Apertureless near-field scanning Raman microscopy using reflection scattering geometry

The combination of near-field scanning optical microscopy and Raman spectroscopy provides chemical/structural specific information with nanometer spatial resolution, which are critically important for a wide range of applications, including the study of Si devices, nanodevices, quantum dots, single molecules of biological samples. In this paper, we describe our near-field Raman study using apertureless probes. Our system has two important features, critical to practical applications. (1) The near-field Raman enhancement was achieved by Ag coating of the metal probes, without any preparation of the sample, and (2) while all other apertureless near-field Raman systems were constructed in transmission mode, our system works in the reflection mode, making near-field Raman study a reality for any samples. We have obtained the first 1D Raman mapping of a real Si device with 1s exposure time. This is a very significant development in near-field scanning Raman microscopy as it is the first demonstration that this technique can be used for imaging purpose because of the short integration time. In addition, the metal tips used in our set-up can be utilized to make simultaneous AFM and electrical mappings such as resistance and capacitance that are critical parameters for device applications.     

表面增强拉曼光谱的研究进展

本文从提高表面拉曼光谱检测灵敏度和空间分辨率两个方面的发展叙述表面增强拉曼光谱和针尖增强拉曼光谱的原理、方法、特点以及最新进展。对利用表面增强拉曼光谱和针尖增强拉曼光谱研究金属表面上分子吸附等方面的应用进行总结 ,并对他们的应用前景做了预测     

Invited review article: combining scanning probe microscopy with optical spectroscopy for applications in biology and materials science

This is a comprehensive review of the combination of scanning probe microscopy (SPM) with various optical spectroscopies, with a particular focus on Raman spectroscopy. Efforts to combine SPM with optical spectroscopy will be described, and the technical difficulties encountered will be examined. These efforts have so far focused mainly on the development of tip-enhanced Raman spectroscopy, a powerful technique to detect and image chemical signatures with single molecule sensitivity, which will be reviewed. Beyond tip-enhanced Raman spectroscopy and/or topography measurements, combinations of SPM with optical spectroscopy have a great potential in the characterization of structure and quantitative measurements of physical properties, such as mechanical, optical, or electrical properties, in delicate biological samples and nanomaterials. The different approaches to improve the spatial resolution, the chemical sensitivity, and the accuracy of physical properties measurements will be discussed. Applications of such combinations for the characterization of structure, defects, and physical properties in biology and materials science will be reviewed. Due to the versatility of SPM probes for the manipulation and characterization of small and/or delicate samples, this review will mainly focus on the apertureless techniques based on SPM probes.     

Zigzag pattern of Brillouin OF sensor for spatial resolution enhancement

Brillouin optical fiber (OF) sensing technology shows superior potential for structural health monitoring with the advantages of distributed strain and temperature measurement, immunity of electromagnetic interference and so on. However most of current commercial Brillouin OF sensing systems have encountered spatial resolution bottleneck, which cannot deal with local high-precision measurement. A zigzag pattern of Brillouin OF sensor is developed explicitly for spatial resolution enhancement in this paper, and a relative zigzag optical fiber sensor is produced and packaged by fiber reinforced polymer (FRP). Their characteristics are studied by using the strain measurement of one small-size uniform strength beam. From the experiments, the zigzag pattern exhibits excellent performance for strain measurement with high-precision and enhances the spatial resolution to a certain degree without changing the Brillouin sensing instrument’s performance itself.     

A method for reconstructing patterns of somatosensory cerebral cortical activity

An interactive graphics package was developed in order to acquire, display, and manipulate images of cerebral cortical autoradiographic data. The primary purpose for development of the system was to reconstruct accurate 2-dimensional maps of the functional activity within the somatosensory cerebral cortex. A Datacube Q-bus graphics module (QVG/QAF-123) was interfaced with the Micro PDP-11/23 to accept a standard RS170 video input signal, and autoradiographs of serial sections (each 20 microns thick) of a cerebral cortex were digitized individually to 768 X 512 X 8 bit resolution. Input look-up tables were used to standardize the autoradiographic data. Boundaries of the somatosensory cortex were entered (with a Summagraphics MM 1201 digitizer), and the image data was stored on disk file (a method of data compression was devised). A method for segmenting the image data for many (sequential) sections was developed that provided arrays from which the maps were generated. Thresholding, histogram equalization, edge detection and edge enhancement, and filters in both the spatial and frequency domains were employed to process the images of the maps. Plots of optical density values along any axis of the maps and gray level histograms of any map region could also be generated. Maps made by the described method are much higher in resolution than those produced by traditional (manual) methods, and permit analysis of the reconstructions in both the frequency and spatial domains.     

