KR101200857B1 - Method for preparing transparent conductive coating film comprising branched nanowire - Google Patents
Method for preparing transparent conductive coating film comprising branched nanowire Download PDFInfo
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- KR101200857B1 KR101200857B1 KR1020110047578A KR20110047578A KR101200857B1 KR 101200857 B1 KR101200857 B1 KR 101200857B1 KR 1020110047578 A KR1020110047578 A KR 1020110047578A KR 20110047578 A KR20110047578 A KR 20110047578A KR 101200857 B1 KR101200857 B1 KR 101200857B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- Computer Hardware Design (AREA)
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Abstract
본 발명은 투명전도성 코팅 필름의 제조방법에 관한 것으로서, 보다 구체적으로 1) 브랜치드(branched) 금속 나노시드(nano seed)를 제조한 후, 정제하는 단계, 2) 상기 브랜치드 금속 나노시드와 폴리올 공정(polyol process)을 이용하여 브랜치드 은 나노와이어를 성장시키는 단계, 및 3) 상기 브랜치드 은 나노와이어를 기판 상에 코팅하여 코팅층을 형성한 후, 상기 코팅층을 어닐링(annealing)하는 단계를 포함한다. 본 발명에 따라 제조되는 투명전도성 코팅 필름은 전기적, 광학적, 기계적 특성 등이 우수할 뿐만 아니라, 브랜치드 은 나노와이어의 균일도를 향상시킬 수 있고, 전자 소자 등에 유용하게 적용할 수 있다.The present invention relates to a method for manufacturing a transparent conductive coating film, and more specifically, 1) preparing a branched metal nanoseed (nano seed), and then refining, 2) the branched metal nanoseed and polyol Growing branched silver nanowires using a polyol process, and 3) coating the branched silver nanowires on a substrate to form a coating layer, followed by annealing the coating layer. do. The transparent conductive coating film prepared according to the present invention not only has excellent electrical, optical and mechanical properties, but also can improve the uniformity of the branched silver nanowires, and can be usefully applied to electronic devices.
Description
본 발명은 투명전도성 코팅 필름의 제조방법에 관한 것으로서, 보다 구체적으로 브랜치드 나노와이어를 포함함으로써 전기적, 광학적, 기계적 특성 등이 우수한 투명전도성 코팅 필름 및 이의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a transparent conductive coating film, and more particularly, to a transparent conductive coating film having excellent electrical, optical, mechanical properties, and the like by including branched nanowires, and a method for manufacturing the same.
투명 도전체는 고투과율 절연 표면 또는 기판 상에 코팅된 얇은 도전막을 말한다. 투명 도전체는 적절한 광학적 투명성을 유지하면서 표면 도전성을 갖도록 제조될 수 있다. 그러한 표면 도전 투명 도전체는 평판 액정 표시 장치(flat liquid crystal display), 터치 패널(touch panel), 전자 발광 장치(electroluminescent device), 박막 광전지(thin film photovoltaic cell) 등에서 투명 전극들로서 널리 사용되고, 대전 방치층 및 전자기파 차폐층으로 널리 사용되고 있다.Transparent conductor refers to a thin conductive film coated on a high transmittance insulating surface or substrate. The transparent conductor can be made to have surface conductivity while maintaining proper optical transparency. Such surface conducting transparent conductors are widely used as transparent electrodes in flat liquid crystal displays, touch panels, electroluminescent devices, thin film photovoltaic cells, etc. It is widely used as a layer and an electromagnetic shielding layer.
현재, 인듐 주석 산화물(indium tin oxide, ITO)과 같은 진공 증착 금속 산화물(vacuum deposited metal oxide)은 글래스(glass)와 중합체 막(polymeric film)과 같은 유전체 표면들에 대해 광학적 투명성 및 전기적 도전성을 제공하기 위한 산업 표준 물질이다. 그러나, 금속 산화막은 약하고 휨이나 다른 물리적인 스트레스들에 의해 손상되기 쉽다. 또한, 이들은 높은 도전성 수준들을 달성하기 위해 높은 증착온도 및/또는 높은 어닐링(annealing) 온도를 요한다. 플라스틱 및 유기 기판들, 예를 들어 폴리카보네이트와 같이 습기를 흡착하기 쉬운 기판들에게 급속 산화막의 접착력이 또한 문제될 수 있다. 따라서, 플렉서블(flexible) 기판 상에 금속 산화막을 적용하는 것은 매우 제한된다. 또한, 진공 증착은 비용이 많이 드는 공정이고 특수한 장비를 요구한다. 더구나, 진공 증착 공정은 패턴 및 회로를 형성하는데 있어서 도움이 되지 않으며, 이는 전형적으로 포토리소그래피와 같이 비용이 많이 드는 패터닝 공정들로 귀결된다.Currently, vacuum deposited metal oxides such as indium tin oxide (ITO) provide optical transparency and electrical conductivity to dielectric surfaces such as glass and polymeric films. Industry standard material. However, the metal oxide film is weak and prone to damage by warping or other physical stresses. In addition, they require high deposition temperatures and / or high annealing temperatures to achieve high conductivity levels. Adhesion of the rapid oxide film to substrates that are susceptible to moisture, such as plastic and organic substrates, such as polycarbonate, may also be a problem. Therefore, application of a metal oxide film on a flexible substrate is very limited. In addition, vacuum deposition is a costly process and requires specialized equipment. Moreover, vacuum deposition processes are not helpful in forming patterns and circuits, which typically results in costly patterning processes such as photolithography.
