Multifunctional Boron‐Doped Diamond Colloidal AFM Probes

Scanning probe microscopy techniques providing information on conductivity, chemical fluxes, and interfacial reactivity synchronized with topographical information have gained importance within the last decades. Herein, a novel colloidal atomic force microscopy (AFM) probe is presented using a spherical boron‐doped diamond (BDD) electrode attached and electrically connected to a modified silicon nitride cantilever. These conductive spherical BDD–AFM probes allow for electrochemical force spectroscopy. The physical robustness of these bifunctional probes, and the excellent electrochemical properties of BDD renders this concept a unique multifunctional tool for a wide variety of scanning probe studies including conductive AFM, hybrid atomic force–scanning electrochemical microscopy, and tip‐integrated chem/bio sensing.     

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.     

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.     

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.     

Integrating an ultramicroelectrode in an AFM cantilever: combined technology for enhanced information

We present a novel approach to develop and process a microelectrode integrated in a standard AFM tip. The presented fabrication process allows the integration of an electroactive area at an exactly defined distance above of the end of a scanning probe tip and the subsequent remodeling and sharpening of the original AFM tip using a focused ion beam (FIB) technique (See ref 1 for patent information). Thus, the functionality of scanning electrochemical microscopy (SECM) can be integrated into any standard atomic force microscope (AFM). With the demonstrated approach, a precisely defined and constant distance between the microelectrode and the sample surface can be obtained, alternatively to the indirect determination of this distance usually applied in SECM experiments. Hence, a complete separation of the topographical information and the electrochemical signal is possible. The presented technique is a significant step toward electrochemical imaging with submicrometer electrodes as demonstrated by the development of the first integrated frame submicroelectrode.     

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.     

Fabrication and characterization of a silicon cantilever probe with an integrated quartz-glass (fused-silica) tip for scanning near-field optical microscopy

A cantilever-based probe is introduced for use in scanning near-field optical microscopy (SNOM) combined with scanning atomic-force microscopy (AFM). The probes consist of silicon cantilevers with integrated 25-mum-high fused-silica tips. The probes are batch fabricated by microfabrication technology. Transmission electron microscopy reveals that the transparent quartz tips are completely covered with an opaque aluminum layer before the SNOM measurement. Static and dynamic AFM imaging was performed. SNOM imaging in transmission mode of single fluorescent molecules shows an optical resolution better than 32 nm.     

Frequency dependence of the electrochemical activity contrast in AC-scanning electrochemical microscopy and atomic force microscopy-AC-scanning electrochemical microscopy imaging

Alternating current mode scanning electrochemical microscopy (AC-SECM) enables local detection of electrochemical surface activity without any redox mediator present in solution. Z-approach curves toward the substrate result in a negative feedback curve of the ac signal for insulating samples. On conducting samples, however, the shape of the feedback curve was found to be dependent on the ac perturbation frequency. Approach curves over a wide range of frequencies were performed, and the results were applied to interpret laterally resolved frequency-dependent measurements obtained with combined atomic force microscopy-AC-SECM (AFM-AC-SECM). For the first time, this frequency dependence of the signal was utilized to fine-tune the electrochemical contrast in lateral imaging in AC-SECM. An array of gold microelectrodes embedded in silicon nitride displaying significant changes in electrochemical activity as well as in topography was investigated using a bifunctional AFM-SECM tip with an integrated recessed ring microelectrode. Due to the unique geometrical conditions the electrochemical contrast between the conducting gold spots and the insulating SixNy is reversed, crosses zero, and inverts as a function of the applied ac frequency.     

Scanning electrochemical microscopy. 55. Fabrication and characterization of micropipet probes

The fabrication and characterization of novel micropipet probes for use in scanning electrochemical microscopy (SECM) are described. These can be used to dispense small (pL) amounts of a solution while monitoring the electrochemical response at a substrate and at a ring electrode tip on the micropipet probe. The probes were constructed by insulating gold-coated borosilicate micropipets with electrophoretic paint and exposing a ring electrode at the tip by heat treatment. Characterization of the probes was performed using scanning electron microscopy, cyclic voltammetry, and SECM approach curve experiments. Routine construction of tips with diameters of the order of 3 microm was possible using this technique. The probes exhibited stable steady-state currents and positive and negative feedback approach curves that agreed with those predicted by theory. Demonstrative SECM imaging experiments were performed using a picodispenser to continuously dispense an electroactive solution (ferrocenemethanol) to the SECM cell while the probe was located within a few micrometers of a Pt substrate surface. Oxidation of the dispensed electroactive solution was performed at the substrate, and feedback currents were measured at the probe tip by holding the gold ring at a reducing potential. This mode of tip-dispensing SECM was used to obtain images of a platinum substrate electrode while monitoring both the substrate current and the feedback current at the probe.     

Multifunctional probe array for nano patterning and imaging

This letter reports the design, fabrication, and testing of a multifunctional scanning probe array for nanoscale imaging and patterning. The probe array consists of multiple cantilever probes, with each probe being able to perform a dedicated function such as scanning probe lithography (e.g., dip pen nanolithography and scanning probe contact printing) or scanning probe microscopy (e.g., atomic force microscopy and lateral force microscopy). The bending states of each probe can be controlled by using an integrated thermal electric actuator so that it is possible to engage any individual probe(s) independently for writing or imaging purposes. The multifunctional probe array is therefore capable of performing a rich variety of operations with minimal chemical crosstalk and high registration accuracy. It will eliminate the need for probe chip exchanges and increase the operational efficiency. The probe tips in a given array may be made of different materials. Further, the tip and cantilever may be made of different materials for a given probe. In this work, we focus on the development of a probe array consisting of dip pen nanolithography probes, scanning probe contact printing probes (of various tip sizes), and scanning probe microscopy probes.     

