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Chemical etching of silicon assisted by various types of carbon materials is drawing much attention for the fabrication of silicon micro/nanostructures. We developed a method of chemical etching of silicon that utilizes graphene oxide (GO) sheets to promote the etching reaction in a hydrofluoric acid–nitric acid (HF–HNO₃) etchant. By using an optimized composition of the HF–HNO₃ etchant, the etching rate under the GO sheets was 100 times faster than that of our HF–H₂O₂ system used in a previous report. Kinetic analyses showed that the activation energy of the etching reaction was almost the same at both the bare silicon and GO-covered areas. We propose that adsorption sites for the reactant in the GO sheets enhance the reaction frequency, leading to a deeper etching in the GO areas than the bare areas. Furthermore, GO sheets with more defects were found to have higher catalytic activities. This suggests that defects in the GO sheets function as adsorption sites for the reactant, thereby enhancing the etching rate under the sheets.

The surface potentials and local conductivity of self-assembled monolayers (SAMs) formed using aromatic molecules covalently bonded to n-type silicon (111) via Si–C and Si–O bonds were measured using Kelvin probe force microscopy (KPFM) and conductive AFM (CAFM). Surface potential measurements were done using micropatterned SAMs with hexadecyl SAM as a reference to eliminate surface potential variations due to the cantilever tips. Micropatterning was conducted via vacuum ultraviolet photolithography at λ = 172 nm. Ellipsometry, X-ray photoelectron spectroscopy, static water contact angle and atomic force microscopy tests show that the aromatic SAMs were well-organized despite the short molecular lengths of the precursors. KPFM results show that Si–C bonded SAMs have higher surface potentials compared to Si–O SAMs, which is in agreement with dipole moments estimated by Molecular Orbital Package semi-empirical computations. CAFM scans showed conductive domains for the aromatic SAM regions, and Si–O SAMs exhibited a higher current than Si–C SAMs.

Simultaneous detection of vertical and lateral forces at the nanoscale by atomic force microscopy (AFM) yields important knowledge on nanotribology. Although silicon (Si) cantilevers are capable of detecting both the forces, it has not been achieved by quartz tuning fork sensors including qPlus sensors. In this study, we found that the tip apex of the qPlus sensor with a long tip oscillates vertically at the lowest resonance frequency (ƒ₁) and laterally at the second lowest resonance frequency (ƒ₂) by the finite element method simulation. The lateral oscillation was experimentally confirmed by atomic resolution imaging, where the imaged atoms were apparently connected when increasing the oscillating amplitude at ƒ₂. We also demonstrated the nanometer-scale friction force measurement by using the developed bimodal AFM. The obtained result was in good agreement with the contact-mode lateral force microscopy utilizing a Si cantilever.

The creation of a model that explains the dependency of the voltammetric characteristics of ferrocene-terminated Si (Si-Fc) samples on the type of substrate (n- or p-type) would be helpful in understanding the electronic characteristics of these materials. To explain the dependency, Si-Fc samples are treated like diodes. As diodes, the samples may allow charge flow in a certain direction while inhibiting the opposite flow. The treatment of a sample as a diode is done to facilitate analysis of charge flow within the sample, thus enabling easy prediction of its electrochemical characteristics. Likewise, the trend of the anodic peak potential versus light intensity plot (of the samples with n-type substrate) is also associated with the sample’s diode characteristics. Our proposed model opens many scientific possibilities, especially in relating the voltammetric characteristics of electroactive molecules on a Si surface with the properties of a diode (e.g., open-circuit voltage)., Article first published online: 15 SEP 2014

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)molcm(-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 (VUV, λ = 172 nm) patterning of alkyl monolayer on silicon surface has been demonstrated with emphasis on the diffusion of VUV induced oxygen-derived active species, which are accountable for the pattern broadening. The VUV photons photo-dissociates the atmospheric oxygen and water molecules into the oxygen-derived active species (oxidants). These oxidants photo-oxidize the hexadecyl (HD) monolayer in VUV irradiated regions (Khatri et al., Langmuir. 24 (2008) 12077), as well as the little concentration of oxidants diffuses towards the masked areas. In this study, we performed VUV patterning at a vacuum pressure of 10 Pa to track the diffusion pathways for the oxidants with help of gold nanoparticles (AuNPs; = 10 nm) immobilization. At VUV irradiated sites AuNPs are found as uniformly distributed, but adjacent to the pattern boundary we observed quasi-linear arrays of AuNPs, which are determined by diffusion pathways of the oxidants. The diffusion of oxidants plays vital role in pattern broadening. The site selective anchoring of AuNPs demonstrates the utility of VUV photons for the construction of functional materials with microstructural architecture.

We demonstrate the formation of two-dimensional (2D) arrays of gold nanoparticles (AuNPs) by controlled functionalization in a regular linear fashion, on the basis of the self-assembly and vacuum ultraviolet (VUV) lithography approaches. An octadecyltrimethoxysilane (ODS) monolayer, self-assembled on an indium tin oxide (ITO) surface, was exposed to VUV light (172 nm) through a photomask to construct the linear pattern by photodegradation of the ODS monolayer. Subsequently, an aminopropyltriethoxysilane (APS) monolayer was deposited on VUV-exposed sites by chemical vapor deposition. The immobilization of AuNPs on amino-terminated sites is due to the electrostatic attraction between citrate-stabilized AuNPs and amino groups of the APS monolayer, while the methyl-terminated sites remain unexposed. The structural organization of AuNPs in an alternating linear fashion was demonstrated by scanning electron microscope (SEM) analysis. The X-ray photoelectron microscopy (XPS) measurements were performed to probe the self-assembly of ODS, the APS monolayer, photopatterning and AuNPs immobilization.