KR20130104867A - Transparent conductive films by graphene oxide/silver nanowire having high flexibilities - Google Patents
Transparent conductive films by graphene oxide/silver nanowire having high flexibilities Download PDFInfo
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Abstract
Description
본 발명은 고유연성을 가지는 산화 그라핀/은 나노와이어 하이브리드를 기반으로 하는 투명전도성 필름에 관한 것으로, 모세관 유동을 구동력으로 이용하여 나노 두께의 산화 그라핀 필름을 제조한 후 그 위에 은 나노와이어 네트워크를 형성시킴으로써 산화 그라핀과 은 나노와이어와의 강한 상호작용으로 기계적 안정성과 유연성이 우수한 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 및 그 제조방법에 관한 것이다. The present invention relates to a transparent conductive film based on graphene oxide / silver nanowire hybrid having high flexibility, and to preparing a nano-thick graphene oxide film using capillary flow as a driving force thereon, the silver nanowire network thereon. The present invention relates to a graphene oxide / silver nanowire hybrid transparent conductive film having excellent mechanical stability and flexibility in a strong interaction between graphene oxide and silver nanowires by forming a nanowire and a method of manufacturing the same.
투명전도성 필름은 전자장치의 많은 분야에서 필수적이며, 터치스크린, 유기 발광 다이오드, 평판 디스플레이, 태양전지 등에 널리 사용되고 있다.Transparent conductive films are essential in many fields of electronic devices, and are widely used in touch screens, organic light emitting diodes, flat panel displays, and solar cells.
일반적으로, 투명전도성 필름으로 인듐 주석 산화물(ITO)을 주로 사용하는데, 그 이유는 가시광 영역 전체에서 우수한 투명성을 가지며, 상대적으로 면저항이 낮고, 유기반도체에서 전하 운반체가 주입되고 모아지는데 적절한 일함수를 갖기 때문이다. In general, indium tin oxide (ITO) is mainly used as a transparent conductive film because of its excellent transparency throughout the visible region, relatively low sheet resistance, and a suitable work function for injecting and collecting charge carriers in organic semiconductors. Because it has.
그러나, 인듐 주석 산화물은, 고온 공정을 통해 합성되기 때문에 플라스틱 기판 위에서는 사용될 수 없고, 매우 고가이며, 깨지기 쉬운 성질 때문에 플렉시블 투명전도성 필름으로 사용하는데 많은 제약이 따른다. 그러므로 인듐 주석 산화물 기판이 전자산업에서 사용되기 위해서는 개발이 필요하다.
However, indium tin oxide cannot be used on plastic substrates because it is synthesized through a high temperature process, and due to its very expensive and fragile nature, there are many limitations in using it as a flexible transparent conductive film. Therefore, indium tin oxide substrate needs to be developed for use in the electronics industry.
국내특허공개 제10-2011-0107197호를 비롯하여 많은 연구를 통해 인듐 주석 산화물을 대체 할 수 있으면서 그와 투명전도성 필름으로써 상응하는 물질들의 개발이 진행되어 왔다. 대체 물질들 중에서도 은(Ag) 나노와이어(nanowire, NW)는 종횡비가 크고, 전기전도도가 6.3×107 S/m로 모든 금속 중에서 가증 높아 플렉시블한 전자기기에 사용할 수 있는 투명전도성 필름으로 매우 유망한 물질로 알려져 있다(C.-H. Liu and X. Yu, Nanoscale Res. Lett., 6, 75-82, 2011; L. Hu, H. S. Kim, J.-Y. Lee, P. Peumans and Y. Cui, ACS nano, 4, 2955-2963, 2010).
Through many studies, including Korean Patent Publication No. 10-2011-0107197, development of corresponding materials has been progressed as a transparent conductive film that can replace indium tin oxide. Among the alternative materials, silver (Ag) nanowires (NW) have a high aspect ratio and an electrical conductivity of 6.3 × 10 7 S / m, which is highly abominable among all metals. Substances are known (C.-H. Liu and X. Yu, Nanoscale Res. Lett ., 6 , 75-82, 2011; L. Hu, HS Kim, J.-Y. Lee, P. Peumans and Y. Cui, ACS nano , 4 , 2955-2963, 2010).
한편, 2차원의 카본 구조인 그라핀(graphene)은 높은 캐리어 이동도, 양극성 전계효과, 양자홀 효과와 같은 유일한 전기적 성질 때문에 상당한 관심을 받고 있다. 산소 기능기를 많이 함유하고 있는 산화 그라핀(graphene oxide, GO)는 흑연을 화학적으로 산화시켜서 쉽게 얻을 수 있다.On the other hand, graphene, a two-dimensional carbon structure, has received considerable attention because of its unique electrical properties such as high carrier mobility, bipolar field effect, and quantum hole effect. Graphene oxide (GO), which contains many oxygen functional groups, can be easily obtained by chemically oxidizing graphite.
산화 그라핀은 많은 산소 기능기로 인해 수용액과 극성 유기용매에서 안정하다. 더불어 산화 그라핀의 극성부분은 금속과 매우 강한 정전기적 상호작용을 유발할 수 있다.Graphene oxide is stable in aqueous solutions and polar organic solvents due to its many oxygen functional groups. In addition, the polar portion of graphene oxide can cause very strong electrostatic interaction with metals.
그라핀과 은 사이의 강한 상호작용에 대해 보고된 몇 편의 논문이 있지만(J. Lee, K. S. Novoselov and H. S. Shin, ACS nano, 5, 608-612, 2011; J. Li and C. Liu, Eur. J. Inorg. Chem., 2010, 1244-1248, 2010), 은-그라핀 하이브리드를 이용한 투명전도성 필름에 대한 연구는 찾아볼 수 없다.
There are several papers reported on the strong interaction between graphene and silver (J. Lee, KS Novoselov and HS Shin, ACS nano , 5 , 608-612, 2011; J. Li and C. Liu, Eur. J. Inorg. Chem ., 2010 , 1244-1248, 2010), studies of transparent conductive films using silver-graphene hybrids have not been found.
산화 그라핀 현탁액의 작은 방울은 건조될 때, "커피 링 얼룩"의 전형적인 패턴을 보이는데, 이는 보통의 물에 용해되거나 분산 가능한 물질에서 나타나는 패턴이다. 상기 링 패턴은 분산된 고체를 포함하는 물방울이 기판 위에서 증발될 때 보통 생기며, 인쇄, 세척, 코팅 등의 과정에 영향을 준다.
