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Fabrication of oriented thin films using lyotropic chromonic liquid crystals and its templating applications = 유방성 크로모닉 액정을 이용한 배향 박막 제작 및 이의 템플릿 응용 연구
서명 / 저자 Fabrication of oriented thin films using lyotropic chromonic liquid crystals and its templating applications = 유방성 크로모닉 액정을 이용한 배향 박막 제작 및 이의 템플릿 응용 연구 / Yun Jeong Cha.
발행사항 [대전 : 한국과학기술원, 2018].
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8034452

소장위치/청구기호

학술문화관(문화관)B1층 보존서고

DNST 18005

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Soft materials have inherent properties that show an excellent self-assembly phenomenon and can react sensitively to external stimuli such as electric field. Thus, they can be applied not only to display field but also to various fields like new electronic materials, organic devices, and biosensors. Among the various soft materials, lyotropic chromonic liquid crystal (LCLC) phase appears in biocompatible materials such as various food coloring dyes and DNA. Recently, biotechnological applications have become important, thus studies for applying LCLCs in material science have been conducted. In particular, the LCLCs are inexpensive and abundant on the earth, it can be easily used without risk of depletion compared with other industrial materials, and thus it has received considerable attention in the material science. In addition, the LCLCs are well known for its interesting structural characteristics exhibiting self-organization by non-covalent interactions to form column structure, and have electrical and optical anisotropy along the column axis. In order to give new functions to LCLC materials and to apply them in various research fields, control of ordering of the LCLC molecules is very important. For this, various methods using external force such as magnetic field or confined geometry have been introduced. However, there was a limit for controlling the LCLC alignment in large areas. This Ph D. thesis will discuss the structural control of LCLCs including DNA in a large area. In this study, a system to orient LCLC by applying simple mechanical force, here shear force, have been developed in which the competitive interaction between elasticity of the molecules and shear forces induces various configurations of LCLCs. The fabricated thin films can be applied as templates due to the structural features of LCLCs, and furthermore, a thin film having high performance such as surface plasmonic properties can be produced by mixing with other metal nanoparticles.

연성 소재는 우수한 자기조립 현상 및 전기장과 같은 외부 자극에 민감하게 반응할 수 있는 고유의 성질을 가지고 있어 디스플레이 분야뿐만 아니라, 새로운 전자재료, 유기소자, 바이오센서, 생체시스템 모사 등 다양한 분야에 응용될 수 있다. 다양한 연성 소재 중, 라이오 트로픽 크로모닉 액정 (Lyotropic Chromonic Liquid Crystal) 상은 식용 색소나 DNA 같은 생체 물질에서 나타나며, 최근 생물 공학적 응용이 중요해지면서 이를 하나의 소재로서 응용하는 연구가 활발히 진행되고 있다. 특히, 라이오 트로픽 크로모닉 액정상은 값이 저렴하고, 지구상에 풍부하게 존재하기 때문에 다른 산업 재료에 비해 고갈될 위험 없이 쉽게 사용할 수 있어 재료로서 많은 관심을 받았다. 또한 분자체가 비공유 상호 작용에 의한 자기 조립에 의해 컬럼과 같은 흥미로운 구조를 형성하며 이 컬럼축을 따라 전기적 및 광학적 이방성을 가진다. 이러한 라이오 트로픽 크로모닉 액정 물질에 새로운 기능성을 부여하고 다양한 분야에 응용하기 위해서는 분자체의 구조제어가 매우 중요하기 때문에 자기장 같은 외부적 힘을 가하거나, 한정된 공간을 이용하는 구조 제어 방법이 도입되었지만 분자들을 대면적에서 제어하기에 한계가 있었다. 본 박사학위 논문에서는 DNA 를 포함한 LCLC 분자체를 대면적에서 정밀하게 구조 제어하는 연구에 관해 논하고자 한다. 본 연구에서는 매우 간단한 기계적 힘을 가하는 전단 코팅 방법으로, 전단 속도에 따른 전단응력과 탄성력의 균형조절 및 전단 응력을 가하는 방식을 달리하여 LCLC 분자체를 다양한 형태로 배향시키는 시스템을 정립하였다. 제작된 배향 박막은 LCLC의 정교한 구조적 특징에 의하여 나노 물질 템플릿과 같은 기능성 재료로 응용될 수 있으며, 더 나아가 다른 금속 나노 입자와의 혼성을 통해 표면 플라즈모닉 특성과 같은 고기능의 박막을 제작할 수 있다.