High-resolution microscope for tip-enhanced optical processes in ultrahigh vacuum

An optical microscope based on tip-enhanced optical processes that can be used for studies on adsorbates as well as thin layers and nanostructures is presented. The microscope provides chemical and topographic informations with a resolution of a few nanometers and can be employed in ultrahigh vacuum as well as gas phase. The construction involves a number of improvements compared to conventional instruments. The central idea is to mount, within an UHV system, an optical platform with all necessary optical elements to a rigid frame that also carries the scanning tunneling microscope unit and to integrate a high numerical aperture parabolic mirror between the scanning probe microscope head and the sample. The parabolic mirror serves to focus the incident light and to collect a large fraction of the scattered light. The first experimental results of Raman measurements on silicon samples as well as brilliant cresyl blue layers on single crystalline gold and platinum surfaces in ultrahigh vacuum are presented. For dye adsorbates a Raman enhancement of approximately 10(6) and a net signal gain of up to 4000 was observed. The focus diameter ( approximately lambda2) was measured by Raman imaging the focal region on a Si surface. The requirements of the parabolic mirror in terms of alignment accuracy were experimentally determined as well.     

Scanning differential interference contrast microscope

An optical microscope has been developed based on the differential interference contrast method to evaluate the roughness of supersmooth surfaces. The instrument uses a Bragg cell and a translation stage driven by a DC motor to produce an image of an area of a sample. Its lateral resolution is 2 μm and its vertical resolution is subangstrom. It takes only 7 seconds to scan an area of 1 mm². Three different curve fits can be used to remove the tilt, the curvature, and the low spatial frequency features of the sample. A figure for surface roughness is produced that is repeatable to 0.01 Å. The instrument is described and the noise sources and repeatability are discussed. The results of measurements of ring laser gyroscope mirror substrates are shown.     

A versatile multipurpose scanning probe microscope

A combined scanning probe microscope has been developed that allows simultaneous operation as a non‐contact/tapping mode atomic force microscope, a scattering near‐field optical microscope, and a scanning tunnelling microscope on conductive samples. The instrument is based on a commercial optical microscope. It operates with etched tungsten tips and exploits a tuning fork detection system for tip/sample distance control. The system has been tested on a p‐doped silicon substrate with aluminium depositions, being able to discriminate the two materials by the electrical and optical images with a lateral resolution of 130 nm.     

Secondary ion quadrupole mass spectrometer for depth profiling--design and performance evaluation

A quadrupole-based secondary ion mass spectrometer designed for depth profiling is described which combines ultrahigh vacuum construction with high sputtering rate, detection sensitivity, depth resolution, mass spectral purity, and abundance sensitivity. Impurities such as B and Al implanted in Si can be profiled to levels below one part per million atomic (ppma), at a depth resolution equal to that obtained by commercial ion microprobes. The primary beam consists of 5-keV, mass-analyzed (40)Ar(+) ions, focused to about 70 microm in diameter. Its high current density (>25mA/cm(2)) permits adequate beam rastering and electronic signal-gating to optimize depth resolution. A secondary ion extraction lens and spherical energy filter are responsible for achieving abundance sensitivities of five to six orders of magnitude on the low mass side of a matrix peak. The ultrahigh vacuum environment of the sample dramatically reduces molecular peaks containing H, C, and O, allowing even hydrogen to be profiled to concentrations below 10 ppma. Because large amounts of data are generated by multi-element depth profiling, means for automated instrument control and data acquisition have been developed.     

