Development and Application of Multiple‐Probe Scanning Probe Microscopes

In the research of advanced materials based on nanoscience and nanotechnology, it is often desirable to measure nanoscale local electrical conductivity at a designated position of a given sample. For this purpose, multiple‐probe scanning probe microscopes (MP‐SPMs), in which two, three or four scanning tunneling microscope (STM) or atomic force microscope (AFM) probes are operated independently, have been developed. Each probe in an MP‐SPM is used not only for observing high‐resolution STM or AFM images but also for forming an electrical contact enabling nanoscale local electrical conductivity measurement. The world's first double‐probe STM (DP‐STM) developed by the authors, which was subsequently modified to a triple‐probe STM (TP‐STM), has been used to measure the conductivities of one‐dimensional metal nanowires and carbon nanotubes and also two‐dimensional molecular films. A quadruple‐probe STM (QP‐STM) has also been developed and used to measure the conductivity of two‐dimensional molecular films without the ambiguity of contact resistance between the probe and sample. Moreover, a quadruple‐probe AFM (QP‐AFM) with four conductive tuning‐fork‐type self‐detection force sensing probes has been developed to measure the conductivity of a nanostructure on an insulating substrate. A general‐purpose computer software to control four probes at the same time has also been developed and used in the operation of the QP‐AFM. These developments and applications of MP‐SPMs are reviewed in this paper.     

Batch fabrication of atomic force microscopy probes with recessed integrated ring microelectrodes at a wafer level

A batch fabrication process at the wafer-level integrating ring microelectrodes into atomic force microscopy (AFM) tips is presented. The fabrication process results in bifunctional scanning probes combining atomic force microscopy with scanning electrochemical microscopy (AFM-SECM) with a ring microelectrode integrated at a defined distance above the apex of the AFM tip. Silicon carbide is used as AFM tip material, resulting in reduced mechanical tip wear for extended usage. The presented approach for the probe fabrication is based on batch processing using standard microfabrication techniques, which provides bifunctional scanning probes at a wafer scale and at low cost. Additional benefits of batch fabrication include the high processing reproducibility, uniformity, and tuning of the physical properties of the cantilever for optimized AFM dynamic mode operation. The performance of batch-fabricated bifunctional probes was demonstrated by simultaneous imaging micropatterned platinum structures at a silicon dioxide substrate in intermittent (dynamic) and contact mode, respectively, and feedback mode SECM. In both, intermittent and contact mode, the bifunctional probes provided reliable correlated electrochemical and topographical data. In addition, simulations of the diffusion-limited steady-state currents at the integrated electrode using finite element methods were performed for characterizing the developed probes.     

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.     

Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM-SECM

We demonstrate a reliable microfabrication process for a combined atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) measurement tool. Integrated cone-shaped sensors with boron doped diamond (BDD) or gold (Au) electrodes were fabricated from commercially available AFM probes. The sensor formation process is based on mature semiconductor processing techniques, including focused ion beam (FIB) machining, and highly selective reactive ion etching (RIE). The fabrication approach preserves the geometry of the original AFM tips resulting in well reproducible nanoscaled sensors. The feasibility and functionality of the fully featured tips are demonstrated by cyclic voltammetry, showing good agreement between the measured and calculated currents of the cone-shaped AFM-SECM electrodes.     

Electrical Scanning Probe Microscopy on Active Organic Electronic Devices

Polymer‐ and small‐molecule‐based organic electronic devices are being developed for applications including electroluminescent displays, transistors, and solar cells due to the promise of low‐cost manufacturing. It has become clear that these materials exhibit nanoscale heterogeneities in their optical and electrical properties that affect device performance, and that this nanoscale structure varies as a function of film processing and device‐fabrication conditions. Thus, there is a need for high‐resolution measurements that directly correlate both electronic and optical properties with local film structure in organic semiconductor films. In this article, we highlight the use of electrical scanning probe microscopy techniques, such as conductive atomic force microscopy (c‐AFM), electrostatic force microscopy (EFM), scanning Kelvin probe microscopy (SKPM), and similar variants to elucidate charge injection/extraction, transport, trapping, and generation/recombination in organic devices. We discuss the use of these tools to probe device structures ranging from light‐emitting diodes (LEDs) and thin‐film transistors (TFT), to light‐emitting electrochemical cells (LECs) and organic photovoltaics.     

