Combined scanning electrochemical/optical microscopy with shear force and current feedback

A technique that combines scanning electrochemical microscopy (SECM) and scanning optical microscopy (OM) was developed. Simultaneous scanning electrochemical/optical microscopy (SECM/OM) was performed by a special probe tip, which consists of an optical fiber core for light passage, surrounded by a gold ring electrode, and an outermost electrophoretic insulating sheath, with the tip attached to a tuning fork. To regulate the tip-substrate distance, either the shear force or the SECM tip current was employed as the feedback signal. The application of a quartz crystal tuning fork (32.768 kHz) for sensing shear force allowed simultaneous topographic, along with SECM and optical imaging in a constant-force mode. The capability of this technique was confirmed by obtaining simultaneously, for the first time, topographic, electrochemical, and optical images of an interdigitated array electrode. Current feedback from SECM also provided simultaneous electrochemical and optical images of relatively soft samples, such as a polycarbonate membrane filter and living diatoms in a constant-current mode. This mode should be useful in mapping the biochemical activity of a living cell.     

Patterning and characterization of surfaces with organic and biological molecules by the scanning electrochemical microscope

A novel approach for micropatterning of surfaces with organic and biological microstructures using the scanning electrochemical microscope (SECM) is described. The approach is based on the introduction of the spatial resolution by local deposition of gold particles followed by monolayer formation and functionalization. Specifically, gold patterns were deposited locally on silicon wafers with the SECM as a result of the controlled anodic dissolution of a gold microelectrode. The gold patterns were further used as microsubstrates for assembling cystamine monolayers to which either fluoresceine isothiocyanate (FIT) or glucose oxidase (GOD) were covalently attached. Characterization of the organic monolayers, as well as the biological activity of the enzyme patterns, was carried out by fluorescence microscopy and the SECM, respectively.     

基于纳米运动平台的原子力显微镜开发

采用一种无耦合、三轴精确定位的纳米运动平台作为扫描器,研制了一种新型原子力显微镜(AFM).该AFM有效消除了通常使用的单管式压电陶瓷扫描器扫描过程中运动耦合产生的两种结构误差--交叉耦合误差和扫描范围误差,极大提高了纳米测量及操作的精度.     

Noncontact electrochemical imaging with combined scanning electrochemical atomic force microscopy

Combined scanning electrochemical atomic force microscopy (SECM-AFM) is a recently introduced scanned probe microscopy technique where the probe, which consists of a tip electrode and integrated cantilever, is capable of functioning as both a force sensor, for topographical imaging, and an ultramicroelectrode for electrochemical imaging. To extend the capabilities of the technique, two strategies for noncontact amperometric imaging-in conjunction with contact mode topographical imaging-have been developed for the investigation of solid-liquid interfaces. First, SECM-AFM can be used to image an area of the surface of interest, in contact mode, to deduce the topography. The feedback loop of the AFM is then disengaged and the stepper motor employed to retract the tip a specified distance from the sample, to record a current image over the same area, but with the tip held in a fixed x-y plane above the surface. Second, Lift Mode can be employed, where a line scan of topographical AFM data is first acquired in contact mode, and the line is then rescanned to record SECM current data, with the tip maintained at a constant distance from the target interface, effectively following the contours of the surface. Both approaches are exemplified with SECM feedback and substrate generation-tip collection measurements, with a 10-microm-diameter Pt disk UME serving as a model substrate. The approaches described allow electrochemical images, acquired with the tip above the surface, to be closely correlated with the underlying topography, recorded with the tip in intimate contact with the surface.     