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.     

Elastic property of vertically aligned nanowires

An atomic force microscopy (AFM) based technique is demonstrated for measuring the elastic modulus of individual nanowires/nanotubes aligned on a solid substrate without destructing or manipulating the sample. By simultaneously acquiring the topography and lateral force image of the aligned nanowires in the AFM contacting mode, the elastic modulus of the individual nanowires in the image has been derived. The measurement is based on quantifying the lateral force required to induce the maximal deflection of the nanowire where the AFM tip was scanning over the surface in contact mode. For the [0001] ZnO nanowires/nanorods grown on a sapphire surface with an average diameter of 45 nm, the elastic modulus is measured to be 29 +/- 8 GPa.     

Characterization of batch-microfabricated scanning electrochemical-atomic force microscopy probes

A procedure for the batch microfabrication of scanning electrochemical-atomic force microscopy (SECM-AFM) probes is described. The process yields sharp AFM tips, incorporating a triangular-shaped electrode (base width 1 microm, height 0.65 microm) at the apex. Microfabrication was typically carried out on (1)/(4) 3-in. wafers, yielding 60 probes in each run. The measured spring constant of the probes was in the range 1-1.5 N m(-1). To date, processing has been carried out twice successfully, with an estimated success rate for the fabrication process in excess of 80%, based on field emission-scanning electron microscopy imaging of all probes and current-voltage measurements on a random selection of approximately 30 probes. Steady-state voltammetric measurements for the reduction of Ru(NH(3))(6)(3+) in aqueous solution indicate that the electrode response is well-defined, reproducible, and quantitative, based on a comparison of the experimental diffusion-limited current with finite element simulations of the corresponding mass transport (diffusion) problem. Topographical imaging of a sputtered Au film with the SECM-AFM probes demonstrates lateral resolution comparable to that of conventional Si(3)N(4) AFM probes. Combined electrochemical-topographical imaging studies have been carried out on two model substrates: a 10-microm-diameter disk ultramicroelectrode (UME) and an array of 1-microm-diameter UMEs, spaced 12.5 microm apart (center to center). In both cases, an SECM-AFM probe was first employed to image the topography of the substrates. The tip was then moved back a defined distance from the surface and use to detect Ru(NH(3))(6)(2+) produced at the substrate, biased at a potential to reduce Ru(NH(3))(6)(3+), present in bulk solution, at a diffusion-controlled rate (substrate generation-tip collection mode). These studies establish the success of the batch process for the mass microfabrication of SECM-AFM tips.     

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.     

Mechanism and development of dip-pen nanolithography (DPN)

Dip-Pen Nanolithography is a new scanning probe lithography (SPL) technique based on atomic force microscopy (AFM), and now has made a great progress. The process of dip pen lithography involves the adsorption of ink molecules on AFM tip, the formation of water meniscus, the transport of ink molecules, and diffusion of ink molecules on the substrate. More factors such as temperature, humidity, tip, scanning speed and so on will influence the process of dip pen lithography. The paper analyzed in detail the mechanism of this technique, introduced synthetically the latest development, including Electrochemical DPN, more –mode DPN, multiple DPN, multi-probe array DPN and so on. Finally, the paper described the characteristics and the application of DPN.     

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.     

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.     

A quadruple-scanning-probe force microscope for electrical property measurements of microscopic materials

Four-terminal electrical measurement is realized on a microscopic structure in air, without a lithographic process, using a home-built quadruple-scanning-probe force microscope (QSPFM). The QSPFM has four probes whose positions are individually controlled by obtaining images of a sample in the manner of atomic force microscopy (AFM), and uses the probes as contacting electrodes for electrical measurements. A specially arranged tuning fork probe (TFP) is used as a self-detection force sensor to operate each probe in a frequency modulation AFM mode, resulting in simultaneous imaging of the same microscopic feature on an insulator using the four TFPs. Four-terminal electrical measurement is then demonstrated in air by placing each probe electrode in contact with a graphene flake exfoliated on a silicon dioxide film, and the sheet resistance of the flake is measured by the van der Pauw method. The present work shows that the QSPFM has the potential to measure the intrinsic electrical properties of a wide range of microscopic materials in situ without electrode fabrication.     

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.     

Mechanochemistry: targeted delivery of single molecules

The use of scanning probe microscopy-based techniques to manipulate single molecules and deliver them in a precisely controlled manner to a specific target represents a significant nanotechnological challenge. The ultimate physical limit in the design and fabrication of organic surfaces can be reached using this approach. Here we show that the atomic force microscope (AFM), which has been used extensively to investigate the stretching of individual molecules, can deliver and immobilize single molecules, one at a time, on a surface. Reactive polymer molecules, attached at one end to an AFM tip, are brought into contact with a modified silicon substrate to which they become linked by a chemical reaction. When the AFM tip is pulled away from the surface, the resulting mechanical force causes the weakest bond - the one between the tip and polymer - to break. This process transfers the polymer molecule to the substrate where it can be modified by further chemical reactions.