用于音叉式原子力显微镜的探针制备

建立了一种电化学腐蚀法钨探针制备系统,通过对电化学腐蚀过程中微弱电流信号的实时检测,实现对腐蚀电路快速通断的自动控制,断电时间0.3 ms。该系统制备出了具有与理想轮廓一致的指数形探针。分析了电解电压、电解液浓度与腐蚀电流的关系,得出腐蚀最佳参数。将石英音叉与钨探针粘接构成原子力显微镜测头,完成了调幅模式下的力曲线测试。实验结果表明:制作的钨探针满足原子力显微镜测头性能要求,音叉信号稳定,能识别10 nm的运动变化,为研制高性能音叉式原子力显微镜提供了实验技术基础。     

One nanometer resolution electrical probe via atomic metal filament formation

Scanning probe microscopy has been widely used to investigate various interactions in microscopic nature. Particularly, conductive atomic force microscopy (C-AFM) can provide local electronic signals conveniently, but the probe resolution of C-AFM has been limited by the tip geometry. Here, we improve the probe resolution greatly by forming an atomic-size metallic filament on a commercial C-AFM tip. We demonstrate ～1 nm lateral resolution in C-AFM using the metal filament tip. The filament tip is mechanically robust and electrically stable in repeated scans under ambient conditions since it is imbedded in a stable insulating matrix. The formation of the atomic filament is highly controllable and reproducible and can be easily integrated to existing AFM tip technologies to produce the next generation of high-resolution electrical and other scanning probes.     

原子力显微镜的双探针接触测量研究

为实现双探针原子力显微镜的探针对准,用探针A对探针B的成像进行了深入的研究。首先对音叉探针进行有限元仿真,分析探针的机械特性。其次用锁相放大器获取探针的幅度和频率信号,让探针接近样品（硅片）以获得系统的分辨率。最后在YOZ平面用探针A对探针B扫描成像,逐步缩小扫描范围并同时减小扫描步进。实验表明,探针的分辨率优于1 nm,双探针对准精度可达5 nm。     

Preventing Nanoscale Wear of Atomic Force Microscopy Tips Through the Use of Monolithic Ultrananocrystalline Diamond Probes

Nanoscale wear is a key limitation of conventional atomic force microscopy (AFM) probes that results in decreased resolution, accuracy, and reproducibility in probe‐based imaging, writing, measurement, and nanomanufacturing applications. Diamond is potentially an ideal probe material due to its unrivaled hardness and stiffness, its low friction and wear, and its chemical inertness. However, the manufacture of monolithic diamond probes with consistently shaped small‐radius tips has not been previously achieved. The first wafer‐level fabrication of monolithic ultrananocrystalline diamond (UNCD) probes with <5‐nm grain sizes and smooth tips with radii of 30–40 nm is reported, which are obtained through a combination of microfabrication and hot‐filament chemical vapor deposition. Their nanoscale wear resistance under contact‐mode scanning conditions is compared with that of conventional silicon nitride (SiN_x) probes of similar geometry at two different relative humidity levels (≈15 and ≈70%). While SiN_x probes exhibit significant wear that further increases with humidity, UNCD probes show little measurable wear. The only significant degradation of the UNCD probes observed in one case is associated with removal of the initial seed layer of the UNCD film. The results show the potential of a new material for AFM probes and demonstrate a systematic approach to studying wear at the nanoscale.     

Local Electrochemical Functionality in Energy Storage Materials and Devices by Scanning Probe Microscopies: Status and Perspectives

Energy storage and conversion systems are an integral component of emerging green technologies, including mobile electronic devices, automotive, and storage components of solar and wind energy economics. Despite the rapidly expanding manufacturing capabilities and wealth of phenomenological information on the macroscopic device behaviors, the microscopic mechanisms underpinning battery and fuel cell operations in the nanometer–micrometer range are virtually unknown. This lack of information is due to the dearth of experimental techniques capable of addressing elementary mechanisms involved in battery operation, including electronic and ion transport, vacancy injection, and interfacial reactions, on the nanometer scale. In this article, a brief overview of scanning probe microscopy (SPM) methods addressing nanoscale electrochemical functionalities is provided and compared with macroscopic electrochemical methods. Future applications of emergent SPM methods, including near field optical, electromechanical, microwave, and thermal probes and combined SPM‐(S)TEM (scanning transmission electron microscopy) methods in energy storage and conversion materials are discussed.     

