Polypyrrole-modified tips for functional group recognition in scanning tunneling microscopy

Tailored chemical modification of scanning tunneling microscopy (STM) tips is a promising method for the recognition of specific chemical species and functional groups in STM images. The present study shows for the first time that tips modified with polypyrrole can be used to measure STM images with molecular resolution. A high conductivity of the polypyrrole film was found to be important for the observation of STM images, while the thickness of the polymer film did not affect the images significantly. Furthermore, it was shown that recognition of functional groups in STM images is possible with tips coated with conductive polypyrroles. 1-Octadecanol and 1-octadecanoic acid monolayers with polypyrrole-modified tips gave high-resolution STM images in which aligned OH and COOH residues were represented by easily recognizable elevated bands. These selective contrast enhancements resemble those observed by us previously with gold tips modified with self-assembled monolayers (SAMs) and seem to be due to hydrogen bond interactions between functional groups of the tip-modifying molecules and the sample. The reproducibility of contrast enhancements in this study was significantly higher than for SAM-modified tips, suggesting that polymer modification of STM tips is particularly promising for specific functional group recognition with chemically modified STM tips.     

Direct imaging of molecular orbitals of metal phthalocyanines on metal surfaces with an O2-functionalized tip of a scanning tunneling microscope

High-resolution scanning tunneling microscope images of iron phthalocyanine and zinc phthalocyanine molecules on Au(111) have been obtained using a functionalized tip of a scanning tunneling microscope (STM), and show rich intramolecular features that are not observed using clean tips. Ab initio density functional theory calculations and extended Hückel theory calculations revealed that the imaging of detailed electronic states is due specifically to the decoration of the STM tip with O₂. The detailed structures are differentiated only when interacting with the highly directional orbitals of the oxygen molecules adsorbed on a truncated, [111]-oriented tungsten tip. Our results indicate a method for increasing the resolution in generic scans and thus, have potential applications in fundamental research based on high-resolution electronic states of molecules on metals, concerning, for example, chemical reactions, and catalysis mechanisms.     

Carbon nanotube scanning tunneling microscopy tips for chemically selective imaging

Carboxyl-terminated single-walled carbon nanotubes (SWNTs) were successfully immobilized from solution phases onto the apexes of gold tips for scanning tunneling microscopy (STM). Gold STM tips were first modified with self-assembled monolayers of 4-mercaptobenzoic acid, and its carboxyl groups were used to anchor carboxylated SWNTs through Zn2+ ion-bridged coordination. These SWNT tips gave high-resolution STM images of a diether monolayer formed on the graphite surface. In addition and more importantly, the ether oxygens of the sample molecules were selectively observed as bright spots with the SWNT tips with significantly high reproducibility, which is due to the facilitation of electron tunneling through hydrogen bond interactions between the ether oxygens and carboxyl groups at the end of the SWNT tips.     

MgB2 Superconducting Tips for Scanning Tunneling Microscopy Study

We report a simple method for the fabrication of reproducible, clean, and stable MgB₂ superconducting tips. The quality of these tips has been verified by imaging the surface of a thin Au(111) film sample, using a low temperature scanning tunneling microscopy (STM). Using the MgB₂ superconducting tip, high-quality semiatomically resolved STM surface images of the thin Au(111) film sample have been observed, which unambiguously indicates that the fabrication of relatively superconducting MgB₂, suitable for use as STM tips, is feasible.     

MgB2 Superconducting Tips for Scanning Tunneling Microscopy Study

We report a simple method for the fabrication of reproducible, clean, and stable MgB₂ superconducting tips. The quality of these tips has been verified by imaging the surface of a thin Au(111) film sample, using a low temperature scanning tunneling microscopy (STM). Using the MgB₂ superconducting tip, high-quality semiatomically resolved STM surface images of the thin Au(111) film sample have been observed, which unambiguously indicates that the fabrication of relatively superconducting MgB₂, suitable for use as STM tips, is feasible.     