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서지기타정보
청구기호 {DNST 18005
형태사항 iv, 58 p. : 삽화 ; 30 cm
언어 영어
일반주기 저자명의 한글표기 : 차윤정
지도교수의 영문표기 : Dong Ki Yoon
지도교수의 한글표기 : 윤동기
학위논문 학위논문(박사) - 한국과학기술원 : 나노과학기술대학원,
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States of matter. Liquid crystal is the intermediate between well-ordered crystalline solid andisotropic liquid.

Schematic diagram for classifying various types ofliquid crystals (LCs). (a) Thermotropic liquid crystal (TLC) having various LC phases depending on temperature. (b) Lyotropic liquidcrystal (LLC) havingLCphases like vesicle, hexagonal and lamellar depending on concentration ofthe solute in solution.2

SchematicdiagramofLyotropic chromonic liquidcrystal(LCLC)(a) Molecular structure ofSunsetyellow a representative LCLC. (b) Plank-like molecule with a hydrophobic core and hydrophilic groups at the periphery. (c) Cylindrical aggregate ofLCLC in water.

Magnetic field induced DNA orientation. POM images with a retardation plate show that the anisotropic 20 DNA film formed by applying magnetic field (the direction ofthe magnetic field denoted byred arrows)

Alignment of LCLCs by confined geometries. (a) Alignment of nano-DNA by confinement in microchannels. Nano-DNA molecules are filled in the channel, where LD is the loading direction of the concentrated DNA sample. Illustration shows that nano-DNAs are oriented perpendicular to the channel direction.21 (b) Orientational control ofLCLCs using micro-post patterns. In the Nematic phase, the LCLCs are

Alignment ofLCLC by mechanical shearing method. (a) Schematic representation ofshear-flow induced coating method. (b) The axis of'columns are aligned parallel to the pulling direction.

Interaction ofthermotropic liquidcrystals (TLCs) with LCLCfilm(a)Alignment ofrod-shaped TLCsl well-oriented LCLC film atbottom. ThedirectorofTLC(nTLC) isparallel to the director ofLCLC(nLCLC).( The alignment ofTLC along the director ofsingle-stranded DNA (InssDNA). (c) TLCs on double-stranded DN (dsDNA) surface, whichrotates at an oblique angle (~30이) with respect to the orientation ofdsDNA(ndsDNA

Schematic illustration ofthe shear flow induced method with various pulling speeds and corresponding molecular orientation ofthe LCLC film. (a) Schematic illustrations ofthe shear flow induced process and (b) the different orientations of LCLCs at different pulling speeds. Stacks of plank-shaped molecules indicate SSY aggregates, and the double-headed arrows indicate the LC director. SSY columns a

Molecular orientations according to an Ericksen number (Er). (a) Er~6atv~ 100 nm/s, an uniform configuration parallel to the contact line is preferred because ithas the lowest elastic energy since there is no deformation. (b) Er~ 18atv~ 300pm/s is much larger than that atv~ 100 pm/s. This can be regarded as the shear flow dominant condition.

