• Korean Journal of Materials Research
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• v.19 no.8
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• pp.437-442
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• 2009

This paper describes an improved strategy for controlling the adhesion force using both the antiadhesion and adhesion layers for a successful large-area transfer process. An MPTMS (3-mercaptopropyltrimethoxysilane) monolayer as an adhesion layer for Au/Pd thin films was deposited on Si substrates by vapor self assembly monolayer (VSAM) method. Contact angle, surface energy, film thickness, friction force, and roughness were considered for finding the optimized conditions. The sputtered Au/Pd ($\sim$17 nm) layer on the PDMS stamp without the anti-adhesion layer showed poor transfer results due to the high adhesion between sputtered Au/Pd and PDMS. In order to reduce the adhesion between Au/Pd and PDMS, an anti-adhesion monolayer was coated on the PDMS stamp using FOTS (perfluorooctyltrichlorosilane) after $O_2$ plasma treatment. The transfer process with the anti-adhesion layer gave good transfer results over a large area (20 mm $\times$ 20 mm) without pattern loss or distortion. To investigate the applied pressure effect, the PDMS stamp was sandwiched after 90$^{\circ}$ rotation on the MPTMS-coated patterned Si substrate with 1-${\mu}m$ depth. The sputtered Au/Pd was transferred onto the contact area, making square metal patterns on the top of the patterned Si structures. Applying low pressure helped to remove voids and to make conformal contact; however, high pressure yielded irregular transfer results due to PDMS stamp deformation. One of key parameters to success of this transfer process is the controllability of the adhesion force between the stamp and the target substrate. This technique offers high reliability during the transfer process, which suggests a potential building method for future functional structures.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.108-109
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• 2012

This talk will begin with the demonstration of facile synthesis of silicon nanostructures using the magnesiothermic reduction on silica nanostructures prepared via self-assembly, which will be followed by the characterization results of their performance for energy storage. This talk will also report the fabrication and characterization of highly porous, stretchable, and conductive polymer nanocomposites embedded with carbon nanotubes (CNTs) for application in flexible lithium-ion batteries. It will be presented that the porous CNT-embedded PDMS nanocomposites are capable of good electrochemical performance with mechanical flexibility, suggesting these nanocomposites could be outstanding anode candidates for use in flexible lithium-ion batteries. Directed self-assembly (DSA) of block copolymers (BCPs) can generate uniform and periodic patterns within guiding templates, and has been one of the promising nanofabrication methodologies for resolving the resolution limit of optical lithography. BCP self-assembly processing is scalable and of low cost, and is well-suited for integration with existing semiconductor manufacturing techniques. This talk will introduce recent research results (of my research group) on the self-assembly of Si-containing block copolymers for the achievement of sub-10 nm resolution, fast pattern generation, transfer-printing capability onto nonplanar substrates, and device applications for nonvolatile memories. An extraordinarily facile nanofabrication approach that enables sub-10 nm resolutions through the synergic combination of nanotransfer printing (nTP) and DSA of block copolymers is also introduced. This simple printing method can be applied on oxides, metals, polymers, and non-planar substrates without pretreatments. This talk will also report the direct formation of ordered memristor nanostructures on metal and graphene electrodes by the self-assembly of Si-containing BCPs. This approach offers a practical pathway to fabricate high-density resistive memory devices without using high-cost lithography and pattern-transfer processes. Finally, this talk will present a novel approach that can relieve the power consumption issue of phase-change memories by incorporating a thin $SiO_x$ layer formed by BCP self-assembly, which locally blocks the contact between a heater electrode and a phase-change material and reduces the phase-change volume. The writing current decreases by 5 times (corresponding to a power reduction of 1/20) as the occupying area fraction of $SiO_x$ nanostructures varies.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.230-230
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• 2012

Graphene have showed promising performance as electrodes of organic devices such as organic transistors, light-emitting diodes, and photovoltaic solar cells. In particular, among various organic materials of graphene-based organic devices, pentacene has been regarded as one of the promising organic material because of its high mobility, chemical stability. In the bottom-contact device configuration generally used as graphene based pentacene devices, the morphology of the organic semiconductors at the interface between a channel and electrode is crucial to efficient charge transport from the electrode to the channel. For the high quality morphology, understanding of initial stages of pentacene growth is essential. In this study, we investigate self-assembly of pentacene molecules on graphene formed on a 6H-SiC (0001) substrate by scanning tunneling microscopy. At sub-monolayer coverage, adsorption of pentacene molecules on epitaxial graphene is affected by $6{\times}6$ pattern originates from the underlying buffer layer. And the orientation of pentacene in the ordered structure is aligned with the zigzag direction of the edge structure of single layer graphene. As coverage increased, intermolecular interactions become stronger than molecule-substrate interaction. As a result, herringbone structures the consequence of higher intermolecular interaction are observed.