Scanning tunneling microscopy with chemically modified tips: discrimination of porphyrin centers based on metal coordination and hydrogen bond interactions

STM gold tips chemically modified with 4-mercaptopyridine (4MP) were found capable of discriminating zinc(II) 5,15-bis(4-octadecyloxyphenyl)porphyrin (Por-Zn) from its metal-free porphyrin (Por-2H) and nickel(II) complexes (Por-Ni) in the mixed monolayers of these compounds, spontaneously formed at the solution/graphite interface. The porphyrin centers in STM images observed with 4MP-modified tips exhibited bright spots, while those measured with unmodified tips exhibited the porphyrin centers as dark depressions. The centers of Por-Zn were brighter than those of Por-2H and Por-Ni, thereby allowing the discrimination of Por-Zn from Por-2H or Por-Ni in mixed monolayers. The changes in the contrasts of porphyrin centers of Por-2H and Por-Zn/ Por-Ni were explained by facilitated electron tunneling due to hydrogen bond and metal coordination interactions, respectively, between porphyrin centers and the pyridyl group of 4MP on the tip.     

Localized deposition of coronene molecules on Si(001)-2x1 using a scanning tunneling microscope tip source

The deposition of coronene molecules from scanning tunneling microscope (STM) tips onto a clean Si(001)-2x1 surface at 25 degrees C was investigated. The STM tips, contaminated with coronene, were found to deposit coronene molecules on the clean Si(001) surface, allowing patterns to be generated. Covalent Si-C chemical bonds, formed between the coronene molecules and the Si substrate, froze the flip-flop motion of the adjacent Si-Si dimers on the substrate. In most cases, the mode of coronene bonding to Si(001) is independent of whether deposition occurs from the gas phase or from the STM tip. Despite the covalent chemical bonds formed between the coronene molecule and the Si substrate, the STM tip can drag the coronene laterally on the Si substrate without inducing a chemical change in the molecule. Sharp spikes observed in the tunneling current during the coronene deposition reflect the abrupt decrease of the tip-substrate distance at the instant of transport of the molecule from tip to surface.     

Reproducible fabrication of a fiber probe with a nanometric protrusion for near-field optics

We propose a new type of fiber probe with a nanometric protruding tip emerging from a metal film and describe a novel method, called the selective resin-coating method, for fabricating such probes. It is a reproducible etching process consisting of four steps and can be applied to silica fibers sharpened by selective chemical etching. With this method, we obtained tips with the apex diameter and the foot diameter of the protrusion being less than 10 and 30 nm, respectively, when the gold film was ~120 nm thick.     

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.     

A method employing STM for the estimation of relative changes in the work function of modified metal tips

I-z spectroscopy measurements using a scanning tunnelling microscope (STM) were carried out to determine the change in the work function of a W tip following one monolayer (1 ML) deposition of Ni and subsequent annealing at 700 K. The variation in the actual gap voltage obtained from the I-z data of the clean tip was used in the calculation. The estimated values of the change in work function, 016 eV and 0.59 eV, for as-deposited and annealed tips, respectively match closely with the reported values. The method is generally applicable to chemically modified metal tips.     

Long-range order induced by cobalt porphyrin adsorption on aminothiophenol-functionalized Au(111): the influence of the induced dipole

Porphyrins are useful in materials science for optical, photoelectrochemical and chemical sensor applications. Solid films of oriented porphyrins on gold can be realized through a simple procedure and without synthesizing thiol-derivatized porphyrins. In order to immobilize the porphyrin rings on the surface, we prepared a 4-aminothiophenol (4-ATP) self-assembled monolayer (SAM) on gold(111) followed by axial legation, in situ, of cobalt(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin (CoTBPP). Ultrahigh vacuum (UHV) Scanning Tunneling Microscopy (STM) studies performed on the SAMs revealed the Au(111) herringbone structure reconstruction, probably due to adsorption/desorption processes of molecules. STM images and Scanning Tunneling Spectroscopy (STS) measurements clearly showed that the immobilization of molecules also induced an electronic perturbation on the gold surface. This effect is ascribed to the presence of oriented molecular dipole layers between the metal and the organic material.     

