?nm, demonstrating the potential of this technique for studying non-transparent nanoscale materials.     

Nanoscale chemical imaging using top-illumination tip-enhanced Raman spectroscopy

We present a new top-illumination scheme for tip-enhanced Raman spectroscopy (TERS) in a gap-mode configuration with illumination and detection in a straightforward fashion perpendicular to the sample surface. This illumination focuses the light tightly around the tip end, which effectively diminishes far-field background contributions during TERS measurements. The setup maintains the entire functionality range of both the scanning probe microscopy and the confocal optical microscopy of the setup. For the first time, we show large (64 × 64 up to 200 × 200 pixels), high-resolution TERS imaging with full spectral information at every pixel, which is necessary for the chemical identification of sample constituents. With a scanning tunneling microscope tip and feedback, these TERS maps can be recorded with a resolution better than 15 nm (most likely even less, as discussed with Figure 6). An excellent enhancement (～10(7)×, sufficient for detection of few molecules) allows short acquisition times (<1 s/pixel) and reasonably low laser power (in the microwatt regime) yielding spectroscopic images with high pixel numbers in reasonable time (128 × 128 pixels in <25 min). To the best of our knowledge, no Raman maps with similar pixel numbers and full spectral information have ever been published.     

The SERS and TERS effects obtained by gold droplets on top of Si nanowires

We show that hemispherical gold droplets on top of silicon nanowires when grown by the vapor-liquid-solid (VLS) mechanism, can produce a significant enhancement of Raman scattered signals. Signal enhancement for a few or even just single gold droplets is demonstrated by analyzing the enhanced Raman signature of malachite green molecules. For this experiment, trenches (approximately 800 nm wide) were etched in a silicon-on-insulator (SOI) wafer along <110> crystallographic directions that constitute sidewalls ({110} surfaces) suitable for the growth of silicon nanowires in <111> directions with the intention that the gold droplets on the silicon nanowires can meet somewhere in the trench when growth time is carefully selected. Another way to realize gold nanostructures in close vicinity is to attach a silicon nanowire with a gold droplet onto an atomic force microscopy (AFM) tip and to bring this tip toward another gold-coated AFM tip where malachite green molecules were deposited prior to the measurements. In both experiments, signal enhancement of characteristic Raman bands of malachite green molecules was observed. This indicates that silicon nanowires with gold droplets atop can act as efficient probes for tip-enhanced Raman spectroscopy (TERS). In our article, we show that a nanowire TERS probe can be fabricated by welding nanowires with gold droplets to AFM tips in a scanning electron microscope (SEM). TERS tips made from nanowires could improve the spatial resolution of Raman spectroscopy so that measurements on the nanometer scale are possible.     

Enhancement of Raman signals with silver-coated tips

Silver coated SiN and SiO(2) tips have been fabricated for use with a bottom-illumination tip-enhanced Raman spectroscopy (TERS) setup with a 488 nm laser excitation. SiN tips with 50-60 nm of deposited Ag give the best TERS enhancements for brilliant cresyl blue test analyte spin-coated on a glass slide. Ag nanoparticles on SiN or SiO(2) rather than Si tips are better for TERS because of the proximity of the wavelengths of their surface plasmon resonance to 488 nm. Adjustments of tilt angle of the metallized tip with respect to the surface plane is shown to considerably raise the intensities of the TERS signals, even from tips that initially appear to be rather non-enhancing. This work helps to enable the more frequent use of the 488 nm laser for nanoscale chemical analysis with both TERS and fluorescence imaging in the same setup.     

Light depolarization induced by metallic tips in apertureless near-field optical microscopy and tip-enhanced Raman spectroscopy

We have investigated the depolarization effects of light scattered by sharp tips used for apertureless near-field optical microscopy. Dielectric and metal coated tips have been investigated and depolarization factors between 5 and 30% have been measured, changing as a function of the incident light polarization and of the tip shape. The experimental results are in good agreement with theoretical calculations performed by the finite element method, giving a near-field depolarization factor close to 10%. The effect of depolarization has been investigated in polarized tip-enhanced Raman spectroscopy (TERS) experiments; the depolarization gives rise to forbidden Raman modes in Si crystals.     

