• Bulletin of the Korean Chemical Society
• /
• v.29 no.2
• /
• pp.438-444
• /
• 2008

A self-assembled monolayer of 2,2'-bipyridine (22BPY) molecules on Au(111) underwent a structural phase transition when the polarity of a bias voltage was switched in scanning tunneling microscopy (STM) experiments. The nature of two bright spots representing each 22BPY molecule on Au(111) in the high-resolution STM images was identified by calculating the partial density plots for a monolayer of 22BPY molecules adsorbed on Au(111) using tight-binding electronic structure calculations. The stacking pattern of the chains of 22BPY molecules on Au(111) was explained by examining the intermolecular interactions between the 22BPY molecules based on first principles electronic structure calculations for a 22BPY dimer, (22BPY)2. The structural instability of the 22BPY molecule arrangement caused by a change in the bias voltage switch was investigated by estimating the adsorbate-surface interaction energy using a point-charge approximation for Au(111).

• Proceedings of the Korean Vacuum Society Conference
• /
• 2015.08a
• /
• pp.109.1-109.1
• /
• 2015

Understanding the reaction mechanisms and structures underlying the adsorption of biomolecules on semiconductors is important for functionalizing semiconductor surfaces for various bioapplications. Herein, we describe the characteristic behavior of a primary nucleobase adsorbed on the semiconductor Ge(100). The adsorption configuration of guanine, a primary nucleobase found in DNA and RNA, on the semiconductor Ge(100) at an atomic level was investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. When adsorbed on Ge(100) at room temperature, guanine appears dark in STM images, indicating that the adsorption of guanine on Ge(100) occurs through N-H dissociation. In addition, DFT calculations revealed that "N(1)-H dissociation through an O dative bonded structure" is the most favorable adsorption configuration of all the possible ones. We anticipate that the characterization of guanine adsorbed on Ge(100) will contribute to the development of semiconductor-based biodevices.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.2
• /
• pp.441-444
• /
• 2009

The formation and structure of self-assembled monolayers (SAMs) by the adsorption of acetyl-protected octylthioacetate (OTA) on Au(111) in a catalytic tetrabutylammonium cyanide (TBACN) solution were examined by means of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV). Molecular-scale STM imaging revealed that OTA molecules on Au(111) in a pure solvent form disordered SAMs, whereas they form well-ordered SAMs showing a c(4 × 2) structure in a catalytic TBACN solution. XPS and CV measurements also revealed that OTA SAMs on Au(111) formed in a TBACN solution have a stronger chemisorbed peak in the S 2p region at 162 eV and a higher blocking effect compared to OTA SAMs formed in a pure solvent. In this study, we clearly demonstrate that TBACN can be used as an effective deprotecting reagent for obtaining well-ordered SAMs of thioacetyl-protected molecules on gold.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2010.02a
• /
• pp.94-94
• /
• 2010

Scanning tunneling microscopy (STM) was used to study the electronic structure of cobalt(II) tetraphenylporphyrin (CoTPP) on the Fe/W(110) substrate. Clover-like conformation of CoTPP was observed and showed bias dependent STM images. The central Co(II) ion of this porphyrin was protruded on the positive biases, but it was depressed on the negative biases. On the positive biases, the phenyl rings of CoTPP appeared to be bright contrary to the invisible pyrrole rings. These results were compared the first-principles calculations using GGA and GGA+U to elucidate the influence of the Fe substrate. GGA+U results agreed well with the experimental results; however, GGA did not. These results show that proper treatment of the on-site Coulomb repulsion of the Fe ions is crucial to describe the electronic structure of this system. By the comparison between the GGA+U calculations on the Fe substrate and the gas phase calculations, it can be noted that chemical potential shift occurred accompanying charge transfer from the Fe ions of the substrate to the pyrrole ligand of the porphyrin.

• Analytical Science and Technology
• /
• v.8 no.4
• /
• pp.723-730
• /
• 1995

Cyclic voltammetry and in situ STM were employed to examine the interfacial structures of a Pt(111) electrode in 0.1 mM KCN (pH9.5) and 0.1 mM KSCN (pH7) solutions. In situ STM atomic resolution revealed well ordered (2${\surd}$3${\times}$2${\surd}$3)$R30^{\circ}$-6CN and ($2{\times}2$)-2SCN structures within the double layer charging region. Six CN adsorbates formed a hollow hexagon, which embraced a coadsorbed $K^+$ cation. In contrast, the coadsorbed $K^+$ cations on the SCN covered Pt(111) were poorly ordered, despite adsorbed SCN formed a long range ordered ($2{\times}2$)-2SCN adlattice. In situ STM revealed the pronounced influence of potential in controlling the structures of compact layers at the proximity of a Pt electrode. Cathodic polarization facilitated the replacement of the coadsorbed cations by protons.