STM induced modification of gold surface in the presence of TMP amine

In this paper we present scanning tunneling microscopy (STM) investigations of gold with 2,2,6,6-Tetramethylpiperidine (TMP) overlayer. During the STM experiments the creation of holes and hills or no changes of the surface were observed depending on the applied bias voltage and polarity. No modifications were observed in the bias range from −0.5 to +0.5 V. The holes were created for the bias voltages greater than +0.5 V and hills for the bias voltages lower than −0.5 V. The observed changes of the surface morphology suggest the presence of electrochemical reaction between the tip and the surface. Additionally, our results suggest that TMP lowers the electrochemical activation energy of gold to +0.5 eV.     

On mapping subangstrom electron clouds with force microscopy

In 2004 Hembacher et al. (Science 2004, 305, 380-383) reported simultaneous higher-harmonics atomic force mocroscopy (AFM)/scanning tunneling microscopy (STM) images acquired while scanning a graphite surface with a tungsten tip. They interpreted the observed subatomic features in the AFM images as the signature of lobes of increased electron density at the tungsten tip apex. Although these intriguing images have stirred controversy, an in-depth theoretical feasibility study has not yet been produced. Here we report on the development of a method for simulating higher harmonics AFM images and its application to the same system. Our calculations suggest that four lobes of increased electron density are expected to be present at a W(001) tip apex atom and that the corresponding higher harmonics AFM images of graphite can exhibit 4-fold symmetry features. Despite these promising results, open questions remain since the calculated amplitudes of the higher harmonics generated by the short-range forces are on the order of hundredths of picometers, leading to very small corrugations in the theoretical images. Additionally, the complex, intermittent nature of the tip-sample interaction, which causes constant readjustment of the tip and sample orbitals as the tip approaches and retracts from the surface, prevents a direct quantitative connection between the electron density and the AFM image features.     

Enzyme-assisted nanolithography

We have chemically immobilized alkaline phosphatase molecules onto the apex of a tip of an atomic force microscope. When the substrate BCIP is dephosphorylated by alkaline phosphatase, it will precipitate in the presence of NBT. By bringing the tip in the vicinity of a suitable sample, we could locally deposit this complex on the sample. Thus we combined the activity of an enzyme with the accuracy in positioning a tip in scanning probe microscopy to demonstrate a novel technique referred to as enzyme-assisted nanolithography. By use of other enzymes, this method will open the possibility to chemically modify surfaces on a nanometer scale.     

Bioadhesion of polymers for BioMEMS

Polymers are gaining significant importance in biomedical microelectromechanical systems (bioMEMS) owing to their advantages in microfabrication techniques over conventional silicon-based components and promising biocompatibility. Bioadhesion is a major issue in the reliability and performance of bioMEMS. In this study, the bioadhesion of two surface-modified polymers, poly(methylmethacrylate) and poly(dimethylsiloxane), were studied. The surfaces were modified by coating them with a self-assembled monolayer (SAM) of perfluorodecyltriethoxysilane. Contact angle measurements were made to understand the effect of surface modification. Adhesion of these SAM-modified surfaces were measured with fetal bovine serum dip-coated silicon-nitride atomic force microscope tip in phosphate-buffered saline. The SAM-modified surfaces exhibited lower bioadhesion compared with virgin surfaces.     

Contact mechanics modeling of pull-off measurements: effect of solvent,probe radius,and chemical binding probability on the detection of single-bond rupture forces by atomic force microscopy

Pull-off forces for chemically modified atomic force microscopy tips in contact with flat substrates coated with receptor molecules are calculated using a Johnson, Kendall, and Roberts contact mechanics model. The expression for the work of adhesion is modified to account for the formation of discrete numbers of chemical bonds (nBonds) between the tip and substrate. The model predicts that the pull-off force scales as nBonds(1/2), which differs from a common assumption that the pull-off force scales linearly with nBonds. Periodic peak progressions are observed in histograms generated from hundreds of computed pull-off forces. The histogram periodicity is the signature of discrete chemical interactions between the tip and substrate and allows estimation of single-bond rupture forces. The effects of solvent, probe tip radius, and chemical binding probability on the detection of single-bond forces are examined systematically. A dimensionless parameter, the effective force resolution, is introduced that serves as a quantitative predictor for determining when periodicity in force histograms can occur. The output of model is compared to recent experimental results involving tips and substrates modified with self-assembled monolayers. An advantage of this contact mechanics approach is that it allows straightforward estimation of solvent effects on pull-off forces.     