또한, 도전성 중합체는 광학적으로 투명한 전기적 도전체로서 사용되어 왔다. 그러나, 이들은 일반적으로 금속 산화막에 비해 낮은 전도율 값과 높은 광흡수성을 가지며, 화학적 및 장기적 안정성이 부족하다.In addition, conductive polymers have been used as optically transparent electrical conductors. However, they generally have lower conductivity values and higher light absorption than metal oxide films, and lack chemical and long term stability.
따라서, 저비용, 고처리율 공정으로 제조될 수 있고, 적절한 전기적, 광학적, 기계적 특성 등을 갖는 투명 도전체를 제조하는 연구가 필요하다.Therefore, there is a need for research to manufacture a transparent conductor that can be manufactured in a low cost, high throughput process, and has appropriate electrical, optical, and mechanical properties.
한편, 최근 나노 크기의 입자에 대한 관심이 증대되면서 나노 크기의 금속 물질에 대한 제조 및 응용 분야 연구가 활발히 진행되고 있다. 나노 입자는 같은 화학적 조성을 갖는 벌크상의 재료들과 비교하여 독특한 전기적, 자기적, 광학적, 기계적 성질들을 나타내기 때문에 전자재료, 센서, 흡착제, 크로마토그래피의 충진제, 촉매 담체 등 광범위한 분야에서 응용되고 있다. 특히, 그 중에서도 일차원적 구조(rods, wires, tubes, belts)를 가진 여러 금속 물질들은 나노 크기의 장치를 이루는데 중요한 역할을 할 것이라 기대되고 있다. 이러한 기대는 일차원적 구조를 지닌 물질들이 가지는 특별한 전기적, 기계적 물성에 기인하고, 일반적으로 나노 크기 금속 물질의 물성은 그것들의 크기와 구조에 따라 변화된다. 필요한 물성을 얻기 위한 방법은 나노 크기 물질의 형태를 어떻게 조절하는가에 따라 달라지며, 따라서 형태조절의 중요성이 부각되고 있는 상황이다. 나노와이어는 최근 일차원 구조를 가진 물질 중 그것들의 제조와 특성 평과에 관한 연구들이 활발히 수행되고 있다.Recently, as interest in nano-sized particles has increased, studies on manufacturing and application of nano-sized metal materials have been actively conducted. Nanoparticles have been used in a wide range of fields including electronic materials, sensors, adsorbents, chromatography fillers, and catalyst carriers because they exhibit unique electrical, magnetic, optical, and mechanical properties compared to bulk phase materials with the same chemical composition. In particular, many metallic materials with one-dimensional structures (rods, wires, tubes, belts) are expected to play an important role in forming nanoscale devices. These expectations are due to the particular electrical and mechanical properties of materials with one-dimensional structures, and in general, the properties of nano-sized metal materials vary with their size and structure. The way to obtain the necessary properties depends on how the shape of the nanoscale material is controlled, and therefore the importance of shape control is becoming more important. In recent years, nanowires have been actively studied for their production and evaluation of properties among materials having a one-dimensional structure.
은(Ag)은 모든 금속 중에서 가장 높은 전기 및 열전도도를 가지는 특성으로 많은 관심과 연구가 진행되고 있다. 또한, 은은 상업적으로 응용분야가 넓고, 이러한 은의 일차원적 구조로의 변화는 높은 종횡비(aspect ratio)와 잘 정제된 결정면의 조절을 통해 여러 응용분야로의 확대가 기대되고 있는 바이다. 예를 들면, 은과 고분자의 혼합체에서 은 나노와이어가 혼재되었을 때 은 나노 입자가 혼재되어 있을 때보다 현저하게 낮은 전기적 부하가 발생된다.Silver (Ag) has the highest electrical and thermal conductivity among all metals, and much attention and research are underway. In addition, silver has a wide range of applications in commerce, and the change to silver one-dimensional structure is expected to expand to various application fields through control of high aspect ratio and well-refined crystal plane. For example, when silver nanowires are mixed in a mixture of silver and a polymer, a significantly lower electrical load is generated than when nanoparticles are mixed.
대부분의 연구에서는 반도체로서부터 유전체까지의 쓰임을 위해서 와이어를 제조하고 있다. 이러한 와이어들은 대부분 전기적 또는 전기화학적 방법을 포함한 주형(template)을 이용하여 제조하고 있고, 세공막(macroporous membranes), 메조포러스 물질(mesoporous materials), 탄소 나노튜브(carbon nanotubes), DNA 체인(DNA chain), 블록공중합체(block copolymer) 등이 와이어 성장을 위한 주형으로 이용되고 있다. 그러나, 이러한 주형을 이용한 방법은 최종 결과물인 와이어의 형상을 조절하기는 쉬우나, 주형의 이용은 주형의 제조와 와이어 형성, 주형의 제거 등 다단계 제조공정과 주형 이용의 제한성으로 대량생산에 적합하지 않아서, 상업적으로 의미 있는 생산성 확보를 위해서는 개선해야 할 과제가 많이 남아있다.Most studies produce wires for use from semiconductors to dielectrics. Most of these wires are manufactured using templates, including electrical or electrochemical methods, and include macroporous membranes, mesoporous materials, carbon nanotubes, and DNA chains. ), Block copolymers (block copolymer), etc. are used as a template for the growth of wire. However, the method using the mold is easy to control the shape of the final result wire, but the use of the mold is not suitable for mass production due to the multi-step manufacturing process such as the manufacture of the mold, the formation of the wire, and the removal of the mold. However, there are many challenges to improve in order to obtain commercially meaningful productivity.
