Takashi Ichii

True-molecular resolution imaging by frequency modulation atomic force microscopy in various environments

In this study, we discuss the relationship between Q factor of the cantilever in various environments and frequency noise in frequency modulation atomic force microscopy (FM-AFM). We first present true-molecular resolution FM-AFM images of alkanethiol self-assembled monolayers taken in a moderate vacuum environment (vacuum pressure: 6 Pa) and in air (cantilever Q factor: 390) using FM-AFM with a low noise cantilever deflection sensor. The results reveal that the minimum Q factor to obtain true-molecular resolution in FM-AFM can be less than a few hundred.

Alkyl and Alkoxyl Monolayers Directly Attached to Silicon: Chemical Durability in Aqueous Solutions

For practical application of self-assembled monolayers (SAMs), knowledge of their chemical durability in acidic or basic solutions is important. In the present work, a series of SAMs directly immobilized on a silicon (111) surface through Si-C or Si-O-C covalent bonds without a native oxide layer were prepared by thermally activated chemical reactions of a hydrogen-terminated Si(111) substrate with linear molecules, i.e., 1-hexadecene, 1-hexadecanol, 1-dodecanol, and n-dodecanal, to investigate the durability of the SAMs to HF and Na2CO3 solutions. While grazing incidence X-ray reflectivity measurements showed that all the as-prepared SAMs had almost the same film density and molecular coverage, keeping the original step and terrace structure of Si(111) as is observed by atomic force microscopy, they gave different degradation behaviors, i.e., pitting and concomitant surface roughening in both solutions. 1-hexadecene SAM was stable against immersion in both solutions, while the other SAMs were damaged within 60 min, most likely due to the difference in chemical bonding modes at the SAM/Si interface, i.e., Si-C and Si-O-C.

Molecular-scale noncontact atomic force microscopy contrasts in topography and energy dissipation on c(4x2) superlattice structures of alkanethiol self-assembled monolayers

Alkanethiol self-assembled monolayers formed on Au(111) surfaces were investigated by noncontact atomic force microscopy (NC-AFM). Dodecanethiol monolayers prepared at 78 °C were imaged by NC-AFM, which revealed that the film is composed predominantly of two different phases of c(4×2) superlattice structures. The obtained molecular-scale NC-AFM contrasts are discussed in comparison with previously reported scanning tunneling microscopy images. We found that the energy dissipation image exhibits a clear difference in its molecular-scale contrast between the two phases. Possible origins of the difference are discussed in relation to the fluctuation and/or stability of the packing structures.

Site-Selective Assembly and Reorganization of Gold Nanoparticles along Aminosilane-Covered Nanolines Prepared on Indium–Tin Oxide

We have fabricated gold nanoparticle (AuNP) arrays on indium-tin oxide (ITO) substrates in a nearly one-dimensional fashion. AuNPs were site-selectively immobilized on ITO of which the surface had been patterned by a nanolithography process based on scanning probe microscopy. The fabricated nanoscale lines covered with aminosilane self-assembled monolayer served as chemisorption sites for citrate-stabilized AuNPs of 20 nm in diameter, accordingly, AuNP nanolines with a thickness of single nanoparticle diameter were spontaneously assembled on the lines. In this 1D array, the AuNPs were almost separated from each other due to the electrostatic repulsion between their negatively charged surface layers. Furthermore, a reorganization process of the immobilized AuNP arrays has been successfully demonstrated by replacing each AuNPs surface layer from citric acid to dodecanethiol. By this process, the AuNPs lost their electrostatic repulsion and became hydrophobic so as to be attracted to each other through hydrophobic interaction, resulting in reorganization of the AuNP array. By repeating the deposition and reorganization cycle, AuNPs were more densely packed. The optical absorption peak of the arrays due to their plasmonic resonance was found to shift from 526 to 590 nm in wavelength with repeating cycles, indicating that the resonance manner was changed from the single nanoparticle mode to the multiple particle mode with interparticle coupling.

Surface Chemical Conversion of Organosilane Self-Assembled Monolayers with Active Oxygen Species Generated by Vacuum Ultraviolet Irradiation of Atmospheric Oxygen Molecules

The chemical conversion of the top surface of n-octadecyltrimethoxy silane self-assembled monolayers (ODS-SAMs) on oxide-covered Si substrates using active oxygen species generated from atmospheric oxygen molecules irradiated with vacuum ultraviolet (VUV) light at 172 nm in wavelength has been studied on the basis of water contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy. An ODS-SAM whose water contact angle was 104° on average was prepared using chemical vapor deposition with substrate and vapor temperatures of 150 °C. The VUV treatment of an ODS-SAM sample was carried out by placing the sample in air and then irradiating the sample surface with a Xe-excimer lamp. The distance between the lamp and the sample was regulated so that the VUV light emitted from the lamp was almost entirely absorbed by atmospheric oxygen molecules to generate active oxygen species, such as ozone and atomic oxygen before reaching the sample surface. Hence, the surface chemical conversion of the ODS-SAM was primarily promoted through chemical reactions with the active oxygen species. Photochemical changes in the ODS-SAM were found to be the generation of polar functional groups, such as –COOH, –CHO, and –OH, on the surface and the subsequent etching of the monolayer. Irradiation parameters, such as irradiation time, were optimized to achieve a better functionalization of the SAM top surface while minimizing the etching depth of the ODS-SAM. The ability to graft another SAM onto the modified ODS-SAM bearing polar functional groups was demonstrated by the formation of alkylsilane bilayers.