POM images ofthe sheared SSY film produced by a constant slow pulling speed of 100 nm/s at 65'C. (a)Ashear aligned SSYfilm when the pullingdirection was diagonal to theanalyzerand (b)parallel to the analyzer (c-d) (c,d) POM images with a retardation plate (= 530 nm) when the pulling direction was perpendicular and parallelwith respect to the slow axis of retardation plate (magenta color arrow in t

POM images ofthe sheared SSY film fabricated bya constantfastpullingspeed of300 um/sat 65'C. (a) A POM image ofshear aligned SSY film, in which the pulling direction at -45o with respect to the analyzer and (b) parallel to the analyzer. (c,d) POM images with a retardation plate (2 = 530 nm) when the pulling direction was perpendicular and parallel, respectively, with respect to the slow axis ofthe

Sequential changes ofnssY under various pulling speeds of upper substrate: (a-c) 100 nm/s, (d-f) 200 nm/s, and (g-i) 300 pm/s. The white dashed lines indicate the contact line of the meniscus. (j, k) Schematic illustrations showing vertical cross sections ofthe meniscus at slow (j) and fast (k) pulling speeds, which denoted cyan and green dotted lines, respectively (a and g).

Orientation diagram as a function ofpullingspeeds and POMimages ateach orientation. (a) Diagram for nsSY depending on the pullingspeeds and temperatures. Yellow circles, green triangles, and blue squares represent nssY 1 shear direction, transition point, and nssY // shear direction, respectively. (b-g) Various orientations of SSY are shown using POM (b,d,f) and POM with retardation plate a= 530nm

Orthogonally oriented SSY film. (a)POMimageofthe SSY film with a slow (100 pm/s)anda fastpulling speed (300 nm/s). (b) Intensity profiles ofthepolarized lightpassing through the slow sheared region(red circles and the fast sheared region (black squares) ofthe film as a function ofthe rotational angle (0) between the shear direction and the polarizer (P), in which only one P was used. (c, d) POM im

GIXD patterns ofthe orthogonal SSY film obtained from (a) the fast sheared domain and (b) the slow sheared domain. The schematic illustrations represent the nSSY and the incident beam direction (yellow arrows) in the GIXD experiment.

LC cell using an orthogonal SSY alignment layer. POM images show the N and TN domains of 5CB molecules in the cell, where RD 1S parallel (a, c) and tilted (b) to the crossed polarizers. (d) Schematic illustration ofthe LC cell, in which RD is parallel and perpendicular with nSSY in the N and TN domains, respectively. (e) Intensity profiles from the hybrid LC cell show the transmitted intensities o

Fabrication of DNA films without/with shearing process. Polarized optical microscopy (POM) images and inserted schematic diagrams of(a) DNA film fabricated by evaporation ofthe DNA droplet and (b) sheared DNA film using brush. Schematic diagrams corresponding nDNA (c) without shearing and (d) shearing representing the (c) randomly oriented and (d) periodically aligned DNA chains.

Atomic force microscopy (AFM) images ofDNA film (a) without shearing (b) with shearing. The AFM images clearly showed the (a) randomly arranged and (b) periodically undulated DNA chains.

Sequential change ofDNA arrangement duringthe evaporation of water without/with shearing process. Polarized optical microscopy (POM) images with retardation plate, a-c) without shearing, and d-f) with shearing In the DNA zigzag film, the modulation ofnDNA is developed as the water evaporates at d)0 S, e) 10 S, f) 20S (scale bars of(d)-(f), and inset are 100 nm). ED and SD are an evaporation direct

Control of the periodicity (P) of the DNA zigzag pattern. (a) Schematic illustration and (b) scanning electron microscope (SEM) image ofthe typical topographic pattern ofthe microchannel (d~5 nm and w~5 um). Polarized optical microscopy (POM) images ofthe DNA zigzag patterns with various channel depths ofb) 3 rm c)5 um, and d) 10 cm at the fixed width of50 nm. e)Pversus channel depth represents th

Optical textures of DNA zigzag patterns with different widths. Polarized optical microscopy (POM) images ofDNA zigzags in the microchannels ofa) 5 um, b)20 um, and c) 50 nm at the fixed depth, 5 um.