Ultrasharp and high aspect ratio carbon nanotube atomic force microscopy probes for enhanced surface potential imaging

The resolution of scanning surface potential microscopy (SSPM) is mainly limited by non-local electrostatic interactions due to the finite probe size. Here we present high resolution surface potential imaging with ultrasharp and high aspect ratio carbon nanotube (CNT) atomic force microscopy (AFM) probes fabricated via dielectrophoresis. Enhancement of surface potential contrast by several factors is reported for integrated circuit structures and purple membrane fragments for these CNT AFM probes as compared to conventional probes. In particular, ultrahigh lateral resolution (～2?nm) surface potential images of self-assembled bacteriorhodopsin proteins are reported at ambient conditions, with the implication of label-free protein detection by SSPM techniques.     

Identifying the Genotypes of Hepatitis B Virus (HBV) with DNA Origami Label

The hepatitis B virus (HBV) genotyping may profoundly affect the accurate diagnosis and antiviral treatment of viral hepatitis. Existing genotyping methods such as serological, immunological, or molecular testing are still suffered from substandard specificity and low sensitivity in laboratory or clinical application. In a previous study, a set of high‐efficiency hybridizable DNA origami‐based shape ID probes to target the templates through which genetic variation could be determined in an ultrahigh resolution of atomic force microscopy (AFM) nanomechanical imaging are established. Here, as a further confirmatory research to explore the sensitivity and applicability of this assay, differentially predesigned DNA origami shape ID probes are also developed for precisely HBV genotyping. Through the specific identification of visualized DNA origami nanostructure with clinical HBV DNA samples, the genetic variation information of genotypes can be directly identified under AFM. As a proof‐of‐concept, five genotype B and six genotype C are detected in 11 HBV‐infected patients' blood DNA samples of Han Chinese population in the single‐blinded test. The AFM image‐based DNA origami shape ID genotyping approach shows high specificity and sensitivity, which could be promising for virus infection diagnosis and precision medicine in the future.     

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.     

A combined imaging,microthermal and spectroscopic study of a multilayer packaging system

The effectiveness of a packaging solution for the pharmaceutical and food industry is dependent on the integrity of the constituent layers and the interfaces formed between them. The deconvolution and analysis of the many intimate layers found in packaging is analytically challenging, requiring techniques capable of identifying sub‐micron regions. Here we have characterized the chemical and physical nature of the layers in a multilayer packaging system along with the interfaces, using a combination of high‐resolution atomic force microscopy (AFM), microthermal analysis using scanning thermal microscopy (SThM), and Fourier transform infrared (FT‐IR) spectroscopy. In particular, localized thermal analysis is shown to reveal the thermal transitions of the individual layers, but it was found that care must be exercised when melting through one layer to the next, as this can result in overestimates of melting temperatures of the underlying layer due to excess power loss from the SThM probe to the already molten top layer surrounding the probe. Copyright © 2004 John Wiley & Sons, Ltd.     

Influence of electron irradiation on the electronic transport mechanisms during the conductive AFM imaging of InAs/GaAs quantum dots capped with a thin GaAs layer

We have used conductive atomic force microscopy (C-AFM) to study the electronic transport mechanisms through InAs quantum dots (QDs) grown by molecular beam epitaxy on an n-type GaAs(001) substrate and covered with a 5?nm thick GaAs cap layer. The study is performed with a conductive atomic force microscope working inside a scanning electron microscope. Electric images can be obtained only if the sample is preliminarily irradiated with an electron probe current sufficiently high to generate strong electron beam induced current. In these conditions holes are trapped in QDs and surface states, so allowing the release of the Fermi level pinning and thus conduction through the sample. The electronic transport mechanism depends on the type of AFM probe used; it is explained for a metal (Co/Cr) coated probe and p-doped diamond coated probe with the aid of energy band diagrams. The writing (charge trapping) and erasing (untrapping) phenomena is conditioned by the magnitude of the electron probe current. A strong memory effect is evidenced for the sample studied.     