Vacuum-ultraviolet photoreduction of graphene oxide: Electrical conductivity of entirely reduced single sheets and reduced micro line patterns

We here report a scanning probe method to locally and directly research the electrical properties of vacuum-ultraviolet (VUV) reduced graphene oxide. The measured electrical conductivity of individual VUV-reduced GO (VUV-rGO) sheets by using conductive atomic force microscopy (CAFM) reached 0.20 S·m−1 after 64 min irradiation, which was clearly enhanced compared with the pristine GO. According to the X-ray photoelectron spectroscopy results, the recovered conductivity of VUV-rGO could be ascribed to the partial elimination of oxygen-containing functional groups and the rapid reconstruction of the C=C bonds. Heterogeneously distributed low- and high-conductivity domains (with a diameter of tens of nanometer to ca. 500 nm) were found from current mapping of the VUV-rGO sheet. By applying photomask lithography, rGO regions were drawn into single GO sheet and were researched by CAFM. The in-plane lateral conductivity of rGO regions increased obviously compared with pristine GO regions.

Formation of uniform ferrocenyl-terminated monolayer covalently bonded to Si using reaction of hydrogen-terminated Si(111) surface with vinylferrocene/n-decane solution by visible-light excitation.

Electrochemically active self-assembled monolayers (SAM) have been successfully fabricated with atomic-scale uniformity on a silicon (Si)(111) surface by immobilizing vinylferrocene (VFC) molecules through Si-C covalent bonds. The reaction of VFC with the hydrogen-terminated Si (H-Si)(111) surface was photochemically promoted by irradiation of visible light on a H-Si(111) substrate immersed in n-decane solution of VFC. We found that aggregation and polymerization of VFC was avoided when n-decane was used as a solvent. Voltammetric quantification revealed that the surface density of ferrocenyl groups was 1.4×10(-10) mol cm(-2), i.e., 11% in substitution rate of Si-H bond. VFC-SAMs were then formed by the optimized preparation method on n-type and p-type Si wafers. VFC-SAM on n-type Si showed positive photo-responsivity, while VFC-SAM on p-type Si showed negative photo-responsivity.

Vacuum-Ultraviolet Promoted Oxidative Micro Photoetching of Graphene Oxide

Microprocessing of graphene oxide (GO) films is of fundamental importance in fabricating graphene-based devices. We demonstrate the photoetching of GO sheets using vacuum-ultraviolet (VUV, λ = 172 nm) light under controlled atmospheric pressure. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and differential interference contrast microscopy (DIC) studies revealed that the photoetching of GO films successfully proceeded in the regions exposed to VUV irradiation in the oxygen-containing atmosphere. Precise photoetching of the GO sheets was achieved at a vacuum pressure of 5 × 10(3) Pa with VUV light irradiation for 20 min. This was followed by VUV irradiation in a high vacuum (<10(-3) Pa) and sonication in water. The photoetched GO sheets then transformed into reduced GO (rGO) patterns. The minimum feature fabricated by this method was 2 μm wide lines aligned at an interval of 4 μm. This method provides a cost-effective way to fabricate rGO patterns with fewer boundaries between rGO sheets and offers a better integrity of rGO, which can be promising for further applications in micro mechanics, micro electrochemistry, optoelectronics, etc.

Reductive patterning of graphene oxide by vacuum–ultraviolet irradiation in high vacuum

A dry photoprocess for converting graphene oxide (GO) to reduced GO (rGO) by vacuum?ultraviolet (VUV) irradiation is reported. The rapid reduction of GO was achieved by irradiating a GO sheet in vacuum with 172 nm VUV light at a low power density of 10 mW?cm?2. This VUV reduction photochemistry was successfully applied to photolithography by which rGO lines could be drawn on a GO microsheet at a sub-micrometer resolution. This method will be promising for the fabrication of graphene-based microdevices.

Frequency Modulation Atomic Force Microscopy in Ionic Liquid Using Quartz Tuning Fork Sensors

Frequency modulation atomic force microscopy (FM-AFM) imaging in ionic liquids (ILs) were carried out. A quartz tuning fork sensor with a sharpened tungsten tip was used as a force sensor instead of a Si cantilever. Only the tip apex was immersed in ILs and the quality factor of the sensors was kept more than 100 in spite of the high viscosity of ILs. Atomic-resolution topographic imaging was successfully achieved in an IL as well as in an aqueous solution. In addition, frequency shift versus tip-to-sample distance curves were obtained and the structures of local solvation layers were studied.