Nanoscale uniaxial pressure effect of a carbon nanotube bundle on tip-enhanced near-field Raman spectra

In situ measurement of tip-enhanced near-field Raman spectra of an isolated single-wall carbon nanotube (SWNT) bundle has been demonstrated by applying a uniaxial pressure up to approximately 2 GPa to the bundle via a metal-coated atomic force microscope tip. We investigated the pressure dependences of Raman frequencies and the intensity of the radial breathing mode bands, the D-band and the G-band, which were related to deformation of SWNTs caused by the tip pressure.     

Novel ultrananocrystalline diamond probes for high-resolution low-wear nanolithographic techniques

A hard, low-wear probe for contact-mode writing techniques, such as dip-pen nanolithography (DPN), was fabricated using ultrananocrystalline diamond (UNCD). Molding within anisotropically etched and oxidized pyramidal pits in silicon was used to obtain diamond tips with radii down to 30 nm through growth of UNCD films followed by selective etching of the silicon template substrate. The probes were monolithically integrated with diamond cantilevers and subsequently integrated into a chip body obtained by metal electroforming. The probes were characterized in terms of their mechanical properties, wear, and atomic force microscopy imaging capabilities. The developed probes performed exceptionally well in DPN molecular writing/imaging mode. Furthermore, the integration of UNCD films with appropriate substrates and the use of directed microfabrication techniques are particularly suitable for fabrication of one- and two-dimensional arrays of probes that can be used for massive parallel fabrication of nanostructures by the DPN method.     

Simultaneous spectroscopic and topographic near-field imaging of TiO2 single surface states and interfacial electronic coupling

We have probed single surface states and the involved interfacial charge transfer coupling on the TiO(2) surface using confocal as well as tip-enhanced near-field topographic-spectroscopic imaging analysis on a niobium-doped rutile TiO(2)(110) surface. The confocal images excited with a radially polarized donut mode render ring-shaped excitation patterns typical for quantum systems with two perpendicular transition dipole moments. The tip-enhanced near-field optical images of single surface states are visualized by the strong exciton plasmon-polariton coupling localized at the subdomain boundaries with a spatial resolution of ～15 nm (far beyond the optical diffraction limit). We suggest that the abundant surface states in the doped TiO(2) generate excitons under laser excitation which are strongly coupled to the surface plasmon-polaritons of the Au tip. Moreover, the interfacial electronic molecule-substrate coupling has been characterized by probing the molecule-perturbed surface states distribution and the associated specific Raman vibrational modes. The imaging and characterization of the surface states and their distributions on TiO(2) surfaces at nanoscale are critically relevant to a deep understanding of interfacial electron transfer dynamics and energetics involving in solar energy conversion, photocatalysis, and mechanistic understanding of surface-enhanced Raman scattering spectroscopy.     

Diamond-modified AFM probes: from diamond nanowires to atomic force microscopy-integrated boron-doped diamond electrodes

In atomic force microscopy (AFM), sharp and wear-resistant tips are a critical issue. Regarding scanning electrochemical microscopy (SECM), electrodes are required to be mechanically and chemically stable. Diamond is the perfect candidate for both AFM probes as well as for electrode materials if doped, due to diamond's unrivaled mechanical, chemical, and electrochemical properties. In this study, standard AFM tips were overgrown with typically 300 nm thick nanocrystalline diamond (NCD) layers and modified to obtain ultra sharp diamond nanowire-based AFM probes and probes that were used for combined AFM-SECM measurements based on integrated boron-doped conductive diamond electrodes. Analysis of the resonance properties of the diamond overgrown AFM cantilevers showed increasing resonance frequencies with increasing diamond coating thicknesses (i.e., from 160 to 260 kHz). The measured data were compared to performed simulations and show excellent correlation. A strong enhancement of the quality factor upon overgrowth was also observed (120 to 710). AFM tips with integrated diamond nanowires are shown to have apex radii as small as 5 nm and where fabricated by selectively etching diamond in a plasma etching process using self-organized metal nanomasks. These scanning tips showed superior imaging performance as compared to standard Si-tips or commercially available diamond-coated tips. The high imaging resolution and low tip wear are demonstrated using tapping and contact mode AFM measurements by imaging ultra hard substrates and DNA. Furthermore, AFM probes were coated with conductive boron-doped and insulating diamond layers to achieve bifunctional AFM-SECM probes. For this, focused ion beam (FIB) technology was used to expose the boron-doped diamond as a recessed electrode near the apex of the scanning tip. Such a modified probe was used to perform proof-of-concept AFM-SECM measurements. The results show that high-quality diamond probes can be fabricated, which are suitable for probing, manipulating, sculpting, and sensing at single digit nanoscale.     