An optical NMR spectrometer for Larmor-beat detection and high-resolution POWER NMR

Optical nuclear magnetic resonance (ONMR) is a powerful probe of electronic properties in III-V semiconductors. Larmor-beat detection (LBD) is a sensitivity optimized, time-domain NMR version of optical detection based on the Hanle effect. Combining LBD ONMR with the line-narrowing method of POWER (perturbations observed with enhanced resolution) NMR further enables atomically detailed views of local electronic features in III-Vs. POWER NMR spectra display the distribution of resonance shifts or line splittings introduced by a perturbation, such as optical excitation or application of an electric field, that is synchronized with a NMR multiple-pulse time-suspension sequence. Meanwhile, ONMR provides the requisite sensitivity and spatial selectivity to isolate local signals within macroscopic samples. Optical NMR, LBD, and the POWER method each introduce unique demands on instrumentation. Here, we detail the design and implementation of our system, including cryogenic, optical, and radio-frequency components. The result is a flexible, low-cost system with important applications in semiconductor electronics and spin physics. We also demonstrate the performance of our systems with high-resolution ONMR spectra of an epitaxial AlGaAs/GaAs heterojunction. NMR linewidths down to 4.1 Hz full width at half maximum were obtained, a 10(3)-fold resolution enhancement relative any previous optically detected NMR experiment.     

Light emission induced by tunneling electrons from surface nanostructures observed by novel conductive and transparent probes

We have developed an ultrahigh-vacuum low-temperature scanning tunneling microscope (STM) equipped with a near-field optical detection system using novel conductive and optically transparent probes. Tunneling-electron induced photons generated in a nanometer-scale area just under the STM probe can be collected directly into the core of the optical fiber probe within the optical near-field region. Firstly, optical fiber probes coated with indium-tin-oxide thin film are applied to quantitative analysis of p-type GaAs(110) surface, where a decrease of light emission in photon mapping clearly extracts the existence of Zn accepter atoms located at the sub-surface layers. Secondly, in order to enhance the efficiency for inelastic tunneling excitation of a tip-induced plasmon mode, a STM probe coated with an Ag/ITO dual-layer film has been developed and applied to an Ag(111) surface, where photon mapping with a step resolution has been achieved by near-field detection.     

Surface studies in a UHV field emission gun scanning electron microscope

Recent instrumental advances have enabled scanning electron microscopy using a field emission gun (FEG) to be combined with an ultra high vacuum specimen chamber. The resulting instrument, the UHV-FEG-SEM, allows high spatial resolution microstructural and micro-analytic information to be obtained reliably from clean surfaces for the first time. Such an instrument has been installed and developed at the University of Sussex. It incorporates SEM at ～5 nm resolution, scanning Auger microscopy at ～30 nm resolution, and various diffraction techniques, including RHEED and electron backscattering pattern (EBSP) techniques, at (lateral) resolutions which can approach 10 nm. The work function can also be measured microscopically as demonstrated in this paper. Combined with facilities for in situ cleaning and molecular beam deposition, these techniques represent a considerable improvement in our ability to study surface and near-surface phenomena on a microscopic scale. Examples of recent work on technique development, including work-function measurement and backscattering patterns, are described. Recent applications to metal and semiconductor systems are described, including the crystal growth of Ag on Si (111) and Mo (100), the composition profiles of GaAs lasers, and adsorbed Cs layers on tungsten.     

Femtosecond near-field scanning optical microscopy

We have developed an instrument for optically measuring carrier dynamics in thin-film materials with approximately 150 nm lateral resolution, approximately 250 fs temporal resolution and high sensitivity. This is accomplished by combining an ultrafast pump-probe laser spectroscopic technique with a near-field scanning optical microscope. A diffraction-limited pump and near-field probe configuration is used, with a novel detection system that allows for either two-colour or degenerate pump and probe photon energies, permitting greater measurement flexibility than that reported in earlier published work. The capabilities of this instrument are proven through near-field degenerate pump-probe studies of carrier dynamics in GaAs/AIGaAs single quantum well samples locally patterned by focused ion beam (FIB) implantation. We find that lateral carrier diffusion across the nanometre-scale FIB pattern plays a significant role in the decay of the excited carriers within approximately 1 microm of the implanted stripes, an effect which could not have been resolved with a far-field system.     