본 발명은, 저비용, 고처리율 공정으로 제조될 수 있고, 전기적, 광학적, 기계적 특성 등이 우수한 투명전도성 코팅 필름의 제조방법을 제공하고자 한다.The present invention is to provide a method for producing a transparent conductive coating film that can be produced in a low cost, high throughput process, and excellent in electrical, optical, mechanical properties and the like.
이에, 본 발명은Therefore,
1) 브랜치드(branched) 금속 나노시드(nano seed)를 제조한 후, 정제하는 단계,1) preparing a branched metal nanoseed (nano seed), and then purifying,
2) 상기 브랜치드 금속 나노시드와 폴리올 공정(polyol process)을 이용하여 브랜치드 은 나노와이어를 성장시키는 단계, 및2) growing branched silver nanowires using the branched metal nanoseed and a polyol process, and
3) 상기 브랜치드 은 나노와이어를 기판 상에 코팅하여 코팅층을 형성한 후, 상기 코팅층을 어닐링(annealing)하는 단계3) coating the branched silver nanowires on a substrate to form a coating layer, and then annealing the coating layer.
를 포함하는 투명전도성 코팅 필름의 제조방법을 제공한다.It provides a method for producing a transparent conductive coating film comprising a.
또한, 본 발명은 상기 투명전도성 코팅 필름의 제조방법으로 제조되는 투명전도성 코팅 필름을 제공한다.In addition, the present invention provides a transparent conductive coating film prepared by the method for producing a transparent conductive coating film.
또한, 본 발명은 상기 투명전도성 코팅 필름을 포함하는 전자 소자를 제공한다.In addition, the present invention provides an electronic device comprising the transparent conductive coating film.
본 발명은, 저비용, 고처리율 공정으로 전기적, 광학적, 기계적 특성 등이 우수한 투명전도성 코팅 필름을 제조할 수 있다. 또한, 별도로 생성된 크기가 균일한 브랜치드 금속 나노시드를 이용함으로써, 브랜치드 은 나노와이어의 균일도를 향상시킬 수 있고, 이러한 브랜치드 은 나노와이어는 투명전도성 코팅필름 등에 유용하게 적용할 수 있다.The present invention can produce a transparent conductive coating film excellent in electrical, optical, mechanical properties, etc. in a low cost, high throughput process. In addition, by using a branched metal nanoseed uniformly generated size, it is possible to improve the uniformity of the branched silver nanowires, the branched silver nanowires can be usefully applied to a transparent conductive coating film.
도 1은 본 발명에 따른 일구체예로서, 브랜치드 금속 나노시드로부터 성장시킨 브랜치드 은 나노와이어를 개략적으로 나타낸 도이다.1 is a view schematically showing a branched silver nanowire grown from a branched metal nanoseed as one embodiment according to the present invention.
이하, 본 발명을 보다 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 투명전도성 코팅 필름의 제조방법의 일구체예는 1) 브랜치드(branched) 금속 나노시드(nano seed)를 제조한 후, 정제하는 단계, 2) 상기 브랜치드 금속 나노시드와 폴리올 공정(polyol process)을 이용하여 브랜치드 은 나노와이어를 성장시키는 단계, 및 3) 상기 브랜치드 은 나노와이어를 기판 상에 코팅하여 코팅층을 형성한 후, 상기 코팅층을 어닐링(annealing)하는 단계를 포함한다.One embodiment of the method for producing a transparent conductive coating film according to the present invention is 1) preparing a branched metal nanoseed (nano seed), and then purifying, 2) the branched metal nanoseed and polyol process growing a branched silver nanowire using a polyol process, and 3) coating the branched silver nanowire on a substrate to form a coating layer, and then annealing the coating layer. .
종래에는 금속 나노시드의 형성공정과 상기 금속 나노시드를 이용한 나노와이어의 제조공정을 하나의 반응기에서 연속적으로 수행하는 방법으로서 나노와이어를 제조하였다. 그러나, 이러한 방법은 금속 나노시드의 형성속도가 일정하지 않아서 금속 나노시드의 생성속도 및 크기의 균일도가 떨어지게 되고, 이에 따라 생성되는 나노와이어의 길이 및 두께 또한 균일하게 형성되지 못하는 문제점이 있었다.Conventionally, a nanowire was manufactured as a method of continuously forming a metal nanoseed and a process of manufacturing a nanowire using the metal nanoseed in one reactor. However, this method has a problem that the formation rate of the metal nanoseed is not constant, thereby decreasing the uniformity of the generation rate and size of the metal nanoseed, and thus the length and thickness of the nanowires produced are not uniformly formed.
한편, 본 발명은 별도로 브랜치드 금속 나노시드를 제조 및 정제함으로써 브랜치드 금속 나노시드의 생성속도 및 크기의 균일도를 향상시킬 수 있고, 이에 따라 최종적으로 제조되는 브랜치드 은 나노와이어의 길이, 두께 등의 균일도 또한 향상시킬 수 있는 특징이 있다.On the other hand, the present invention can improve the uniformity of the production rate and size of the branched metal nanoseed separately by preparing and purifying the branched metal nanoseed separately, according to the length, thickness, etc. of the branched silver nanowire finally produced There is also a feature that can improve the uniformity of.