Coaxial atomic force microscope probes for imaging with dielectrophoresis

We demonstrate atomic force microscope (AFM) imaging using dielectrophoresis (DEP) with coaxial probes. DEP provides force contrast allowing coaxial probes to image with enhanced spatial resolution. We model a coaxial probe as an electric dipole to provide analytic formulas for DEP between a dipole, dielectric spheres, and a dielectric substrate. AFM images taken of dielectric spheres with and without an applied electric field show the disappearance of artifacts when imaging with DEP. Quantitative agreement between our model and experiment shows that we are imaging with DEP.     

Fabrication and buckling dynamics of nanoneedle AFM probes

A new method for the fabrication of high-aspect-ratio probes by electron beam induced deposition is described. This technique allows the fabrication of cylindrical 'nanoneedle' structures on the atomic force microscope (AFM) probe tip which can be used for accurate imaging of surfaces with high steep features. Scanning electron microscope (SEM) imaging showed that needles with diameters in the range of 18-100?nm could be obtained by this technique. The needles were shown to undergo buckling deformation under large tip-sample forces. The deformation was observed to recover elastically under vertical deformations of up to ～ 60% of the needle length, preventing damage to the needle. A technique of stabilizing the needle against buckling by coating it with additional electron beam deposited carbon was also investigated; it was shown that coated needles of 75?nm or greater total diameter did not buckle even under tip-sample forces of ～ 1.5?μN.     

适用于TERS系统的金修饰钨丝探针制备和研究

提出了一种适用于针尖增强拉曼光谱(TERS)系统的金修饰钨丝探针,研究了其制备方法。有限元仿真设计了针尖的形状为内弧形针尖,并进行二氧化硅粘结层和金颗粒外层双镀膜结构纳米修饰;通过调节实验室自主研制的电化学腐蚀探针装置的溶液浓度、电机位移和浸入深度制备符合形状要求的钨丝针尖;在此基础上,通过电感耦合等离子体化学气相沉积技术(ICP-CVD)进行二氧化硅涂层镀制,电子束加热物理气象沉积技术(EB-PVD)进行金涂层镀制。最终完成该探针制备,双层镀膜后针尖曲率半径达30~80nm,可用于TERS研究。     

Calibration of Coercive and Stray Fields of Commercial Magnetic Force Microscope Probes

Variable-field magnetic force microscope (MFM) is introduced to characterize the magnetic behavior of commercially available MFM probes that is relevant to interpret MFM imaging. A Nanotec Electronica S.L. microscope has been conveniently modified to apply magnetic fields in axial direction (up to 1.5 kOe) and in-plane direction (up to 2.0 kOe). Axial and transeverse hysteresis loops of the probes have been generated by measuring the changes in the MFM contrast observed when the magnetic field is applied. The variation of the MFM signal is ascribed to the modification of the magnetic state of the tips. This is enabled by the large coercitivity (~1.7 kOe) of the checked longitudinal recording media. The properties of the probes depend on the coating material, the macroscopic tip shape, and tip radius. In only a few cases, the magnetization of the probe can be oriented along in-plane orientation. In addition, the stray field of the tips has been deduced by measuring the influence of the probe in the magnetic state of the checked samples.     

Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy

Heterogeneous catalysts play a pivotal role in the chemical industry, but acquiring molecular insights into functioning catalysts remains a significant challenge. Recent advances in micro-spectroscopic approaches have allowed spatiotemporal information to be obtained on the dynamics of single active sites and the diffusion of single molecules. However, these methods lack nanometre-scale spatial resolution and/or require the use of fluorescent labels. Here, we show that time-resolved tip-enhanced Raman spectroscopy can monitor photocatalytic reactions at the nanoscale. We use a silver-coated atomic force microscope tip to both enhance the Raman signal and to act as the catalyst. The tip is placed in contact with a self-assembled monolayer of p-nitrothiophenol molecules adsorbed on gold nanoplates. A photocatalytic reduction process is induced at the apex of the tip with green laser light, while red laser light is used to monitor the transformation process during the reaction. This dual-wavelength approach can also be used to observe other molecular effects such as monolayer diffusion.     