Imaging and strain analysis of nano-scale SiGe structures by tip-enhanced Raman spectroscopy

The spatial resolution and high sensitivity of tip-enhanced Raman spectroscopy allows the characterization of surface features on a nano-scale. This technique is used to visualize silicon-based structures, which are similar in width to the transistor channels in present leading-edge CMOS devices. The reduction of the intensive far-field background signal is crucial for detecting the weak near-field contributions and requires beside a careful alignment of laser polarization and tip axis also the consideration of the crystalline sample orientation. Despite the chemical identity of the investigated sample surface, the structures can be visualized by the shift of the Raman peak positions due to the patterning induced change of the stress distribution within lines and substrate layer. From the measured peak positions the intrinsic stress within the lines is calculated and compared with results obtained by finite element modeling. The results demonstrate the capability of the tip-enhanced Raman technique for strain analysis on a sub-50 nm scale.     

Note: improving spatial resolution of optical frequency-domain reflectometry against frequency tuning nonlinearity using non-uniform fast Fourier transform

We propose using non-uniform FFT to minimize the degrading effect of frequency tuning nonlinearity of a tunable laser source (TLS) in an optical frequency-domain reflectometry (OFDR) system. We use an auxiliary interferometer to obtain the required instantaneous optical frequency of the TLS and successfully demonstrate 100 times enhancement in spatial resolution of OFDR with only a 20% increase in computation time. The corresponding measurement reflectivity sensitivity is better than -80 dB, sufficient to detect bending induced index changes in an optical fiber.     

Femtosecond near-field scanning optical microscopy

We have developed an instrument for optically measuring carrier dynamics in thin-film materials with ≈150 nm lateral resolution, ≈250 fs temporal resolution and high sensitivity. This is accomplished by combining an ultrafast pump–probe laser spectroscopic technique with a near-field scanning optical microscope. A diffraction-limited pump and near-field probe configuration is used, with a novel detection system that allows for either two-colour or degenerate pump and probe photon energies, permitting greater measurement flexibility than that reported in earlier published work. The capabilities of this instrument are proven through near-field degenerate pump–probe studies of carrier dynamics in GaAs/AlGaAs single quantum well samples locally patterned by focused ion beam (FIB) implantation. We find that lateral carrier diffusion across the nanometre-scale FIB pattern plays a significant role in the decay of the excited carriers within ≈1 μm of the implanted stripes, an effect which could not have been resolved with a far-field system.     

Note: Production of sharp gold tips with high surface quality

We present a simple method to produce sharp gold tips with excellent surface quality based on electrochemical etching with potassium chloride. Radii of curvature lie in the range of 20-40 nm and the surface roughness is measured to less than 0.8?nm. The tips are well suited for field emission, field ion microscopy, and likely for tip-enhanced Raman scattering as well as tip-enhanced near-field imaging.     

Resolution enhancing using cantilevered tip-on-aperture silicon probe in scanning near-field optical microscopy

Scanning near-field optical microscopy (SNOM) achieves a resolution beyond the diffraction limit of conventional optical microscopy systems by utilizing subwavelength aperture probe scanning. A problem associated with SNOM is that the light throughput decreases markedly as the aperture diameter decreases. Apertureless scanning near-field optical microscopes obtain a much better resolution by concentrating the light field near the tip apex. However, a far-field illumination by a focused laser beam generates a large background scattering signal. Both disadvantages are overcome using the tip-on-aperture (TOA) approach, as presented in previous works. In this study, a finite difference time domain analysis of the degree of electromagnetic field enhancement is performed to verify the efficiency of TOA probes. For plasmon enhancement, silver is deposited on commercially available cantilevered SNOM tips with 20nm thicknesses. To form the aperture and TOA in the probes, electron beam-induced deposition and focused ion beam machining were applied at the end of the sharpened tip. The results show that cantilevered TOA probes were highly efficient for improvements of the resolution of optical and topological measurement of nanostructures.     

Near‐field optical microscopy based on microfabricated probes

We demonstrate high resolution imaging with microfabricated, cantilevered probes, consisting of solid quartz tips on silicon levers. The tips are covered by a 60‐nm thick layer of aluminium, which appears to be closed at the apex when investigated by transmission electron microscopy. An instrument specifically built for cantilever probes was used to record images of latex bead projection patterns in transmission as well as single molecule fluorescence. All images were recorded in constant height mode and show optical resolutions down to 32 nm.