新型大扫描范围原子力显微镜的研究

研制了一种大扫描范围原子力显微镜(AFM)。设计了新的扫描驱动电路,使单幅图像的扫描范围大幅度提高;用步进电机和扫描器配合扫描,得到序列图像,序列图像拼接后获得大范围样品图像。实验结果表明,采用这一方法,在±150V 的电压驱动下,AFM 的扫描范围可增大到10 ìm?1 mm 的量级,同时保持 1 nm 量级的测试分辨力。     

Aptamer based electrochemical sensor system for protein using the generation/collection mode of scanning electrochemical microscope (SECM)

To detect the target molecules, aptamers are currently focused on and the use of aptamers for biosensing is particularly interesting, as aptamers could substitute antibodies in bioanalytical sensing. So this paper describes the novel electrochemical system for protein in sandwich manner by using the aptamers and the scanning electrochemical microscope (SECM). For protein detection, sandwich system is ideal since labeling of the target protein is not necessary. To develop the electrochemical protein sensor system, thrombin was chosen as a target protein since many aptamers for it were already reported and two different aptamers, which recognize different positions of thrombin, were chosen to construct sandwich type sensing system. In order to obtain the electrochemical signal, the glucose oxidase (GOD) used for labeling the detection aptamers since it has large amount of stability in aqueous solution. One aptamer was immobilized onto the gold electrode and the other aptamer for detection was labeled with GOD for generation of the electric signal. Thrombin was detected in sandwich manner with aptamer immobilized onto the gold electrode and the GOD labeled aptamer. The enzymatic signal, generated from glucose addition after the formation of the complex of thrombin, was measured. The generation-collection mode of SECM was used for amperometric H2O2 detection.     

Scanning force microscope as a tool for studying optical surfaces

The scanning force microscope (SFM) is used to study the characteristics of optical surfaces, such as polished and precision-machined surfaces and thin-film structures. Previously unreported images of raised surface scratches and clumpiness on the surface of extremely smooth dielectric films are presented. The characteristics of SFM's that are important in studying optical surfaces are discussed. They include the effects of tip geometry, surface charging, particulate contamination, scanner artifacts, and instrument calibration.     

KDP晶体相变界面微观形貌及大台阶形成的AFM观察

采用原子力显微镜实时和非实时观察了不同过饱和度下KDP晶体(100)面相变界面微观形貌,观察到晶体从生长死区恢复生长的过程;首次得到大台阶形成过程的实时AFM图像,解释了大台阶的形成机理;分析了台阶失稳的原因。结果表明,不同实验条件下,KDP(100)面相变界面均呈现为台阶面。在低过饱和度下,生长台阶来源于螺位错;在较高过饱和度下,层状台阶列来源于二维核。     

Quantitative determination of enzyme activity in single cells by scanning microelectrode coupled with a nitrocellulose film-covered microreactor by means of a scanning electrochemical microscope

An electrochemical method for quantitative determination of enzyme activity in single cells was developed by scanning a microelectrode (ME) over a nitrocellulose film-covered microreactor with micropores by means of a scanning electrochemical microscope (SECM). Peroxidase (PO) in neutrophils was chosen as the model system. The microreactor consisted of a microwell with a solution and a nitrocellulose film with micropores. A single cell perforated by digitonin was injected into the microwell. After the perforated cell was lysed and allowed to dry, physiological buffer saline (PBS) containing hydroquinone (H2Q) and H2O2 as substrates of the enzyme-catalyzed reaction was added in the microwell. The microwell containing the extract of the lysed cell and the enzyme substrates was covered with Parafilm to prevent evaporation. The solution in the microwell was incubated for 20 min. In this case, the released PO from the cell converted H2Q into benzoquinone (BQ). Then, the Parafilm was replaced by a nitrocellulose film with micropores to fabricate the microreactor. The microreactor was placed in an electrochemical cell containing PBS, H2Q, and H2O2. After a 10-microm-radius Au ME was inserted into the electrochemical cell and approached down to the microreactor, the ME was scanned along the central line across the microreactor by means of a SECM. The scan curve with a peak was obtained by detecting BQ that diffused out from the microreactor through the micropores on the nitrocellulose film. PO activity could be quantified on the basis of the peak current on the scan curve using a calibration curve. This method had two obvious advantages: no electrode fouling and no oxygen interference.     