Morphological changes of liquid crystal (LC) molecules on the DNA zigzag layer during cooling. (a) Isotropic phase at 45 ㅇC, (b) stripe patterns during phase transition, (c) dividing the stripe patterns into small domains offocal conic domains (FCDs),and d)a linear array ofFCDs on the defectline ofthe DNAtemplate. (e) AFM image ofthe FCD arranged in a low and (f) height profile ofFCDs indicated by

N phase liquid crystals (NLCs) on the DNAzigzag film. Polarized optical microscopy (POM)images of NLCs on DNA template when (a) shearing direction (SD) isparallel and (b) diagonal to the polarizers, respectively.

Fluorescence confocal polarizing microscopy (FCPM) images and Illustrations ofliquid crystals (LCs) on the DNA zigzag film. (a) When the angle (0) between Pol and shearing direction (SD) is 90', the N phase liquid crystals (LCs) showed alternating bright and dark bands. (b) When the sample was rotated to (b) 0 = 45', the intensities ofthe alternating bands changes to similar, and (c) at0', the int

Illustration shows DNA-Gold nanorods (GNR) mixture, in which the GNRs are aligned along the DNA chains.

TEM images ofGNRs used in this study (a) at low magnification, and (b) at magnified scale. Extinction spectra of pristine GNR and DNA-GNR dispersion. Randomly arranged (a) pristine GNRs (b) DNAs-GNRs dispersion. The position ofSPR peaks is red shifted because the dielectric constant of the surrounding medium increases (Refractive index of water n = 1.333 and that ofDNAn= 1.5)

Fabrication processes to make DNA-GNR films (a-c) without(d-k) withshearing. (a) An evaporatec dropletofDNA GNR dispersions on a substrate. b) Cross-section view ofthe droplet, where the DNA GNRs are distributed randomly. (c) Therandomly arranged DNA GNR film. (d) A scheme ofshearflow induced coatinc method. V ertical cross-section ofthe meniscus at(e)slow or(g) fastpulling speed. Thisresults in t

POM images and SPR spectra ofDNA-GNR film by different manufacturing method. (a) POM images inserted retardation plate when the DNA-GNR composite is spread on a substrate, forming short-range ordered columnar crystal structures. The corresponding extinction color when linearly polarized lightis (b) horizontal and (c) vertical, showing the extinction colors mixed with red and green. (d) Extinction

Direct observation of the aligned GNRs. (a) Transmission optical microscopy image at P // pulling direction. (b) SEMimage ofthe DNA-GNRfilm, which was fractured, in which the nGNR//pulling direction. (Red arrows indicate the pulling direction ofthe upper substrate.)

Orthogonal pattern ofDNA-GNR film by shear flow induced coating method with varyingpullingspeeds. (a) Schematic illustration ofthe orthogonally arranged DNA-GNR film. Retardation plate inserted POM images oforthogonally aligned DNA GNR film when (b)14pulling direction and (c)2//pulling direction, respectively. (d)POMimage oforthogonally patterned DNA- GNR film when the pulling direction is diagona

Zigzag pattern of DNA-GNR film prepared by scrubbing method. (a) Schematic illustration of the undulated DNA-GNR film. (b) POM image ofzigzag structured DNA-GNR film when the scrubbing direction was parallel to analyzer (A). (c) POM images ofzigzag structured DNA- GNR film when the crossed polarizers rotated 455. (d) Zigzag pattern observed in the retardation plate inserted POM experiment.

Transmission optical microscopy images ofDNA-GNR film produced byscrubbing method. Theimages taken bychangingthe angle (p) between linear polarization ofincident light(P) andscrubbingdirection as follows: (a)ㅇ= 90~, (b)0 = 80이, (c) 0= 70', (d)ㅇ=60', (d)0=509,(f)p=40',(g)0=30·,(h)o=20',(i)ㅇ=10', and j) (= 0*. (Red arrows indicate the scrubbing direction.)

DNA-GNR film aligned in a large area. (a,c,d) Unidirectionally Oriented DNA-GNR film without (a) polarizer, (c) with polarizer placed horizontally or (d) vertically to the pulling direction. (b) Sample position for SPR intensity measurement. (e) SPR intensity profiles at the wavelength of longitudinal (black square) and transverse (red circle) peak from aligned DNA-GNR film and at the wavelength o