Small droplets of graphene oxide suspension, when dried, exhibit a typical pattern of “coffee ring stains”, which are patterns that appear in materials that are soluble or dispersible in ordinary water. The ring pattern usually occurs when water droplets containing dispersed solids evaporate on the substrate and affect the process of printing, cleaning, coating, and the like.
본 발명자들은 산화 그라핀과 은 나노와이어를 이용하여 플렉시블한 투명전도성 필름을 개발하고자 예의 노력한 결과, 모세관 유동을 구동력으로 이용하여 나노 두께의 그라핀을 제조하고 이를 기판에 코팅한 후 은 나노와이어 네트워크를 형성시킴으로써 본 발명을 성공적으로 완성하였다. The present inventors earnestly tried to develop a flexible transparent conductive film using graphene oxide and silver nanowires. As a result, a nano-nanowire network was prepared by manufacturing a graphene-thick graphene using capillary flow as a driving force and coating it on a substrate. The present invention was successfully completed by forming.
결국, 본 발명의 주된 목적은 산화 그라핀과 은 나노와이어 하이브리드를 기반으로 하는 고유연성을 가지는 투명전도성 필름 및 그 제조방법을 제공하는데 있다.After all, the main object of the present invention is to provide a transparent conductive film having a high flexibility based on graphene oxide and silver nanowire hybrid and a method of manufacturing the same.
상기 목적을 달성하기 위하여, 본 발명은 나노 두께의 산화 그라핀을 코팅한 기판 위에 은 나노와이어 네트워크를 형성시킨 산화 그라핀과 은 나노와이어 하이브리드를 기반으로 하는 고유연성을 가지는 투명전도성 필름 및 그 제조방법을 제공한다. In order to achieve the above object, the present invention is a transparent conductive film having a high flexibility based on a graphene oxide and a silver nanowire hybrid formed with a silver nanowire network on a substrate coated with a nano-thick graphene oxide and its production Provide a method.
본 발명에 따른 산화 그라핀/은 나노와이어 하이브리드를 기반으로 하는 투명전도성 필름은, 산화 그라핀과 은 나노와이어 사이에 정전기적 상호작용이 존재하기 때문에 은 나노와이어는 산화 그라핀 위에 네트워크가 잘 형성되며, 또한 열처리 과정을 거치면서 산화 그라핀과 은 나노와이어가 서로 더 잘 접착하여, 매우 안정하고, 플렉시블하며, 투과도가 86%일 때, 면저항이 150 Ω/□으로 인듐 주석 산화물에 상응하는 성능을 나타낸다.In the transparent conductive film based on the graphene oxide / silver nanowire hybrid according to the present invention, since the electrostatic interaction between the graphene oxide and the silver nanowires exists, the silver nanowires have a good network formation on the graphene oxide. In addition, the graphene oxide and the silver nanowires adhere better to each other during the heat treatment process, so that when the stability is very stable, flexible and the transmittance is 86%, the sheet resistance is 150 Ω / □, which corresponds to the indium tin oxide. Indicates.
또한, 본 발명에 따른 제조방법은 간단하면서도 친화경적인 투명전도성 필름을 제조하는 것이 가능하므로, 터치스크린, 유기 발광 다이오드, 평판 디스플레이, 태양전지 등의 제조에 유용하게 이용될 수 있다.In addition, the manufacturing method according to the present invention can be used to manufacture a touch screen, an organic light emitting diode, a flat panel display, a solar cell, and the like, since it is possible to manufacture a simple and friendly transparent conductive film.
도 1은 본 발명에 따른 나노 두께의 산화 그라핀 필름을 형성하는 과정을 도식화하여 나타낸 것이다.
도 2는 본 발명의 일실시예에 따른 기판 위에 코팅된 산화 그라핀 층의 표면을 관찰한 SEM 사진이다(a: 기판 위의 산화 그라핀 층; b: 산화 그라핀 층의 단면; c: 산화 그라핀 층의 AFM 이미지; 및 d: 산화 그라핀 층의 3D 위상 AFM 이미지).
도 3은 본 발명에 따른 은 나노와이어의 SEM 사진이다(a: 폴리올 공정으로 합성된 은 나노와이어; b: 산화 그라핀 층 위의 은 나노와이어 네트워크; c: 열처리 전 은 나노와이어; 및 d: 열처리 후의 은 나노와이어).
도 4는 본 발명의 일실시예에 따른 다양한 기판 위에 코팅된 산화 그라핀 층의 SEM 사진이다(a: 석영 기판; b: 유리 기판, c: 석영 기판 위의 산화 그라핀/은 나노와이어 네트워크 하이브리드 필름; 및 d: 유리 기판 위의 산화 그라핀/은 나노와이어 네트워크 하이브리드 필름).
도 5는 본 발명에 따른 산화 그라핀/은 나노와이어 하이브리드 필름의 열처리 효과를 도식화하여 나타낸 것이다.
도 6은 본 발명에 따른 산화 그라핀/은 나노와이어 하이브리드 필름의 XP 스펙트라이다(a: C 1s XP 스펙트라; 및 b: Ag 3d XP 스펙트라).
도 7은 본 발명의 일실시예에 따른 다양한 기판 위의 산화 그라핀/은 나노와이어 하이브리드 필름의 UV-Vis 스펙트라이다(a: 석영 기판; b: 유리 기판; 및 c: PET 기판).
도 8은 본 발명의 일실시예에 따른 다양한 기판 위의 산화 그라핀/은 나노와이어 하이브리드 필름의 550 ㎚에서의 투광도 및 시트저항을 나타낸 것이다.
도 9는 본 발명에 따른 산화 그라핀/은 나노와이어 하이브리드 필름의 벤딩 횟수에 대한 시트저항을 나타낸 것이다.
도 10은 본 발명에 따른 산화 그라핀/은 나노와이어 하이브리드 필름의 열처리 전후의 기계적 안정성을 확인한 사진이다.1 is a schematic view showing a process of forming a nano-thick graphene oxide film according to the present invention.
2 is a SEM photograph of the surface of a graphene oxide layer coated on a substrate according to an embodiment of the present invention (a: graphene oxide layer on the substrate; b: cross section of the graphene oxide layer; c: oxidation AFM image of graphene layer; and d: 3D phase AFM image of graphene oxide layer).