Tunneling-stabilized magnetic force microscopy of bit tracks on ahard disk

A scanning tunneling microscope (STM) for surface magnetic force measurements on thin-film longitudinal magnetic storage media is described. The usual rigid PtIr tip of the STM was replaced by a flexible Fe-film tip and the tip position was stabilized near the surface of the sample using the STM feedback system as tunneling occurs between the tip and sample surface. Images of a CoCrTa thin-film hard disk showing 5 μm×3 μm bit tracks written by the ferrite head of a computer disk drive are presented. The images shown are comparable to images of the bit tracks on textured surfaces using either ferrofluid decoration or other magnetic force microscopy (MFM) imaging techniques. The sensitivity of the Fe-film tip was such that the influence on the image due to magnetic forces was larger than the influence due to sample surface topography     

SPM and TOF-SIMS investigation of the physical and chemical modification induced by tip writing of self-assembled monolayers

The nanoelectrochemical modification of alkyl self-assembled monolayers (SAMs) obtained on hydrogenated silicon surfaces via radical-initiated reactions of 1-octadecene has been investigated. Scanning Probe Microscopy (SPM) showed that the modification of the organic layer occurs by applying either positive or negative biases to the tip at a threshold of about ±5 V. When the bias absolute value was ≤6 V, the height of the monolayer was only faintly modified, whereas a consistent increase in tip/sample friction force was observed, in agreement with the formation of hydrophilic moieties at the organic surface. In addition to the increase of friction, bias absolute values larger than 6 V led to a significant raise of the surface height, the application of negative biases resulting in stronger effects. This suggests the occurrence of a concomitant growth of silicon oxide underneath the organic layer. Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) experiments, including chemical imaging and analysis of the retrospective spectra, were performed by writing patterns of some microns in size on the SAM. These experiments allowed to investigate the features of the chemical modification as a function of the applied bias. Positive spectra from the modified regions display the presence of C_xH_yO and C_xH_yN type peaks that increase with the tip bias, whereas an intensity reduction of the SiC_xH_y signals with respect to the unmodified regions was observed.     

用扫描隧道显微镜对材料进行表面修饰的研究

扫描隧道显微镜(STM)是对材料表面进行表面修饰(surface modification)和表面原子操纵(atomcraft)的重要工具。为了了解其机理,选择了场蒸发阈值从大到小有代表性的钨、铂、金、铜做针尖,扫描过程中在针尖与石墨表面之间施加针尖为正的脉冲电压,获得了一些新现象,并对实验结果作了比较,从而在一定程度上确定了脉冲制STM表面修饰实验中针尖与样品之间电场的重要作用。     

Electrochemical sensor for electrochemically inactive beta-D(+)-glucose using alpha-cyclodextrin template molecules

We report an electrochemical sensor for an electrochemically inactive organic compound using a self-assembled monolayer (SAM) formed on the gold surface from a solution of thiolated alpha-cyclodextrin (alpha-CD). The SAM makes up an array of ultramicroelectrodes, which capture electroactive molecules such as those of ferrocene. When this SAM-modified electrode is exposed to a solution containing an electrochemically inactive compound, e.g., glucose, the captured ferrocene molecules are replaced by the electroinactive molecules via an equilibrium established between the two compounds, lowering the current for ferrocene oxidation. The decrease in current is directly proportional to the amount of glucose added and the glucose can be analyzed up to approximately 0.80 mM, which is approximately 1/10 of a typical physiological concentration in blood serum. Formation constants of the surface-bound alpha-CD molecules with ferrocene and glucose are also reported.