본 발명에 따른 투명전도성 코팅 필름의 제조방법에 있어서, 상기 1) 단계의 브랜치드 금속 나노시드는 백금, 금, 은, 구리, 니켈, 철, 알루미늄, 팔라듐, 이리듐 등을 1종 이상 포함할 수 있다.In the method for producing a transparent conductive coating film according to the present invention, the branched metal nanoseed of step 1) may include at least one of platinum, gold, silver, copper, nickel, iron, aluminum, palladium, and iridium. .
상기 1) 단계의 브랜치드 금속 나노시드는 당 기술분야에 알려져 있는 결정핵생성(nucleation) 공정에 의하여 제조 및 정제될 수 있다. 보다 구체적으로 브랜치드 금속 나노시드는 금속염의 환원과정을 통하여 제조될 수 있고, 제조되는 브랜치드 금속 나노시드는 필터, 원심분리 등을 통하여 정제될 수 있다.The branched metal nanoseed of step 1) may be prepared and purified by a nucleation process known in the art. More specifically, the branched metal nanoseeds may be prepared through a reduction process of the metal salt, and the branched metal nanoseeds may be purified through a filter, centrifugation, or the like.
본 발명에 따른 투명전도성 코팅 필름의 제조방법에 있어서, 상기 2) 단계의 브랜치드 은 나노와이어의 성장은 상기 브랜치드 금속 나노시드와 폴리올 공정을 이용하여 수행될 수 있다. 일반적으로, 폴리올 공정에서 금속염의 환원을 통한 나노 크기 입자의 형성은 다음과 같은 과정을 거치게 된다. 최초의 단계로 전구체 물질인 금속염이 액상 폴리올에서 용해되고, 용해된 염이 폴리올에 의해 환원되며, 용액으로부터 금속 입자의 핵생성과 성장과정을 통하여 나노 크기 입자들이 생성되게 된다. 상기 폴리올 공정의 대표적인 환원 반응식은 하기와 같다.In the method for producing a transparent conductive coating film according to the present invention, the growth of the branched silver nanowires of step 2) may be performed using the branched metal nanoseed and polyol process. In general, the formation of nano-sized particles through the reduction of metal salts in the polyol process is as follows. In the first step, the metal salt, the precursor material, is dissolved in the liquid polyol, the dissolved salt is reduced by the polyol, and nano-size particles are produced through nucleation and growth of the metal particles from the solution. Representative reduction scheme of the polyol process is as follows.
2(CH2OH-CH2OH) → 2CH3CHO + 2H2O2 (CH 2 OH-CH 2 OH) → 2CH 3 CHO + 2H 2 O
2CH3CHO + 금속염 → 2M + 2H+ + CH3-CO-CO-CH3 2CH 3 CHO + metal salt → 2M + 2H + + CH 3 -CO-CO-CH 3
상기 반응식은, 에틸렌글리골의 탈수소화 반응으로 우선 아세트알데하이드가 생성되고, 아세트알데하이드의 산화반응을 거쳐서 금속염을 치환하는 환원반응을 거쳐 디아세틸로 형성되는 과정을 나타낸 것이다.
The above reaction scheme shows a process in which acetaldehyde is first generated by dehydrogenation of ethylene glycol, and then formed into diacetyl through a reduction reaction of substituting a metal salt through oxidation of acetaldehyde.
본 발명에 있어서, 상기 2) 단계의 폴리올 공정은 은을 포함하는 화합물과 폴리올을 이용하고, 은의 환원공정에 의해 수행될 수 있다. 상기 은을 포함하는 화합물의 구체적인 예로는 질산은, 은 실리케이트 등을 들 수 있으나, 이에만 한정되는 것은 아니다. 또한, 상기 폴리올의 구체적인 예로는 에틸렌글리콜, 디에틸렌글리콜, 2-에톡시에탄올 등을 들 수 있으나, 이에만 한정되는 것은 아니다.In the present invention, the polyol process of step 2) using a compound and a polyol containing silver, it may be carried out by a reduction process of silver. Specific examples of the compound containing silver include silver nitrate, but are not limited thereto. In addition, specific examples of the polyol may include ethylene glycol, diethylene glycol, 2-ethoxyethanol, and the like, but are not limited thereto.
상기 2) 단계에서, 브랜치드 은 나노와이어의 성장시 캡핑제(capping agent)를 추가로 투입할 수 있다. 상기 캡핑제는 분산 안정화 및 캡핑(capping) 효과를 나타낼 수 있는 물질로서, 폴리비닐피롤리돈(polyvinyl pyrrolidone, PVP), 폴리비닐알콜(polyvinyl alcohol), 폴리(메타)아크릴산(poly(meth)acrylic acid) 등을 들 수 있으나, 이에만 한정되는 것은 아니다. 상기 캡핑제에 의하여 폴리올 공정으로부터 생성되는 나노 입자들이 뭉치지 않고 안정하게 존재하게 되며, 환원공정을 촉지하는 역할 또한 하게 된다.In step 2), the capping agent may be further added during the growth of the branched silver nanowires. The capping agent is a material that may exhibit dispersion stabilization and capping effects, and may include polyvinylpyrrolidone (PVP), polyvinyl alcohol, and poly (meth) acrylic acid. acid), but is not limited thereto. By the capping agent, the nanoparticles generated from the polyol process do not aggregate and stably exist, and also serve to promote the reduction process.
일반적인 선형 나노와이어를 전도성 코팅재료로 이용하는 경우에는 전기전도도가 균일한 일반 금속 코팅에 비해서 저하되는 경향이 있다. 이는 나노와이어 간의 접촉부위의 계면에서의 저항으로 인해서 발생하는 문제로 알려져 있다.When the general linear nanowire is used as the conductive coating material, the electrical conductivity tends to be lower than that of the general metal coating having a uniform electrical conductivity. This is known to be a problem caused by the resistance at the interface of the contact portion between the nanowires.