• Journal of the Korean Vacuum Society
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• v.19 no.2
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• pp.81-90
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• 2010

We introduce a novel and versatile approach for preparing self-assembled nanoporous multilayered films with antireflective properties. Protonated polystyrene-block-poly (4-vinylpyrine) (PS-b-P4VP) and anionic polystyrene-block-poly (acrylic acid) (PS-b-PAA) block copolymer micelles (BCM) were used as building blocks for the layer-by-layer assembly of BCM multilayer films. BCM film growth is governed by electrostatic and hydrogen-bonding interactions between the oppositely BCMs. Both film porosity and film thickness are dependent upon the charge density of the micelles, with the porosity of the film controlled by the solution pH and the molecular weight (Mw) of the constituents. PS7K-b-P4VP28K/PS2K-b-PAA8K films prepared at pH 4 (for PS7K-b-P4VP28K) and pH 6 (for PS2K-b-PAA8K) are highly nanoporous and antireflective. In contrast, PS7K-b-P4VP28K/PS2K-b-PAA8K films assembled at pH 4/4 show a relatively dense surface morphology due to the decreased charge density of PS2K-b-PAA8K. Films formed from BCMs with increased PS block and decreased hydrophilic block (P4VP or PAA) size (e.g., PS36K-b-P4VP12K/PS16K-b-PAA4K at pH 4/4) were also nanoporous. Furthermore, we demonstrate that the nanostructured electrochemical sensors based on patterning methods show the electrochemical activities. Anionic poly(styrene sulfonate) (PSS) layers were selectively and uniformly deposited onto the catalase (CAT)-coated surface using the micro-contact printing method. The pH-induced charge reversal of catalase can provide the selective deposition of consecutive PE multilayers onto patterned PSS layers by causing the electrostatic repulsion between next PE layer and catalase. Based on this patterning method, the hybrid patterned multilayers composed of platinum nanoparticles (PtNP) and catalase were prepared and then their electrochemical properties were investigated from sensing $H_2O_2$ and NO gas. This study was based on the papers reported by our group. (J. Am. Chem. Soc. 128, 9935 (2006); Adv. Mater. 19, 4364 (2007); Electro. Mater. Lett. 3, 163 (2007)).

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.07b
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• pp.811-813
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• 2003

We investigated the electrical properties of self-assembled (4,4'-Di(ethynylphenyl)-2'-nitro-1-thioacetylbenzene), which has been well known as a conducting molecule having possible application to molecular level negative differential resistance(NDR)[1]. Generally, the phenomenon of NDR can be characterized by the decreasing current with the increasing voltage[2]. To deposit the SAM layer onto gold electrode, we transfer the prefabricated nanopores into a 1mM self-assembly molecules in THF solution. Au(111) substrates were prepared by ion beam sputtering method of gold onto the silicon wafer. As a result, we measured the voltage-current properties and confirmed the negative differential resistance properties of self-assembled organic thin film and measured, using Scanning Tunneling Microscopy(STM).

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.75-75
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• 2011

Recently, dye-sensitized solar cell (DSSC) attracts great attention as a promising alternative to conventional silicon solar cells. One of the key components for the DSSC would be the nanocrystalline TiO2 electrode, and the control of interface between TiO2 and TCO is a highly important issue in improving the photovoltaic conversion efficiency. In this work, we applied various interfacial layers, and analyzed their effect in enhancing photovoltaic properties. In overall, introduction of interfacial layers increased both the Voc and Jsc, since the back-reaction of electrons from TCO to electrolyte could be blocked. First, several metal oxides with different band gaps and positions were employed as interfacial layer. SnO2, TiO2, and ZrO2 nanoparticles in the size of 3-5 nm have been synthesized. Among them, the interfacial layer of SnO2, which has lower flat-band potential than that of TiO2, exhibited the best performance in increasing the photovoltaic efficiency of DSSC. Second, long-range ordered cubic mesoporous TiO2 films, prepared by using triblock copolymer-templated sol-gel method via evaporation-induced self-assembly (EISA) process, were utilized as an interfacial layer. Mesoporous TiO2 films seem to be one of the best interfacial layers, due to their additional effect, improving the adhesion to TCO and showing an anti-reflective effect. Third, we handled the issues related to the optimum thickness of interfacial layers. It was also found that in fabricating DSSC at low temperature, the role of interfacial layer turned out to be a lot more important. The self-assembled interfacial layer fabricated at room temperature leads to the efficient transport of photo-injected electrons from TiO2 to TCO, as well as blocking the back-reaction from TCO to I3-. As a result, fill factor (FF) was remarkably increased, as well as increase in Voc and Jsc.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.291-291
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• 2013

The wettability of TiO2 layers is controlled by forming highly ordered arrays of nanocones using nanopatterning, based on self-assembly and dry etching. Nanopatterning of TiO2 layers is achieved via formation of self-assembled monolayers of SiO2 spheres fabricated using the Langmuir-Blodgett technique, followed by dry etching. Compared to a thin film TiO2 layer, the nanopatterned TiO2 samples show a smaller static water contact angle, where the water contact angle decreases as the etching time increases, which is attributed to the Wenzel equation. When TiO2 layers are coated by 1H,1H,2H,2H-perfluorooctyltrichlorosilane, we observed the opposite behavior, exhibiting superhydrophobicity (up to contact angle of $155^{\circ}$) on the nanopatterned TiO2 layers. Self-assembled nanopatterning of the TiO2 layer may provide an advanced method for producing multifunctional transparent layers with self-cleaning properties.