3 is a SEM photograph of silver nanowires according to the present invention (a: silver nanowires synthesized by polyol process; b: silver nanowire network on graphene oxide layer; c: silver nanowires before heat treatment; and d: Silver nanowires after heat treatment).
4 is a SEM photograph of a graphene oxide layer coated on various substrates according to an embodiment of the present invention (a: quartz substrate; b: glass substrate; c: graphene oxide / silver nanowire network hybrid on quartz substrate) Film and d: graphene oxide / silver nanowire network hybrid film on a glass substrate).
5 is a diagram showing the heat treatment effect of the graphene oxide / silver nanowire hybrid film according to the present invention.
6 is XP spectra of graphene oxide / silver nanowire hybrid films according to the present invention (a: C 1s XP spectra; and b: Ag 3d XP spectra).
7 is a UV-Vis spectra of graphene oxide / silver nanowire hybrid films on various substrates in accordance with one embodiment of the present invention (a: quartz substrate; b: glass substrate; and c: PET substrate).
FIG. 8 illustrates light transmittance and sheet resistance at 550 nm of graphene oxide / silver nanowire hybrid films on various substrates according to an embodiment of the present invention.
9 shows sheet resistance with respect to the number of bending of the graphene oxide / silver nanowire hybrid film according to the present invention.
10 is a photograph confirming the mechanical stability before and after heat treatment of the graphene oxide / silver nanowire hybrid film according to the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 산화 그라핀과 은 나노와이어 하이브리드를 기반으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름을 제공한다.The present invention provides a graphene oxide / silver nanowire hybrid transparent conductive film based on graphene oxide and silver nanowire hybrid.
본 발명에서, 상기 투명전도성 필름은 투과도가 80~90%일 때, 면저항이 40~200 Ω/□인 것이 특징이다.
In the present invention, the transparent conductive film is characterized in that the sheet resistance of 40 ~ 200 Ω / □ when the transmittance is 80 ~ 90%.
또한, 본 발명에서 상기 투명전도성 필름은, In addition, the transparent conductive film in the present invention,
(1) 나노 두께의 산화 그라핀 필름을 제조하는 단계;(1) preparing a nano-thick graphene oxide film;
(2) 폴리비닐피롤리돈(PVP) 존재 하에 에틸렌글리콜을 이용하여 질산은을 환원시켜 은 나노와이어를 제조하는 단계; 및(2) preparing silver nanowires by reducing silver nitrate using ethylene glycol in the presence of polyvinylpyrrolidone (PVP); And
(3) 상기 (2) 단계에서 제조한 은 나노와이어를 상기 (1) 단계에서 제조한 산화 그라핀 필름 위에 부착하는 단계; (3) attaching the silver nanowires prepared in step (2) onto the graphene oxide film prepared in step (1);
(4) 상기 (3) 단계에서 제조된 은 나노와이어 네트워크를 포함하는 산화 그라핀 필름을 건조시켜 투명전도성 필름을 제조하는 단계; 및(4) preparing a transparent conductive film by drying the graphene oxide film including the silver nanowire network prepared in step (3); And
(5) 상기 투명전도성 필름을 열처리(thermal annealing)하는 단계;를 포함하여 제조할 수 있다.
(5) heat-treating the transparent conductive film (thermal annealing); may be prepared.
본 발명에서, 상기 나노 두께의 산화 그라핀 필름은 모세관 유동을 구동력으로 이용하여 제조하는 것을 특징으로 한다.In the present invention, the nano-thick graphene oxide film is characterized in that it is prepared using a capillary flow as a driving force.
모세관 유동은 용매가 증발할 때 기판과 액체 사이의 계면에서 발생하며, 상기 힘에 의해 산화 그라핀 현탁액에서 나노 규모의 산화 그라핀 필름이 형성된다. 또한, 상기 산화 그라핀 필름의 두께는 증발 속도와 산화 그라핀 현탁액의 농도 조절을 통해 가능하며, 본 발명에서 산화 그라핀 현탁액의 농도는 0.0001~0.0003중량%인 것이 바람직하다.
Capillary flow occurs at the interface between the substrate and the liquid when the solvent evaporates, and the force forms a nanoscale graphene oxide film in the graphene oxide suspension. In addition, the thickness of the graphene oxide film can be adjusted through the evaporation rate and the concentration of the graphene oxide suspension, in the present invention, the concentration of the graphene oxide suspension is preferably 0.0001 ~ 0.0003% by weight.
또한, 상기 나노 두께의 산화 그라핀 필름은 천연 흑연으로부터 Hummers method(W. S. Hummers, JR. and R. E. Offeman, J. Am . Chem . Soc ., 80, 1339-1339, 1958)를 이용하여 제조할 수 있다.In addition, the nano-thick graphene oxide film can be prepared from natural graphite using the Hummers method (WS Hummers, JR. And RE Offeman, J. Am . Chem . Soc ., 80 , 1339-1339, 1958). .
구체적으로, 본 발명의 나노 두께의 그라핀 필름은, (a) 천연 흑연을 동결건조하는 단계; (b) 상기 동결건조된 천연 흑연을 초음파 처리를 통해 박리시켜 현탁액을 제조하는 단계; 및 (c) 상기 산화 그라핀 현탁액을 기판 위에 코팅하는 단계;를 포함하여 제조한다.Specifically, the nano-thick graphene film of the present invention, (a) lyophilizing natural graphite; (b) exfoliating the lyophilized natural graphite through sonication to prepare a suspension; And (c) coating the graphene oxide suspension onto a substrate.
상기 (a) 단계에서는, 천연 흑연으로 현탁액을 제조한 후, 먼저 액체 질소로 동결시켜 -50℃, 0.04~0.05 mbar의 동결건조기에서 72시간 동안 동결건조시킴으로써 낮고 느슨하게 패킹된 산화 그라핀 파우더를 얻을 수 있으며, 상기 산화 그라핀 파우더를 증류수에 넣고 초음파처리를 통해 박리시키면 상기 (b) 단계의 산화 그라핀 현탁액이 제조된다.In the step (a), after preparing the suspension with natural graphite, first freeze with liquid nitrogen to freeze-dried for 72 hours in a freeze dryer of -50 ℃, 0.04 ~ 0.05 mbar to obtain a low and loosely packed graphene oxide powder The graphene oxide powder of step (b) may be prepared by immersing the graphene oxide powder in distilled water and peeling it through sonication.