이에, 본 발명은 브랜치드 금속 나노시드를 이용함으로써 브랜치드 은 나노와이어를 제조할 수 있고, 상기 3) 단계의 어닐링 공정을 통하여 은 나노와이어 간의 접촉면수를 줄여줄 수 있으며, 이에 따라 브랜치드 은 나노와이어의 전도도를 향상시킬 수 있다.Thus, the present invention can produce a branched silver nanowire by using a branched metal nanoseed, it is possible to reduce the number of contact surface between the silver nanowires through the annealing process of step 3), accordingly branched silver The conductivity of the nanowires can be improved.
상기 3) 단계의 어닐링의 온도는 90 ~ 150℃인 것이 바람직하나, 이에만 한정되는 것은 아니다. 상기 어닐링의 온도가 150℃를 초과하는 경우에는 미량의 산소가 존재하는 경우에도 쉽게 산화할 수 있고, 와이어의 형태를 완전히 잃어버리고 응집이 될 수 있는 문제점이 발생할 수 있고, 90℃ 미만인 경우에는 어닐링 효과가 미미하여 바람직하지 않다.The temperature of the annealing of step 3) is preferably 90 ~ 150 ℃, but is not limited thereto. If the temperature of the annealing exceeds 150 ℃ can be easily oxidized even when a small amount of oxygen is present, there may be a problem that can lose the form of the wire completely and become agglomerated, if less than 90 ℃ The effect is negligible and undesirable.
본 발명에 따른 투명전도성 코팅 필름의 제조방법에 있어서, 상기 3) 단계의 기판은 당 기술분야에 알려진 유리판, 플라스틱 필름 등을 이용할 수 있다. 또한, 상기 3) 단계의 코팅 공정은 당 기술분야에 알려져 있는 방법을 이용할 수 있다.In the method of manufacturing a transparent conductive coating film according to the present invention, the substrate of step 3) may use a glass plate, a plastic film, or the like known in the art. In addition, the coating process of step 3) may use a method known in the art.
또한, 본 발명은 상기 투명전도성 코팅 필름의 제조방법으로 제조되는 투명전도성 코팅 필름을 제공한다.In addition, the present invention provides a transparent conductive coating film prepared by the method for producing a transparent conductive coating film.
은의 벌크 전도도(bulk conductivity)는 약 6.2 × 105 S/cm 이고, 선형 은 나노와이어의 벌크 전도도는 이보다 다소 낮아지는 것으로 알려져 있다(Chem. Mater. 2002, 14, 4736-4745). 한편, 본 발명에 따른 투명전도성 코팅 필름은 브랜치드 은 나노와이어를 포함함으로써, 상기 전도도 값보다 향상된 전도도를 나타낼 수 있다.The bulk conductivity of silver is about 6.2 × 10 5 S / cm, and the bulk conductivity of linear silver nanowires is known to be somewhat lower (Chem. Mater. 2002, 14, 4736-4745). On the other hand, the transparent conductive coating film according to the present invention may include a branched silver nanowire, it can exhibit an improved conductivity than the conductivity value.
또한, 종래의 투명전도성 필름의 대표적인 예인 ITO는 약 85%의 투과도를 나타내나, 본 발명에 따른 투명전도성 필름은 약 85 ~ 95%의 투과도를 나타낼 수 있는 특징이 있다.In addition, ITO, which is a representative example of the conventional transparent conductive film, exhibits a transmittance of about 85%, but the transparent conductive film according to the present invention is characterized by exhibiting transmittance of about 85 to 95%.
본 발명에 따른 투명전도성 코팅 필름은 저비용, 고처리율 공정으로 제조할 수 있을 뿐만 아니라, 전기적, 광학적, 기계적 특성 등이 우수하다. 또한, 별도로 생성된 크기가 균일한 브랜치드 금속 나노시드를 이용함으로써, 브랜치드 은 나노와이어의 균일도를 향상시킬 수 있고, 투명전도성 코팅필름, 이를 포함하는 전자 소자 등에 유용하게 적용할 수 있다.The transparent conductive coating film according to the present invention can be manufactured in a low cost, high throughput process, and excellent in electrical, optical, mechanical properties, and the like. In addition, by using a branched metal nano seed having a uniform size generated separately, it is possible to improve the uniformity of the branched silver nanowires, and may be usefully applied to an electronic device including the transparent conductive coating film.
상기 전자 소자로는 평판 액정 표시 장치(flat liquid crystal display), 터치 패널(touch panel), 전자 발광 장치(electroluminescent device), 박막 광전지(thin film photovoltaic cell) 등을 들 수 있다.
The electronic device may be a flat liquid crystal display, a touch panel, an electroluminescent device, a thin film photovoltaic cell, or the like.
하기 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것일 뿐이며, 이에 의해서 본 발명의 범위 또는 내용을 축소되거나 제한하여 해석할 수 없다.The following examples are only intended to illustrate the present invention in more detail, whereby the scope or content of the present invention can not be reduced or limited to interpret.