Feedback-independent Pt nanoelectrodes for shear force-based constant-distance mode scanning electrochemical microscopy

A new generation of platinum nanoelectrodes for constant-distance mode scanning electrochemical microscopy (CD-SECM) has been prepared, characterized, and used for high spatial resolution electrochemical measurements and visualization of electrochemically induced concentration gradients in microcavities. The probes have long (1-2 cm), narrow quartz tips that were conically polished and have a Pt nanoelectrode that is slightly offset from center. Because of the size and location of the electrode on the probe, it does not exhibit SECM feedback while approaching the analyzed sample surfaces even to distances within a few hundred nanometers. The probe was positioned near the surface while scanning and performing electrochemical measurements through use of nonoptical shear force control of the tip-to-sample distance. Test structures consisted of cylindrically shaped microcavities that are 50 microm in diameter with three individually addressable electrodes: a gold disk at 8-microm depth, a crescent-shaped gold ring at 4-microm depth along the wall, and a top gold electrode at the rim. Different electrodes within the microcavity were used to reduce and oxidize redox species in 250 microL of a solution of 5 mM hexaamineruthenium(III) chloride and 0.1 M potassium chloride, protected from evaporation by mineral oil, while the SECM tip followed the topography of the structures and monitored the current from the oxidation of [Ru(NH3)6]2+. Electrochemically generated concentration profiles were obtained from these complex test structures that are not possible with any other SECM technology at this time.     

Application of scanning electrochemical microscope in the study of corrosion of metals

Scanning electrochemical microscope (SECM) has become a very useful and powerful technique for probing a variety of electrochemical reactions in corrosion process due to its high spatial resolution and electrochemical sensitivity to characterize the topography and redox activities of the metal/electrolyte solution interface. Its capability for the direct identification of chemical species in localized corrosion processes with high spatial resolution would be more advantageous compared to other local probe techniques with only morphological characterization. In this review, the applications of the SECM in the study of early stages of localized corrosion, electroactive defect sites in passive films, local initiation of pits, degradation of coating properties on steels, and some combined methods through SECM integrated with other techniques have been summarized and commented. Finally, the optimization for SECM’s experiment design and operation as well as foreseeable application range has been proposed.     

Topographical and chemical microanalysis of surfaces with a scanning probe microscope and laser-induced breakdown spectroscopy

Spatially resolved chemical imaging is achieved by combining a fiber-optic scanning probe microscope with laser-induced breakdown spectroscopy in a single instrument, TOPOLIBS. Elemental composition of surfaces can be mapped and correlated with topographical data. The experiment is conducted in air with minimal sample preparation. In a typical experiment, surface topography is analyzed by scanning a sharp fiber-optic probe across the sample using shear force feedback. The probe is then positioned over a feature of interest and pulsed radiation is delivered to the surface using a nitrogen laser. The pulse vaporizes material from the surface and generates a localized plasma plume. Optical emission from the plume is analyzed with a compact UV/visible spectrometer. Ablation crater size is controlled by the amount of laser power coupled into the probe. Sampling areas with submicrometer dimensions are achieved by using reduced laser power.     

Correlation between optical and topographical images from an external reflection near-field microscope with shear force feedback

An external reflection scanning near-field optical microscope with shear force regulation of the tip-surface distance is described. Near-field optical and shear force topographical images are compared for various samples. It is shown that the most important correlative relationships between these images can be deduced from symmetry considerations. The possibility of extracting additional information from the optical images is demonstrated on images of human blood cells.     

Topographic measurements of supersmooth dielectric films made with a mechanical profiler and a scanning force microscope

The roughnesses of five supersmooth dielectric films of Si(3)N(4), TiO(2), HfO(2), Ta(2)O(5), and Al(2)O(3) prepared by an ion-beam-sputtering technique were measured with a commercial Talystep mechanical profiler and a sensitive Leica WYKO SPM30 scanning force microscope (SFM) to determine how much roughness the films added to the ～1-?-rms roughness fused-silica substrates on which they were deposited. In all cases the increase in roughness for the three-quarter-wave optical thickness films was a small fraction of an angstrom. SFM measurements showed that the topography of the Ta(2)O(5) and Al(2)O(3) films was less random than that of the other film materials and the substrates.     

Near-field scanning microscope with carbon nanotube probe

A source of local electromagnetic field is created and the conditions of localization of the region of donor-acceptor interaction are optimized so as to implement the Förster type energy transfer that determines the spatial and frequency resolution of a near-field scanning microscope employing a carbon nanotube as the probe.