• Bulletin of the Korean Chemical Society
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• v.24 no.5
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• pp.593-599
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• 2003

The nanoparticle magnetite of which diameter was about 3 nm was synthesized in a homogeneous aqueous solution without a template. The synthesized magnetite nanoparticle was easily oxidized to maghemite in an ambient condition. The magnetic properties of the ferrite nanoparticle show superparamagnetism at room temperature and its blocking temperature is around 93 K. Modifying the sequential adsorption method of metal bisphosphonate, we have prepared a multilayer thin film of the ferrite nanoparticle on planar substrates such as glass, quartz and Si wafer. In this multilayer the ferrite nanoparticle layer and an alkylbisphosphonate layer are alternately placed on the substrates by simple immersion in the solutions of the ferrite nanoparticle and 1, 10-decanediylbis (phosphonic acid) (DBPA), alternately. This is the first example, as far as we know, of nanoparticle/alkyl-bisphosphonate multilayer which is an analogy of metal bisphosphonate multilayer. UV-visible absorption and infrared reflection-absorption studies show that the growth of each layer is very systematic and the film is considerably optically transparent to visible light of 400-700 nm. Atomic force microscopic images of the film show that the surface morphology of the film follows that of the substrate in μm-scale image and the nanoparticle-terminated surface is differentiated from the DBPA-terminated one in nm-scale image. The magnetic properties of this ferrite/DBPA thin film are almost the same as those of the ferrite nanoparticle powder only.

• Korea-Australia Rheology Journal
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• v.15 no.1
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• pp.1-7
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• 2003

A new method is introduced to build up organic/organic multilayer films composed of cationic poly(allylamine hydrochloride) (PAH) and negatively charged poly (sodium 4-styrenesulfonate) (PSS) using the spinning process. The adsorption process is governed by both the viscous force induced by fast solvent elimination and the electrostatic interaction between oppositely charged species. On the other hand, the centrifugal and air shear forces applied by the spinning process significantly enhances desorption of weakly bound polyelectrolyte chains and also induce the planarization of the adsorbed polyelectrolyte layer. The film thickness per bilayer adsorbed by the conventional dipping process and the spinning process was found to be about 4 ${\AA}$ and 24 ${\AA}$, respectively. The surface of the multilayer films prepared with the spinning process is quite homogeneous and smooth. Also, a new approach to create multilayer ultrathin films with well-defined micropatterns in a short process time is Introduced. To achieve such micropatterns with high line resolution in organic multilayer films, microfluidic channels were combined with the convective self-assembly process employing both hydrogen bonding and electrostatic intermolecular interactions. The channels were initially filled with polymer solution by capillary pressure and the residual solution was then removed by the .spinning process.

• Journal of the Korean Chemical Society
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• v.59 no.1
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• pp.36-44
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• 2015

This article describes synthesis and electrochemical properties of layer-by-layer self-assembled multilayer film composed of polyaniline (PANi), graphene oxide (GO) and phytic acid (PA), whereby the GO was electrochemically reduced to ERGO, resulting in $(PANi/ERGO/PANi/PA)_{10}$ film electrode. Especially, we examined the possibility to improve the volumetric capacitive property of $(PANi/ERGO)_{20}$ film electrode via combining a spherical hexakisphosphate PA nanoparticle into the multilayer film that would dope PANi properly and also increase the porosity and surface area of the electrode. The electrochemical performances of the multilayer film electrodes were investigated using a three-electrode configuration in 1 M $H_2SO_4$ electrolyte. As a result, the $(PANi/ERGO)_{20}$ electrode showed the volumetric capacitance of $666F/cm^3$ at a current density of $1A/cm^3$, which was improved to the volumetric capacitance of $769F/cm^3$ for the $(PANi/ERGO/PANi/PA)_{10}$ electrode, in addition to the cycling stability maintained to 79.3% of initial capacitance after 1000 cycles. Thus, the electrochemical characteristics of the $(PANi/ERGO)_{20}$ electrode, which was densely packed by ${\pi}-{\pi}$ stacking between the electron-rich conjugate components, could have been improved through structural modification of the multilayer film via combining a spherical hexakisphosphate PA nanoparticle into the multilayer film.