双探针原子力显微镜针尖对准方法研究

双探针对顶测量可以有效地消除传统原子力显微镜（AFM）的探针形状对关键尺寸（CD）测量的影响。测量前需要将两个探针针尖（A和B）接触到一起作为测量零点,为实现双探针纳米级对准,提出一种渐进式平面扫描方法。首先,通过视觉图像引导两个探针对准到1μm以内。然后,两个探针继续接近,同时探针A在YOZ平面内对探针B扫描成像,并逐步缩小扫描范围和扫描步进,得到其针尖的纳米级坐标（Y_B,Z_B）。最后,将探针A在Y和Z方向分别移动至Y_B和Z_B,在X方向继续接近探针B直至两探针接触。实验证明,该方法可有效地实现双探针对准,且对准精度为10 nm。     

原子力显微镜用于微尺度材料力学性能表征的研究进展

原子力显微镜(AFM)是纳米科学研究的有力工具。从AFM的原理出发,分析了探针与样品之间作用力的计算过程,介绍了确定悬臂弹性常数的几种方法,并综述了AFM在生物材料、薄膜材料、纳米结构、单分子操作和纳米力学实验中的研究进展。     

Plasma-deposited fluorocarbon films: insulation material for microelectrodes and combined atomic force microscopy-scanning electrochemical microscopy probes

Pinhole-free insulation of micro- and nanoelectrodes is the key to successful microelectrochemical experiments performed in vivo or in combination with scanning probe experiments. A novel insulation technique based on fluorocarbon insulation layers deposited from pentafluoroethane (PFE, CF3CHF2) plasmas is presented as a promising electrical insulation approach for microelectrodes and combined atomic force microscopy-scanning electrochemical microscopy (AFM-SECM) probes. The deposition allows reproducible and uniform coating, which is essential for many analytical applications of micro- and nanoelectrodes such as, e.g., in vivo experiments and SECM experiments. Disk-shaped microelectrodes and frame-shaped AFM tip-integrated electrodes have been fabricated by postinsulation focused ion beam (FIB) milling. The thin insulation layer for combined AFM-SECM probes renders this fabrication technique particularly useful for submicro insulation providing radius ratios of the outer insulation versus the disk electrode (RG values) suitable for SECM experiments. Characterization of PFE-insulated AFM-SECM probes will be presented along with combined AFM-SECM approach curves and imaging.     

The manufacturing of a metallic nano-cluster at a tip apex for field-sensitive microscopy applications

Using a conductive atomic force microscopic setup, a metallic nano-cluster at a tip apex was successfully manufactured by an electrochemical redox process from an anodic aluminum oxide template. The diameter of the metallic nano-clusters ranged from 15 nm to 200 nm. The diameters of the nano-clusters could be well-controlled by adjusting the pore size of the templates. The formation of a variety of metallic nano-clusters at the tip apex was accomplished by preparing the electrolyte solution from different metallic salts. The formation mechanism for the nano-cluster is outlined and discussed. Moreover, we were able to enhance the performance of the nano-cluster tips for field-sensitive scanning probe microscopy, including electrostatic force microscopy and scanning Kelvin probe microscopy by laser annealing. Our experimental results indicated that for applications in field-sensitive scanning probe microscopy the stray field effect was significantly suppressed by the nano-cluster tip and hence the spatial resolution was improved.     

The Influence of High Pressure Treatment and Thermal Pasteurization on the Surface of Polymeric Packaging Films

Several common single layer films (PE‐HD, PE‐LD, PP‐BO, PA6‐BO and PET‐BO) and multilayer (PS/PE, PP‐BO/PEpeel and PET‐BO/PE) films were treated by either high pressure (600 MPa) or temperature (80 °C/90 °C) to simulate a high pressure or thermal pasteurization process. The samples were tested by atomic force microscopy (AFM), profile method and surface energy measurements to obtain information about the influence of the treatments on the surface topography and surface energy of the samples and by differential scanning calorimetry and by tensile testing concerning material properties. As key figures arithmetic surface roughness (by AFM at Pulsed Force Mode and profile method), surface energy by surface energy measurement and adhesion between tip and surface by AFM were extracted. Results indicate an influence of both high‐pressure processing and thermal‐processing on the surface roughness of biaxial oriented polymer films as single layer films. Laminated biaxially oriented polymer films showed no changes regardless of which processing was performed. The surface energy was hardly affected by both of the treatments for any stretched, non‐stretched, single or laminated films.