또한, 상기 (c) 단계에서는 상기 산화 그라핀 현탁액을 유리, 석영 및 폴리에틸렌프탈레이트(PET)에서 선택되는 어느 하나의 기판 위에 코팅하여 건조함으로써 10~50 ㎚ 두께의 산화 그라핀 필름을 제조할 수 있다.In addition, in the step (c), the graphene oxide suspension may be coated on a substrate selected from glass, quartz, and polyethylene phthalate (PET) and dried to prepare a graphene oxide film having a thickness of 10 to 50 nm. .
이때, 기판 위에 상기 산화 그라핀 현탁액을 코팅하는 방법은, 특별히 한정시킬 필요는 없으며, 업계에서 통상적으로 사용하는 방법이라면 어떠한 방법도 무방하다.
In this case, the method of coating the graphene oxide suspension on the substrate is not particularly limited, and any method may be used as long as it is a method commonly used in the art.
또한, 본 발명에서, 상기 은 나노와이어는 폴리올 공정(polyol process)을 이용하여 제조하는 것이 특징이며, 이때 제조된 은 나노와이어의 평균 길이는 1~10 ㎛이고, 평균 직경은 70~80 ㎚이다.
In addition, in the present invention, the silver nanowire is characterized in that it is produced using a polyol process (polyol process), wherein the average length of the prepared silver nanowire is 1 ~ 10 ㎛, the average diameter is 70 ~ 80 nm .
또한, 본 발명에서, 상기 은 나노와이어는 상기 산화 그라핀 필름 위에 딥 코팅 방법을 이용하여 부착(네트워킹)시키는 것이 특징이다.
In addition, in the present invention, the silver nanowires are characterized in that the adhesion (networking) on the graphene oxide film using a dip coating method.
또한, 본 발명에서, 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름은 산화 그라핀과 은 나노와이어의 정전기적 상호작용을 이용하여 부착시키는 것을 특징으로 하며, 산화 그라핀과 은 나노와이어가 서로 잘 부착되고, 은 나노와이어의 전기전도성을 증가시키기 위해서는 산소분위기에서 150℃에서 30분간 열처리를 해 주는 것이 바람직하다.
In addition, in the present invention, the graphene oxide / silver nanowire hybrid transparent conductive film is characterized in that by using the electrostatic interaction of the graphene oxide and silver nanowires, the graphene oxide and silver nanowires well with each other In order to increase the electrical conductivity of the silver nanowires, heat treatment is preferably performed at 150 ° C. for 30 minutes in an oxygen atmosphere.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
실시예 1. 산화 그라핀 현탁액 제조Example 1 Graphene Oxide Suspension Preparation
본 발명에서, 산화 그라핀을 천연 흑연으로부터 Hummers method을 이용하여 제조하였다.In the present invention, graphene oxide was prepared from natural graphite using the Hummers method.
구체적으로, 천연 흑연(Sigma-Aldrish)을 액체 질소에 의해 얼린 후, -50℃, 0.045 mbar의 동결건조기(LP3, Jouan, France)에서 72시간 동결건조시켜 얻은 산화 그라핀 파우더 2 ㎎을 1000 ㎖의 증류수에 넣고 초음파처리 하여 박리시켜 산화 그라핀 현탁액을 제조하였다.
Specifically, 1000 mg of 2 mg of graphene oxide powder obtained by freezing natural graphite (Sigma-Aldrish) with liquid nitrogen and freeze-drying for 72 hours in a freeze dryer (LP3, Jouan, France) at -50 ° C and 0.045 mbar To put in distilled water of sonication was peeled to prepare a graphene oxide suspension.
실시예 2. 은 나노와이어 합성Example 2. Silver Nanowire Synthesis
본 발명에서 은 나노와이어는, 폴리비닐피롤리돈(PVP) 존재 하에서 에틸렌글리콜을 이용해 질산은(AgNO3)을 환원시켜 제조하였다.In the present invention, silver nanowires were prepared by reducing silver nitrate (AgNO 3 ) using ethylene glycol in the presence of polyvinylpyrrolidone (PVP).
구체적으로, 용매가 에틸렌글리콜인 질산은 용액(0.1 M) 10 ㎖를 플라스크에 담아 160℃로 가열한 후, 염화나트륨용액(1.7 mM) 1 ㎖를 빠르게 첨가하여 15분간 반응시켰다. 그런 다음, 폴리비닐피롤리돈 용액(0.15 M)을 주사기를 이용하여 10분간 한방울씩 반응기에 주입하고, 주입이 끝난 후에는 160℃의 반응 온도를 2시간 동안 유지하였다. 이때, 전 과정에서 매우 강하게 교반하였다.Specifically, 10 ml of silver nitrate solution (0.1 M) in which the solvent was ethylene glycol was put in a flask and heated to 160 ° C., and then 1 ml of sodium chloride solution (1.7 mM) was quickly added to react for 15 minutes. Then, polyvinylpyrrolidone solution (0.15 M) was injected dropwise into the reactor for 10 minutes using a syringe, and after the injection was completed, a reaction temperature of 160 ° C. was maintained for 2 hours. At this time, the mixture was stirred very vigorously throughout.
반응이 완료되면, 상온으로 용액을 식힌 후에 아세톤을 이용하여 희석시킨 다음 4000 rpm으로 30분간 원심분리하였다. 원심분리 후에 남아있는 에틸렌글리콜이 녹아있는 상부액은 주사기를 이용하여 제거하였으며, 폴리비닐피롤리돈은 증류수를 이용하여 동일한 방법으로 원심분리 후 제거하였다.After the reaction was completed, the solution was cooled to room temperature, diluted with acetone, and then centrifuged at 4000 rpm for 30 minutes. The supernatant in which ethylene glycol remained after centrifugation was removed using a syringe, and polyvinylpyrrolidone was removed after centrifugation in the same manner using distilled water.
상기와 같이 정제된 생성물은 진공오븐에서 건조하였다.
The product thus purified was dried in a vacuum oven.
실시예 3. 하이브리드 투명전도성 필름 제조Example 3. Preparation of Hybrid Transparent Conductive Film
유리와 석영, 폴리에틸렌테레프탈레이트 기판을 0.0002중량%의 산화 그라핀 현탁액에 담가 333 K 온도의 오븐에서 24시간 동안 방치시킨 후 물을 증발시켜 기판 위에 산화 그라핀을 코팅하였다.The glass, quartz, and polyethylene terephthalate substrates were immersed in a 0.0002% by weight graphene oxide suspension and left in an oven at 333 K for 24 hours, followed by evaporation of water to coat the graphene oxide on the substrate.