• The Transactions of the Korean Institute of Electrical Engineers C
• /
• v.55 no.1
• /
• pp.16-19
• /
• 2006

The characteristic of negative differential resistance(NDR) is decreased current when the applied voltage is increased. The NDR is potentially very useful in molecular electronics device schemes. Here, we investigated the NDR characteristic of self-assembled 4,4'-di(ethynylphenyl)-2'-nitro-1-benzenethiolate, which has been well known as a conducting molecule. Self-assembly monolayers(SAMs) were prepared on Au(111), which had been thermally deposited onto $pre-treatment(H_2SO_4:H_2O_2=3:1)$ Si. The Au substrate was exposed to a 1 mM/1 solution of 1-dodecanethiol in ethanol for 24 hours to form a monolayer. After thorough rinsing the sample, it was exposed to a 0.1 ${\mu}M/l$ solution of 4.4'-di(ethynylphenyl)-2'-nitro-1-(thioacetyl)benzene in dimethylformamide(DMF) for 30 min and kept in the dark during immersion to avoid photo-oxidation. After the assembly, the samples were removed from the solutions, rinsed thoroughly with methanol, acetone, and $CH_2Cl_2,$ and finally blown dry with N_2. Under these conditions, we measured electrical properties of self-assembly monolayers(SAMs) using ultra high vacuum scanning tunneling microscopy(UHV-STM). The applied voltages were from -2 V to +2 V with 298 K temperature. The vacuum condition was $6{\time}10^{-8}$ Torr. As a result, we found the NDR voltage of the 4,4'-di(ethynylphenyl)-2'-nitro-1-benzenethiolate were $-1.61{\pm}0.26$ V(negative region) and $1.84{\pm}0.33$ V(positive region). respectively.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.02a
• /
• pp.318-318
• /
• 2011

Etching of an ultrathin aluminum oxide film on NiAl(110) substrate by methanol is studied by home-built scanning tunneling microscopy at room-temperature. We deposited liquid methanol on thin alumina film by using a high speed solenoid valve suitable for deposition of thermally unstable molecules. It is found that only the reflection domain boundary between two domains was preferentially etched by methanol. Since the reflection domain boundary has many oxygen vacancies and irregular structures, judging from the fact, we assume that oxygen vacancies cause the chemically reactive phenomena of methanol in reflection domain boundary on an alumina film. The reactivity of the reflection domain boundary is attributed to the oxygen vacancies due to irregular structures. Similar reactivity is found on the oxygen deficient alumina produced on top of the intact alumina.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2010.02a
• /
• pp.353-353
• /
• 2010

Alcohol is a vesatile polar solvent for molecules. As a preparation to deposit large molecules, we studied interaction of solvent molecules on metallic surface. in this work, we report on methanol adsorption on NiAl(110) with scanning tunneling microscopy (STM). These alcohol solvent molecules were deposited by a pulse injection method suitable for deposition of thermally unstable molecules. The injection of liquid alcohol onto the substrate in UHV was performed by using a high-speed solenoid valve with the back-pressure reduced down to 100 Torr. This technique allowed precise control over the amount of dosing of molecules to less than 1 L. Alcohol-induced features, attributed to methoxy, were found on bare NiAl(110) surface.

• Journal of Electrochemical Science and Technology
• /
• v.4 no.4
• /
• pp.153-156
• /
• 2013

Charge transfer between STM tip and Au(100) has been investigated by using a Scanning Tunneling Microscopy (STM) technique in dry, $H_2O$, and $D_2O$ atmospheres. Dry atmosphere was indicated by humidity as low as 5 % and high humidity as high as 98% was managed by injecting $H_2O$ and $D_2O$ to the chamber. The current decayed more slowly in high humidity than in dry atmosphere. The plateau currents were found to appear at separations larger than ca. $5{\AA}$ where the current decay stopped depending on applied bias voltages. The polarity dependence was observed at the STM junction between Pt-Ir tip and the gold. On the contrary, little dependence was seen at the one between Au tip and the substrate electrode.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2011.08a
• /
• pp.111-111
• /
• 2011

Arrangement of individual atoms and molecules with atomic precision and understanding the resulting properties at the molecular level are ultimate goals of chemistry, biology, and materials science. For the past three decades, scanning probe microscopy has made strides towards these goals through the direct observation of individual atoms and molecules, enabling the discovery of new and unexpected phenomena. This talk will discuss the origin of forces governing motion of small organic molecules and their extended self-assembly into two-dimensional surface structures by direct observation of individual molecules using scanning tunneling microscopy (STM). In addition, atomic force microscopy (AFM) is utilized for the investigation of fundamental mechanisms of bone mineral dissolution by examining atomically well characterized simulated bone minerals under aqueous solution environments.