실시예 1Example 1
세틸트리메틸암모늄 브로마이드(CTAB, 0.1 M) 50 mL에 10 mM HAuCl4 1.5 mL, 5 μL의 농축된 실버 플레이트, 3 mL의 10 mM L-아스코르브산를 넣고 오렌지색이 무색으로 변화되었을 때, 1 M NaOH 수용액 2.5 mL를 한 번에 투입하고 15 시간 동안 반응시켰다. 이 과정을 통해 tripod 형태를 포함하는 금 나노입자를 합성하고, 이 수용액을 원심분리하고 나서, 에틸렌글리콜로 세척하는 과정을 3회 반복하여, 금 나노입자를 분리하였다. 이와 같이 합성된 tripod 금 나노입자를 에틸렌글리콜 용액 0.1 mg/mL 농도로 만들어 seed 주입용액(seed 용액 1)으로 준비하였다.To 50 mL of cetyltrimethylammonium bromide (CTAB, 0.1 M), add 1 mL of 10 mM HAuCl 4 , 5 μL concentrated silver plate, 3 mL of 10 mM L-ascorbic acid, and change the color to orange. 2.5 mL was added at a time and reacted for 15 hours. Through this process, gold nanoparticles including a tripod form were synthesized, the aqueous solution was centrifuged, and the process of washing with ethylene glycol was repeated three times to separate gold nanoparticles. The tripod gold nanoparticles synthesized as described above were prepared in a seed injection solution (seed solution 1) at 0.1 mg / mL concentration of ethylene glycol solution.
에틸렌글리콜 100 mL와 10 mL seed 용액 혼합액에 100 mL의 질산은(silver nitrate) 함유 에틸렌글리콜 용액(질산은 농도: 1.0 × 10-1 mol/L) 및 100 mL의 PVP(polyvinyl pyrrolidone) 함유 에틸렌글리콜 용액(PVP 농도: 5.0 × 10-1 mol/L)을 일정한 유량으로 120 분 동안 투입하였다. 그 후에, 5 시간 동안 160 ℃로 유지시키면서 은 이온을 환원시킴으로써 브랜치드 은 나노와이어를 제조하였다. 반응이 완료된 후 온도를 상온으로 낮추고, 원심분리와 에틸렌글리콜로 3회 세척을 반복하고, 에탄올 100 mL로 생산된 브랜치드 은 나노와이어를 분산시켰다.Ethylene glycol solution containing 100 mL of silver nitrate (silver nitrate concentration: 1.0 × 10 -1 mol / L) and ethylene glycol solution containing 100 mL of polyvinyl pyrrolidone (PVP) in a mixture of 100 mL of ethylene glycol and 10 mL seed solution PVP concentration: 5.0 × 10 −1 mol / L) was added at a constant flow rate for 120 minutes. Thereafter, branched silver nanowires were prepared by reducing silver ions while maintaining at 160 ° C. for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, centrifugation and washing three times with ethylene glycol were repeated, and the branched silver nanowires produced with 100 mL of ethanol were dispersed.
실시예 2Example 2
세틸트리메틸암모늄 브로마이드(CTAB, 0.1 M) 50 mL에 10 mM HAuCl4 1.5 mL, 5 μL의 농축된 실버 플레이트, 3 mL의 10 mM L-아르코브산을 넣고 오렌지색이 무색으로 변화가 되었을 때, 1 M NaOH 수용액 2.5 mL를 한번에 투입하고 15 시간 반응시켰다. 이 과정을 통해 tripod 형태를 포함하는 금 나노입자 을 합성하고, 이 수용액을 원심분리하고, 에틸렌글리콜로 세척하는 과정을 3회 반복하여, 금 나노입자를 분리하였다. 이와 같이 합성된 tripod 금 나노입자를 에틸렌글리콜 용액 0.1 mg/mL 농도로 만들어 seed 주입용액(seed 용액 1)으로 준비하였다.50 mL of cetyltrimethylammonium bromide (CTAB, 0.1 M) was added 1.5 mL of 10 mM HAuCl 4 , 5 μL concentrated silver plate, 3 mL of 10 mM L-arcovic acid and the color of orange turned to colorless. 2.5 mL of M NaOH aqueous solution was added at once and reacted for 15 hours. Through this process, gold nanoparticles including tripod form were synthesized, the aqueous solution was centrifuged, and the process of washing with ethylene glycol was repeated three times to separate gold nanoparticles. The tripod gold nanoparticles synthesized as described above were prepared in a seed injection solution (seed solution 1) at 0.1 mg / mL concentration of ethylene glycol solution.
에틸렌글리콜 100 mL와 20 mL seed 용액 혼합액에 100 mL의 질산은(silver nitrate) 함유 에틸렌글리콜 용액(질산은 농도: 1.0 × 10-1 mol/L) 및 100 mL의 PVP(polyvinyl pyrrolidone) 함유 에틸렌글리콜 용액(PVP 농도: 5.0 × 10-1 mol/L)을 일정한 유량으로 120 분 동안 투입하였다. 그 후에, 5 시간 동안 160 ℃로 유지시키면서 은 이온을 환원시킴으로써 브랜치드 은 나노와이어를 제조하였다. 반응이 완료된 후 온도를 상온으로 낮추고, 원심분리와 에틸렌그리콜로 3회 세척을 반복하고, 에탄올 100 mL로 생산된 브랜치드 은 나노와이어를 분산시켰다.Ethylene glycol solution containing 100 mL of silver nitrate (silver nitrate concentration: 1.0 × 10 -1 mol / L) and 100 mL of polyvinyl pyrrolidone (PVP) in 100 mL of ethylene glycol and 20 mL seed solution mixture PVP concentration: 5.0 × 10 −1 mol / L) was added at a constant flow rate for 120 minutes. Thereafter, branched silver nanowires were prepared by reducing silver ions while maintaining at 160 ° C. for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, centrifugation and washing three times with ethylene glycol were repeated, and the branched silver nanowires produced with 100 mL of ethanol were dispersed.