그런 다음, 에탄올 50 ㎖에 실시예 2에서 얻은 은 나노와이어 50 ㎎을 넣고 초음파처리 하여 0.1 중량%의 나노와이어 현탁액을 제조한 후, 상기 산화 그라핀이 코팅된 기판을 수직으로 담그고 그것을 들어 올리는 딥 코팅 방법을 이용하여 산화 그라핀이 코팅된 기판에 은 나노와이어를 부착시켰다.Then, 50 mg of silver nanowires obtained in Example 2 were added to 50 ml of ethanol to sonicate to prepare a 0.1 wt% nanowire suspension, and then dip the substrate coated with graphene oxide vertically and lift it up. Silver nanowires were attached to the graphene oxide coated substrate using the coating method.
상기 은 나노와이어 네트워크를 포함하는 산화 그라핀 코팅 기판은 진공오븐에서 건조시킨 후, 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름을 튜브식 전기로 안에서 산소 분위기 하, 150℃로 30분간 열처리하였다.The graphene oxide coated substrate including the silver nanowire network was dried in a vacuum oven, and the graphene oxide / silver nanowire hybrid transparent conductive film was heat-treated at 150 ° C. for 30 minutes in an oxygen atmosphere in a tubular electric furnace.
상기 열처리를 통해 산화 그라핀과 은 나노와이어의 접속을 극대화시킬 수 있으며, 은 나노와이어 표면에 남아있는 폴리비닐리돈을 제거하는 것이 가능하다.
Through the heat treatment it is possible to maximize the connection between the graphene oxide and the silver nanowires, it is possible to remove the polyvinylidene remaining on the surface of the silver nanowires.
실시예 4. 특성 분석Example 4. Characterization
상기에서 제조된 하이브리드 투명전도성 필름의 표면을 분석하기 위해서, 먼저 이온 스퍼터링(E-1030, Hitachi, Japan)을 이용하여 백금층을 샘플에 코팅한 후, 주사전자현미경(FESEM, S-4300SE, Hitachi, Japan)을 사용하였으며, 이때 가속전압은 15 ㎸로 측정하였다.In order to analyze the surface of the hybrid transparent conductive film prepared above, first, after coating the platinum layer on the sample by using ion sputtering (E-1030, Hitachi, Japan), the scanning electron microscope (FESEM, S-4300SE, Hitachi) , Japan), where the acceleration voltage was measured at 15 ㎸.
또한, 산화 그라핀의 위상적 특징은 원자현미경(AFM, SPA400, Seiko Ins., Japan)의 탭핑 모드를 이용하여 관측하였다.In addition, the topological characteristics of graphene oxide were observed using a tapping mode of an atomic force microscope (AFM, SPA400, Seiko Ins., Japan).
또한, X-선 광전자분광법(XPS, PHI 5700 ESCA)은 Al Kα 방사(hv = 1486.6 eV) 단색광을 사용하여 수행하였으며, Aglient 8453 UV-Vis 분광광도계(Aglient Technologies, Germany)를 사용하여 380 ㎚에서 750 ㎚ 범위에서 투명전도성 필름의 투과도를 측정하였다.In addition, X-ray photoelectron spectroscopy (XPS, PHI 5700 ESCA) was carried out using Al Kα emission (hv = 1486.6 eV) monochromatic light and at 380 nm using an Aglient 8453 UV-Vis spectrophotometer (Aglient Technologies, Germany). The transmittance of the transparent conductive film in the 750 nm range was measured.
또한, 하이브리드 나노 필름의 전기 전도성을 측정하기 위해서는, 전기 전도성 측정기(electrical conductivity meter, Loresta GP, Mitsubishi Chemical, Japan)의 포 프로브(four probe)방법을 사용하여 수행하였다.
In addition, in order to measure the electrical conductivity of the hybrid nanofilm, it was performed using a four probe method of an electrical conductivity meter (Loresta GP, Mitsubishi Chemical, Japan).
도 1은, 본 발명에 따른 나노 두께의 산화 그라핀 필름을 형성하는 과정을 보여준다. 산화 그라핀 현탁액과 비이커에 세로로 담가둔 기판 사이의 계면에서 용매가 증발할 때, 기판의 가장자리에서 모세관 유동이 발생되며, 용매가 증발하면서 수면이 낮아지기 때문에 산화 그라핀이 기판 위에 연속적으로 코팅된다.
1 shows a process of forming a nano-thick graphene oxide film according to the present invention. When the solvent evaporates at the interface between the graphene oxide suspension and the substrate immersed vertically in the beaker, capillary flow occurs at the edge of the substrate and the graphene oxide is continuously coated onto the substrate as the solvent evaporates to lower the water surface. .
도 2는, 본 발명의 일실시예에 따라 제조된 폴리에틸렌테레프탈레이트 기판 위에 코팅된 산화 그라핀 필름의 표면 형태를 보여준다. 산화 그라핀 필름은 넓은 범위에서 주름진 표면을 가지며 두께는 약 40 ㎚ 정도임을 확인할 수 있다(도 2 (a) 및 (b) 참조). Figure 2 shows the surface shape of the graphene oxide film coated on a polyethylene terephthalate substrate prepared according to an embodiment of the present invention. Graphene oxide film has a corrugated surface in a wide range and can be confirmed that the thickness is about 40 nm (see Fig. 2 (a) and (b)).
국지의 구체적인 형태적 특징을 AFM을 이용하여 측정한 결과, 몇 개의 산화 그라핀으로 구성된 표면에서 주름진 패턴이 관찰되었고, 이는 고분자 용액이 증발하는 동안에 관찰되는 것과 비슷한 패턴이다. 이러한 주름진 패턴은 기계적 불안정성과 유체역학적 대류의 영향으로 형성되며, 베나르-마란고니 불안정성은 자유 표면에서 온도 구배나 농도 구배의 결과로 나타나는데 이는 주름진 표면을 형성하는데 큰 역할을 한다. 따라서, 증발 속도뿐만 아니라 온도와 농도를 조절하면 얇은 필름의 표면 형태를 제어하는 것이 가능해진다.A specific morphological feature of the local area was measured using AFM, and a wrinkled pattern was observed on the surface composed of several graphene oxides, similar to that observed during evaporation of the polymer solution. These corrugated patterns are formed by the effects of mechanical instability and hydrodynamic convection, and Benar-Marangoni instability results from temperature or concentration gradients on the free surface, which plays a large role in forming the corrugated surface. Thus, by controlling the temperature and concentration as well as the evaporation rate, it becomes possible to control the surface morphology of the thin film.