Nanowire probes for high resolution combined scanning electrochemical microscopy - atomic force microscopy

We describe a method for the production of nanoelectrodes at the apex of atomic force microscopy (AFM) probes. The nanoelectrodes are formed from single-walled carbon nanotube AFM tips which act as the template for the formation of nanowire tips through sputter coating with metal. Subsequent deposition of a conformal insulating coating, and cutting of the probe end, yields a disk-shaped nanoelectrode at the AFM tip apex whose diameter is defined by the amount of metal deposited. We demonstrate that these probes are capable of high-resolution combined electrochemical and topographical imaging. The flexibility of this approach will allow the fabrication of nanoelectrodes of controllable size and composition, enabling the study of electrochemical activity at the nanoscale.     

Scanning probe microscope lithography at the micro- and nano-scales

Scanning probe microscopy (SPM)-based lithography at the micro- and nano-scales is presented. Our method in SPM local oxidation involves two SPM tips, one having a robust blunt tip, a "micrometer tip," and the other having a sharp tip, a "nanometer tip." In tapping-mode SPM local oxidation experiments, Si oxide wires with sub-10 nm resolution were produced by precisely tuning the dynamic properties of the nanometer tip such as drive amplitude and quality factor. On the other hand, in order to perform large-scale oxidation, SPM tip with a contact area of microm2, which is about 10(4) times larger than that of the conventional nanometer tip, was prepared. We propose and demonstrate a method of performing micrometer-scale SPM local oxidation using the micrometer tip under contact-mode operation. The width of the Si oxide produced was clearly determined by the contact length of the tip. Furthermore, we explore the possibility of performing the sub-20 nm lithography of Si surfaces using SPM scratching with a diamond-coated tip. The influence of various scan parameters on the groove size was investigated. The groove size could be precisely controlled by the applied force, scan direction, and the number of scan cycles. There is no effect of the scan speed on the groove size. It is concluded that high-speed nanolithography can be achieved without the degradation of patterns by SPM scratching. SPM-based lithography has the advantage of being able to fabricate a desired structure at an arbitrary position on a surface and plays an important role for bridging the gap between micro- and nano-scales.     

High-speed AFM of human chromosomes in liquid

Further developments of the previously reported high-speed contact-mode AFM are described. The technique is applied to the imaging of human chromosomes at video rate both in air and in water. These are the largest structures to have been imaged with high-speed AFM and the first imaging in liquid to be reported. A possible mechanism that allows such high-speed contact-mode imaging without significant damage to the sample is discussed in the context of the velocity dependence of the measured lateral force on the AFM tip.     

Two-photon photopolymerized tips for adhesion-free scanning-probe microscopy

A hydrophobic polymeric tip of atomic force microscopy has been fabricated by two-photon adsorbed photopolymerization methods (TPAP). The fabrication was performed by a layer-by-layer polymerization of sliced multiple three-dimensional computer-aided design data. The used base resin was composed of acrylate and epoxy, which showed hydrophobic properties after the photopolymerization. For the sharp tip fabrication, we used a "dynamic partial polymerization method" which applied "the threshold effect" of TPAP to maximize the fabrication resolution. To investigate the performance of the fabricated polymeric tip, we have imaged several organic, inorganic, and biological samples using contact or dynamic force mode. The imaging results showed the hydrophobic polymeric tips solved various problems related to the tip adhesion to hydrophilic sample surfaces. Finally, the topographic image resolution of sub-5 nm was obtained using the polymeric tips for the hydrophilic mica surface.     

Turn on Nanolight in a Tiny Gap

A new low-temperature scanning tunneling microscopy technique with laser optics allows for optical excitation and spectroscopy at the level of a single atom or molecule. Shape and material of the microscope's tip prove essential for these investigations; thus, the tip is produced with nanoscale precision by Focused Ion-Beam milling. The localized surface plasmon properties of the tips are engineered by altering the tip structures providing spectral tunability. Local optical excitation is performed by a wavelength-tunable laser source. This tip-enhanced resonance Raman spectroscopy provides a new approach for the atomic-scale optical characterization of local electron-phonon coupling and could ultimately lead to new nanoscale optoelectronic devices with exceptional high sensitivity and efficiency.     

Plastic tip arrays for force spectroscopy

The mechanical stability and viability of molecules investigated with the atomic force microscope (AFM) continue to be limiting factors in the duration of force spectroscopy measurements. In an effort to circumvent this problem, we have fabricated an all-plastic array of over 30 000 tips with dimensions similar to common AFM probes using silicon micromolding techniques. This approach enables rapid fabrication of tip arrays with improved properties, as compared to tip arrays made entirely of silicon.