실시예Example 3 3
세틸트리메틸암모늄 브로마이드(CTAB, 0.1 M) 50 mL에 10 mM HAuCl4 1.5 mL, 5 μL의 농축된 실버 플레이트, 3 mL의 10 mM L-아르코브산을 넣고 오렌지색이 무색으로 변화가 되었을 때, 1 M NaOH 수용액 2.5 mL를 한번에 투입하고 15 시간 반응시켰다. 이 과정을 통해 tripod 형태를 포함하는 금 나노입자 을 합성하고, 이 수용액을 원심분리하고, 에틸렌글리콜로 세척하는 과정을 3회 반복하여, 금 나노입자를 분리하였다. 이와 같이 합성된 tripod 금 나노입자를 에틸렌글리콜 용액 0.1 mg/mL 농도로 만들어 seed 주입용액(seed 용액 1)으로 준비하였다.50 mL of cetyltrimethylammonium bromide (CTAB, 0.1 M) was added 1.5 mL of 10 mM HAuCl 4 , 5 μL concentrated silver plate, 3 mL of 10 mM L-arcovic acid and the color of orange turned to colorless. 2.5 mL of M NaOH aqueous solution was added at once and reacted for 15 hours. Through this process, gold nanoparticles including tripod form were synthesized, the aqueous solution was centrifuged, and the process of washing with ethylene glycol was repeated three times to separate gold nanoparticles. The tripod gold nanoparticles synthesized as described above were prepared in a seed injection solution (seed solution 1) at 0.1 mg / mL concentration of ethylene glycol solution.
에틸렌글리콜 100 mL와 30 mL seed 용액 혼합액에 100 mL의 질산은(silver nitrate) 함유 에틸렌글리콜 용액(질산은 농도: 1.0 × 10-1 mol/L) 및 100 mL의 PVP(polyvinyl pyrrolidone) 함유 에틸렌글리콜 용액(PVP 농도: 5.0 × 10-1 mol/L)을 일정한 유량으로 120 분 동안 투입하였다. 그 후에, 5 시간 동안 160 ℃로 유지시키면서 은 이온을 환원시킴으로써 브랜치드 은 나노와이어를 제조하였다.Ethylene glycol solution containing 100 mL of silver nitrate (silver nitrate concentration: 1.0 × 10 -1 mol / L) and 100 mL of polyvinyl pyrrolidone (PVP) in 100 mL of ethylene glycol and 30 mL seed solution mixture PVP concentration: 5.0 × 10 −1 mol / L) was added at a constant flow rate for 120 minutes. Thereafter, branched silver nanowires were prepared by reducing silver ions while maintaining at 160 ° C. for 5 hours.
반응이 완료된 후 온도를 상온으로 낮추고, 원심분리와 에틸렌그리콜로 3회 세척을 반복하고, 에탄올 100 mL로 생산된 브랜치드 은 나노와이어를 분산시켰다.After the reaction was completed, the temperature was lowered to room temperature, centrifugation and washing three times with ethylene glycol were repeated, and the branched silver nanowires produced with 100 mL of ethanol were dispersed.
비교예Comparative example 1 One
에틸렌글리콜 110 mL에 100 mL의 질산은(silver nitrate) 함유 에틸렌글리콜 용액(질산은 농도: 1.0 × 10-1 mol/L) 및 100 mL의 PVP(polyvinyl pyrrolidone) 함유 에틸렌글리콜 용액(PVP 농도: 5.0 × 10-1 mol/L)을 일정한 유량으로 120 분 동안 투입하였다. 그 후에, 5 시간 동안 160 ℃로 유지시키면서 은 이온을 환원시킴으로써 은 나노와이어를 제조하였다. 반응이 완료된 후 온도를 상온으로 낮추고, 원심분리와 에틸렌그리콜로 3회 세척을 반복하고, 에탄올 100 mL로 생산된 은 나노와이어를 분산시켰다.Ethylene glycol solution containing 100 mL of silver nitrate (silver nitrate concentration: 1.0 × 10 -1 mol / L) and 100 mL of polyvinyl pyrrolidone (PVP) in 110 mL of ethylene glycol (PVP concentration: 5.0 × 10) -1 mol / L) was added at a constant flow rate for 120 minutes. Thereafter, silver nanowires were prepared by reducing silver ions while maintaining the temperature at 160 ° C. for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, centrifugation and washing three times with ethylene glycol were repeated, and silver nanowires produced with 100 mL of ethanol were dispersed.
비교예Comparative example 2 2
에틸렌글리콜 120 mL에 100 mL의 질산은(silver nitrate) 함유 에틸렌글리콜 용액(질산은 농도: 1.0 × 10-1 mol/L) 및 100 mL의 PVP(polyvinyl pyrrolidone) 함유 에틸렌글리콜 용액(PVP 농도: 5.0 × 10-1 mol/L)을 일정한 유량으로 120 분 동안 투입하였다. 그 후에, 5 시간 동안 160 ℃로 유지시키면서 은 이온을 환원시킴으로써 은 나노와이어를 제조하였다. 반응이 완료된 후 온도를 상온으로 낮추고, 원심분리와 에틸렌그리콜로 3회 세척을 반복하고, 에탄올 100 mL로 생산된 은 나노와이어를 분산시켰다.Ethylene glycol solution containing 100 mL of silver nitrate (silver nitrate concentration: 1.0 × 10 -1 mol / L) and 120 mL of ethylene glycol solution containing 100 mL of polyvinyl pyrrolidone (PVP concentration: 5.0 × 10) in 120 mL of ethylene glycol -1 mol / L) was added at a constant flow rate for 120 minutes. Thereafter, silver nanowires were prepared by reducing silver ions while maintaining the temperature at 160 ° C. for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, centrifugation and washing three times with ethylene glycol were repeated, and silver nanowires produced with 100 mL of ethanol were dispersed.