본 발명에 따른 최적화된 온도와 산화 그라핀 현탁액의 농도는 각각 60℃ 및 0.0002 중량%이다. 또한, 60℃의 온도에서 제조한 산화 그라핀 필름의 주름진 패턴은 위상차가 약 15 ㎚이다(도 2 (c) 및 (d) 참조).
The optimized temperature and the concentration of the graphene oxide suspension according to the invention are 60 ° C. and 0.0002% by weight, respectively. In addition, the wrinkled pattern of the graphene oxide film produced at a temperature of 60 ℃ has a phase difference of about 15 nm (see Fig. 2 (c) and (d)).
도 3은, 폴리올 공정(polyol process)을 이용하여 합성한 은 나노와이어의 SEM 사진이다. 본 발명에 따른 은 나노와이어의 평균 길이는 6.1±2.9 ㎛이며, 평균 직경은 76.5±2.4 ㎚로 확인되었다.3 is a SEM photograph of silver nanowires synthesized using a polyol process. The average length of the silver nanowires according to the present invention was 6.1 ± 2.9 μm, and the average diameter was found to be 76.5 ± 2.4 nm.
본 발명의 산화 그라핀/은 나노와이어 하이브리드 필름을 제조하기 위해서는 산화 그라핀이 코팅된 기판은 은 나노와이어 현탁액에 수직으로 담근 후 천천히 잡아 당겨서 산화 그라핀이 코팅된 기판 위에 은 나노와이어를 정전기적 상호작용을 이용하여 부착시킨다. 도 3에서 볼 수 있듯이, 산화 그라핀 기판 위에서 은 나노와이어 네트워크가 소량 형성되어도 투명전도성 필름으로 사용하기에 매우 우수한 전기전도성을 갖는다. 산화 그라핀 층이 폴리에틴렌테레프탈레이트 기판이 아닌 석영(a)과 유리(b) 기판에 각각 코팅되었을 때와, 산화 그라핀/은 나노와이어 하이브리드 필름이 석영(c)와 유리(d) 기판에 코팅되었을 때의 SEM 사진은 도 4에 나타내었다.
In order to prepare the graphene oxide / silver nanowire hybrid film of the present invention, the graphene oxide coated substrate is vertically immersed in the silver nanowire suspension, and then slowly pulled to electrostatically treat the silver nanowires on the graphene oxide coated substrate. Attach using interaction. As can be seen in Figure 3, even if a small amount of silver nanowire network is formed on the graphene oxide substrate has a very good electrical conductivity for use as a transparent conductive film. When the graphene oxide layer is coated on the quartz (a) and glass (b) substrates, respectively, rather than on the polyetherene terephthalate substrate, the graphene oxide / silver nanowire hybrid film is the quartz (c) and glass (d) substrate. The SEM photograph when coated on is shown in FIG. 4.
또한, 본 발명에서는 산화 그라핀과 은 나노와이어가 서로 잘 부착되고, 은 나노와이어의 전기전도성을 증가시키기 위해 산소분위기에서 150℃에서 30분간 열처리를 해 주었으며, 열처리 전과 후의 사진은 각각 도 3의 (c)와 (d)에 나타내었다. 열처리 후에는 불순물인 폴리비닐피롤리돈이 제거되고 산화 그라핀과 은 나노와이어의 사이의 접촉성이 향상되었다. 더욱이 은 나노와이어가 용융되면 나노와이어 사이의 접촉뿐만 아니라 산화 그라핀 기판과 은 나노와이어 사이의 접촉성이 좋아지며, 이는 접촉 저항을 감소시켜 전기전도성 향상에 도움을 준다.In addition, in the present invention, the graphene oxide and the silver nanowires are well adhered to each other, and heat treatment is performed at 150 ° C. for 30 minutes in an oxygen atmosphere in order to increase the electrical conductivity of the silver nanowires. It is shown to (c) and (d). After the heat treatment, the polyvinylpyrrolidone as an impurity was removed and the contact between the graphene oxide and the silver nanowires was improved. Furthermore, when the silver nanowires are melted, the contact between the graphene oxide substrate and the silver nanowires as well as the contact between the nanowires is improved, which helps to improve the electrical conductivity by reducing the contact resistance.
열처리에 의한 접촉성이 향상되는 효과는 도 5에 도식화하여 나타내었다.
The effect of improving the contactability by heat treatment is shown schematically in FIG. 5.
도 6은, X-선 광전자분광법(XPS)에 의한 열처리 과정을 거친 산화 그라핀/은 나노와이어 하이브리드 필름의 탄소(C) 1s 스텍트라(a) 및 열처리 전후의 필름의 은(Ag) 3d 스펙트라(b)를 나타낸 것이다. 도 6의 (a)에서 볼 수 있듯이, 몇몇의 구별되는 기능기(산화되지 않은 탄소 C, C-O, C=O, O-C=O)의 피크가 C 1s 스펙트라에서 나타났고, 이는 열처리 후의 필름이 산화가 상당히 많이 되었음을 시사한다. C 1s 스펙트라는 산화 그라핀과 비슷한 양상을 보이는 것으로 보아, 산소 분위기에서 열처리 과정을 거친 후에 산화 그라핀이 열에 의해 환원되지 않았음을 알 수 있다. FIG. 6 shows carbon (C) 1s stack (a) of graphene oxide / silver nanowire hybrid film subjected to heat treatment by X-ray photoelectron spectroscopy (XPS) and silver (Ag) 3d spectra of film before and after heat treatment. (b) is shown. As can be seen in FIG. 6 (a), some distinct functional groups (unoxidized carbon C, CO, C = O, OC = O) peaks appeared in the C 1s spectra, whereby the film after heat treatment was oxidized Suggests that there are quite a few. Since C 1s spectra is similar to graphene oxide, it can be seen that graphene oxide was not reduced by heat after heat treatment in an oxygen atmosphere.