비교예Comparative example 3 3
에틸렌글리콜 130 mL에 100 mL의 질산은(silver nitrate) 함유 에틸렌글리콜 용액(질산은 농도: 1.0 × 10-1 mol/L) 및 100 mL의 PVP(polyvinyl pyrrolidone) 함유 에틸렌글리콜 용액(PVP 농도: 5.0 × 10-1 mol/L)을 일정한 유량으로 120 분 동안 투입하였다. 그 후에, 5 시간 동안 160 ℃로 유지시키면서 은 이온을 환원시킴으로써 은 나노와이어를 제조하였다. 반응이 완료된 후 온도를 상온으로 낮추고, 원심분리와 에틸렌그리콜로 3회 세척을 반복하고, 에탄올 100 mL로 생산된 은 나노와이어를 분산시켰다.Ethylene glycol solution containing 100 mL of silver nitrate (silver nitrate concentration: 1.0 × 10 -1 mol / L) and 130 mL of ethylene glycol solution containing 100 mL of polyvinyl pyrrolidone (PVP concentration: 5.0 × 10) in 130 mL of ethylene glycol -1 mol / L) was added at a constant flow rate for 120 minutes. Thereafter, silver nanowires were prepared by reducing silver ions while maintaining the temperature at 160 ° C. for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, centrifugation and washing three times with ethylene glycol were repeated, and silver nanowires produced with 100 mL of ethanol were dispersed.
시험예Test Example
위와 같이 합성한 나노와이어 용액을 spin coater를 이용하여, 슬라이드 글라스 위에 코팅하고, 코팅 후 진공오븐에서 1 시간 건조하였다. 나노와이어의 전기특성, 광특성 평가를 위해 4 point probe를 이용해서 면저항을 측정하고, 투과율 측정기로 투과율을 측정하였다. 또한, 어닐링 효과를 확인하기 위해 면저항과 투과율은 120 ℃ 오븐 내 질소 분위기 하에서 1 시간 어닐링 전과 후에 각각 측정하였다.The nanowire solution synthesized as above was coated on a slide glass using a spin coater, and dried in a vacuum oven for 1 hour after coating. In order to evaluate the electrical and optical properties of the nanowires, sheet resistance was measured using a 4 point probe, and transmittance was measured using a transmittance meter. In addition, in order to confirm the annealing effect, sheet resistance and transmittance were measured before and after annealing for 1 hour under nitrogen atmosphere in an oven at 120 ° C.
Claims (8)
2) 상기 브랜치드 금속 나노시드와 폴리올 공정(polyol process)을 이용하여 브랜치드 은 나노와이어를 성장시키는 단계, 및
3) 상기 브랜치드 은 나노와이어를 기판 상에 코팅하여 코팅층을 형성한 후, 상기 코팅층을 어닐링(annealing)하는 단계
를 포함하는 투명전도성 코팅 필름의 제조방법.1) preparing a branched metal nanoseed (nano seed), and then purifying,
2) growing branched silver nanowires using the branched metal nanoseed and a polyol process, and
3) coating the branched silver nanowires on a substrate to form a coating layer, and then annealing the coating layer.
Method for producing a transparent conductive coating film comprising a.
상기 1) 단계의 브랜치드 금속 나노시드는 백금, 금, 은, 구리, 니켈, 철, 알루미늄, 팔라듐 및 이리듐으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 투명전도성 코팅 필름의 제조방법.The method of claim 1,
Branched metal nanoseed of step 1) is a method for producing a transparent conductive coating film, characterized in that it comprises at least one selected from the group consisting of platinum, gold, silver, copper, nickel, iron, aluminum, palladium and iridium. .
상기 2) 단계의 폴리올 공정은 은을 포함하는 화합물과 폴리올을 이용하고, 은의 환원공정에 의해 수행되는 것을 특징으로 하는 투명전도성 코팅 필름의 제조방법.The method of claim 1,
The polyol process of step 2) using a compound and a polyol containing silver, the method of producing a transparent conductive coating film, characterized in that carried out by a reduction process of silver.
상기 은을 포함하는 화합물은 질산은 및 은 실리케이트로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 투명전도성 코팅 필름의 제조방법.The method of claim 3,
The silver-containing compound is a method for producing a transparent conductive coating film, characterized in that it comprises one or more selected from the group consisting of silver nitrate and silver silicates.
상기 2) 단계의 수행시 캡핑제(capping agent)를 추가로 투입하는 것을 특징으로 하는 투명전도성 코팅 필름의 제조방법.The method of claim 1,
Method of producing a transparent conductive coating film, characterized in that further adding a capping agent (capping agent) when performing the step 2).
상기 3) 단계의 어닐링의 온도는 90 ~ 150℃인 것을 특징으로 하는 투명전도성 코팅 필름의 제조방법.The method of claim 1,
The temperature of the annealing step 3) is a method for producing a transparent conductive coating film, characterized in that 90 ~ 150 ℃.
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