또한, 도 6의 (b)에서 보면, 열처리 전의 산화 그라핀/은 나노와이어 하이브리드 필름의 Ag 3d 결합에너지는 368.1 eV로 순수한 은의 결합에너지와 동일하였다. 이는 열처리 전에는 산화 그라핀과 은 나노와이어 사이의 어떠한 상호작용도 없음을 증명한다. 그러나, 열처리 후에는 결합에너지가 367.5 eV로 이동하였는데, 그 이유는 은(4.2 eV)과 산화 그라핀(4,48 eV) 사이의 일함수 차이로 인해 전자가 금속인 은으로부터 산화 그라핀으로 이동하였기 때문에 더 낮은 에너지인 367.5 eV로 이동한 것이다.6 (b), the Ag 3d binding energy of the graphene oxide / silver nanowire hybrid film before heat treatment was 368.1 eV, which was the same as that of pure silver. This demonstrates that there is no interaction between graphene oxide and silver nanowires before heat treatment. However, after heat treatment, the binding energy shifted to 367.5 eV because of the work function difference between silver (4.2 eV) and graphene oxide (4,48 eV), the electrons moved from silver, which is a metal, to graphene oxide. As a result, they moved to a lower energy of 367.5 eV.
만약, 산화 그라핀이 환원되었다면 하이브리드 필름의 전도성을 증가할 수 있을지 모르나 투명성을 감소시키는 요인이 되었을 것으로 생각된다.If graphene oxide was reduced, it may be possible to increase the conductivity of the hybrid film, but it is thought to be a factor that reduces transparency.
그러나, 본 발명에서는, 열처리를 통해 산화 그라핀이 환원되지 아니하여 높은 투명성을 가지며, 은 나노와이어가 산화 그라핀과 더욱 강하게 결합되고 은 나노와이어 사이의 접촉저항이 감소하여 높은 전도성을 가지는 필름을 제조할 수 있다. 그 결과, 산화 그라핀에 은 나노와이어를 소량 네트워킹시킴으로써 유연하고 기계적으로 안정한 투명전도성 필름을 제조하는 것이 가능하다.
However, in the present invention, the graphene oxide is not reduced through heat treatment and thus has high transparency, and the silver nanowires are more strongly bonded with the graphene oxide, and the contact resistance between the silver nanowires is reduced, thereby providing a film having high conductivity. It can manufacture. As a result, it is possible to produce a flexible and mechanically stable transparent conductive film by networking a small amount of silver nanowires with graphene oxide.
도 7은 기판이 각각 석영(a), 유리(b) 및 폴리에틸렌테레프탈레이트(c) 일 때, 산화 그라핀/은 나노와이어 하이브리드 필름의 UV-Vis 스펙트라이고, 도 8은 상기 세 가지 기판을 이용해 만든 투명전도성 필름의 성능을 보여준다.FIG. 7 is a UV-Vis spectra of graphene oxide / silver nanowire hybrid films when the substrates are quartz (a), glass (b) and polyethylene terephthalate (c), respectively, and FIG. Show the performance of the transparent conductive film made.
폴리에틸렌테레프탈레이트 기판을 이용해 만든 플렉시블한 투명전도성 필름은 투과도가 86%일 때, 150 Ω/□의 면저항을 가지며, 석영 기판의 경우에는 투과도가 86%일 때, 면저항이 40 Ω/□이고, 유기 기판은 투과도가 89%일 때, 면저항이 200 Ω/□로 세 가지 기판 모두 ITO에 상당하는 성능을 나타내었다.
The flexible transparent conductive film made of a polyethylene terephthalate substrate has a sheet resistance of 150 Ω / □ when the transmittance is 86%, and the sheet resistance is 40 Ω / □ when the transmittance is 86% when the quartz substrate is used. When the substrate had a transmittance of 89%, the sheet resistance was 200 mA / square, and all three substrates exhibited performance equivalent to that of ITO.
투명도와 면저항에 관련한 상대적인 성능은, 아래의 식에 의해 절대치로 표현할 수 있다.The relative performance with respect to transparency and sheet resistance can be expressed by absolute value by the following formula.
상기에서, Z0=377 Ω로 자유공간의 임피던스이고, T는 투명도를, Rs는 면저항을 의미한다. 투과도가 높고 면저항이 낮을 때, σDC/σOP 비는 높은 값을 가진다. 서로 다른 방법으로 합성한 다양한 산화 그라핀 또는 은 나노와이어로 제조한 투명전도성 필름의 σDC/σOP값은 하기 표 1에 나타내었다.In the above description, Z 0 = 377 kHz, which is the impedance of free space, T means transparency, and R s means sheet resistance. When the transmittance is high and the sheet resistance is low, the σ DC / σ OP ratio has a high value. The σ DC / σ OP values of the transparent conductive films made of various graphene oxides or silver nanowires synthesized by different methods are shown in Table 1 below.
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은 나노와이어만을 이용한 필름은, 은 나노와이어가 전기전도성이 매우 우수하기 때문에 σDC/σOP 비가 산화 그라핀을 이용한 필름보다 상대적으로 높은 값은 갖는다. 본 발명에 따른 폴리에틸렌테레프탈레이트 기판 위에 합성한 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름은 σDC/σOP 값이 20.9-90으로 매우 높은 값을 나타내었으며, 매우 유연하고 기계적 안정성이 우수하였다.
It is loaded using only the nanowire, the since the excellent electrical conductivity σ nanowires DC / σ OP relatively higher than the ratio of the film using a graphene oxide has. The graphene oxide / silver nanowire hybrid transparent conductive film synthesized on the polyethylene terephthalate substrate according to the present invention exhibited a very high value of σ DC / σ OP of 20.9-90, and was very flexible and excellent in mechanical stability.
또한, 폴리에틸렌테레프탈레이트 기판 위에 합성한 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름의 유연성을 측정하여 도 9에 나타내었다. 필름의 면저항은 500번의 벤딩 시험을 수행하였을 때까지도 일정한 값을 유지하였으며, 이는 산화 그라핀과 은 나노와이어가 열처리에 의해서 강한 상호작용을 하고 있기 때문인 것으로 생각된다.
In addition, the flexibility of the graphene oxide / silver nanowire hybrid transparent conductive film synthesized on a polyethylene terephthalate substrate was measured and shown in FIG. The sheet resistance of the film was maintained at a constant value even after 500 bending tests, which is considered to be due to the strong interaction between the graphene oxide and the silver nanowires by heat treatment.
또한, 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름의 기계적 안정성 확인을 위한 접착성 시험을 열처리 전과 후의 필름에 각각 접착테이프를 고착시킨 다음 접착테이프를 필름으로부터 벗겨내는 방식으로 수행하였으며, 그 결과, 열처리를 통해 기계적 안정성이 향상된 필름은 접착테이프를 제거한 후에도 필름에 어떠한 얼룩도 생기지 아니하여 산화 그라핀과 은 나노와이어가 잘 부착되어 있음을 확인하였다(도 10 참조).
In addition, the adhesion test for confirming the mechanical stability of the graphene oxide / silver nanowire hybrid transparent conductive film was carried out by fixing the adhesive tape to the film before and after the heat treatment, respectively, and peeling the adhesive tape from the film, as a result, After the heat treatment, the film having improved mechanical stability did not have any stains even after the adhesive tape was removed, thereby confirming that the graphene oxide and silver nanowires were well attached (see FIG. 10).
이상, 본 발명의 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific descriptions are only for the preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (12)
Graphene oxide / silver nanowire hybrid transparent conductive film.
상기 투명전도성 필름은 투과도가 80~90%일 때, 면저항이 40~200 Ω/□인 것이 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름.
The method of claim 1,
The transparent conductive film is a graphene oxide / silver nanowire hybrid transparent conductive film, characterized in that when the transmittance is 80 to 90%, the sheet resistance is 40 ~ 200 Ω / □.
(2) 폴리비닐피롤리돈(PVP) 존재 하에 에틸렌글리콜을 이용하여 질산은을 환원시켜 은 나노와이어를 제조하는 단계; 및
(3) 상기 (2) 단계에서 제조한 은 나노와이어를 상기 (1) 단계에서 제조한 산화 그라핀 필름 위에 부착하는 단계;
(4) 상기 (3) 단계에서 제조된 은 나노와이어 네트워크를 포함하는 산화 그라핀 필름을 건조시켜 투명전도성 필름을 제조하는 단계; 및
(5) 상기 투명전도성 필름을 열처리(thermal annealing)하는 단계;를 포함하는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
(1) preparing a nano-thick graphene oxide film;
(2) preparing silver nanowires by reducing silver nitrate using ethylene glycol in the presence of polyvinylpyrrolidone (PVP); And
(3) attaching the silver nanowires prepared in step (2) onto the graphene oxide film prepared in step (1);
(4) preparing a transparent conductive film by drying the graphene oxide film including the silver nanowire network prepared in step (3); And
(5) a thermal annealing of the transparent conductive film; graphene oxide / silver nanowire hybrid transparent conductive film production method comprising a.
상기 나노 두께의 산화 그라핀 필름은 모세관 유동을 구동력으로 이용하여 제조하는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
The method of claim 3,
The graphene oxide film of the nano-thickness graphene oxide / silver nanowires hybrid transparent conductive film manufacturing method characterized in that the manufacturing using a capillary flow as a driving force.
상기 나노 두께의 그라핀 필름은,
(a) 천연 흑연을 동결건조하는 단계;
(b) 상기 동결건조된 천연 흑연을 초음파 처리를 통해 박리시켜 현탁액을 제조하는 단계; 및
(c) 상기 산화 그라핀 현탁액을 기판 위에 코팅하는 단계;를 포함하여 제조하는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
The method of claim 3,
The nano-thick graphene film,
(a) lyophilizing the natural graphite;
(b) exfoliating the lyophilized natural graphite through sonication to prepare a suspension; And
(c) coating the graphene oxide suspension on a substrate; graphene oxide / silver nanowire hybrid transparent conductive film manufacturing method comprising the step of manufacturing.
상기 (a) 단계에서는, 천연 흑연으로부터 현탁액을 제조하여 액체 질소로 동결시킨 후, -50℃, 0.04~0.05 mbar의 동결건조기에서 72시간 동안 동결건조하는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
The method of claim 5,
In the step (a), the suspension is prepared from natural graphite, frozen with liquid nitrogen, and then lyophilized for 72 hours in a freeze dryer at −50 ° C. and 0.04 to 0.05 mbar. Hybrid transparent conductive film manufacturing method.
상기 (b) 단계에서는, 상기 (a) 단계에서 얻은 산화 그라핀 파우더를 증류수에 넣고 초음파처리를 통해 박리시켜 0.0001~0.0003중량% 농도의 산화 그라핀 현탁액을 제조하는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
The method of claim 5,
In the step (b), the graphene oxide powder obtained in the step (a) is put into distilled water and peeled through sonication to produce a graphene oxide suspension having a concentration of 0.0001 to 0.0003% by weight of graphene oxide / Silver nanowire hybrid transparent conductive film manufacturing method.
상기 (c) 단계에서는, 상기 (b) 단계에서 얻은 산화 그라핀 현탁액을 유리, 석영 및 폴리에틸렌프탈레이트(PET)에서 선택되는 어느 하나의 기판 위에 코팅 후 건조하여 10~50 ㎚ 두께의 산화 그라핀 필름을 얻는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
The method of claim 5,
In the step (c), the graphene oxide suspension obtained in the step (b) is coated on any one of the substrates selected from glass, quartz and polyethylene phthalate (PET) and dried to obtain a graphene oxide film having a thickness of 10 to 50 nm. Graphene oxide / silver nanowires hybrid transparent conductive film production method characterized by obtaining.
상기 은 나노와이어는 폴리올 공정(polyol process)을 이용하여 제조하는 것이 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
The method of claim 3,
The silver nanowires are prepared using a polyol process (polyol process), characterized in that the graphene oxide / silver nanowire hybrid transparent conductive film manufacturing method.
상기 은 나노와이어의 평균 길이는 1~10 ㎛이고, 평균 직경은 70~80 ㎚인 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
10. The method of claim 9,
The average length of the silver nanowire is 1 ~ 10 ㎛, average diameter is 70 ~ 80 nm characterized in that the graphene oxide / silver nanowire hybrid transparent conductive film production method.
상기 은 나노와이어는 상기 산화 그라핀 필름 위에 딥 코팅 방법을 이용하여 부착시키는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법.
The method of claim 3,
The silver nanowires are graphene oxide / silver nanowires hybrid transparent conductive film manufacturing method characterized in that the adhesion on the graphene oxide film using a dip coating method.
상기 투명전도성 필름은 산소분위기에서 150℃에서 30분간 열처리(thermal annealing)를 하는 것을 특징으로 하는 산화 그라핀/은 나노와이어 하이브리드 투명전도성 필름 제조방법. The method of claim 3,
The transparent conductive film is a graphene oxide / silver nanowire hybrid transparent conductive film production method characterized in that the heat treatment (thermal annealing) for 30 minutes at 150 ℃ in an oxygen atmosphere.
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