KR102313100B1 - Silver nanowire and manufacturing method thereof - Google Patents
Silver nanowire and manufacturing method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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Abstract
Description
본 발명은 은 나노와이어 및 그 제조방법에 관한 것으로서, 특히 은 나노와이어가 가지고 있는 단점인 코팅 후 노란색을 띄는 현상을 극복하고, 수율을 향상시킬 수 있는 은 나노와이어의 제조방법에 관한 것이다.The present invention relates to a silver nanowire and a method for producing the same, and more particularly, to a method for producing a silver nanowire capable of overcoming a yellowish phenomenon after coating, which is a disadvantage of silver nanowires, and improving the yield.
디스플레이 분야 및 태양전지 산업의 급속한 발달와 함께 투명도전막에 대한 수요도 급증하고 있다. 현재 투명전극소재로 ITO(Indium Tin Oxide), CNT, Graphen, ZnO, PEDOT 등 다양한 소재가 개발되어 있고, 양산기술 및 용도에 대한 적합성으로 인해 이중 ITO가 주로 사용되어 지고 있다.With the rapid development of the display field and the solar cell industry, the demand for transparent conductive films is also increasing rapidly. Currently, various materials such as ITO (Indium Tin Oxide), CNT, Graphen, ZnO, and PEDOT have been developed as transparent electrode materials.
ITO 전극은 전극층의 유연성이 부족하기 때문에 플렉시블 디스플레이(flexible display)용 투명전극으로 사용하기 쉽지 않고, 또한 ITO 전극은 제조비용이 많이 들며 원재료인 인듐(In)은 중국이 과점하고 있고 공급량도 충분하지 않기 때문에 커다란 가격상승요인 가지고 있다.The ITO electrode is not easy to use as a transparent electrode for a flexible display because the electrode layer lacks flexibility. Also, the ITO electrode is expensive to manufacture, and China has an oligopoly on indium (In), a raw material, and the supply is not sufficient. Because of this, there is a huge price increase factor.
최근 플렉시블 디스플레이(flexible display) 수요가 증대되며 제조원가절감에 대한 시장요구가 커지면서 ITO 투명전극을 대체하기 위한 소재의 필요성이 적극 대두되어지고 있다. ITO 투명전극을 대체할 수단으로 은이 갖는 양호한 전기적 성질과 물리적 성질을 지닌 은 나노와이어를 이용한 투명전극소재가 개발되고 있다.Recently, as the demand for flexible display increases and the market demand for manufacturing cost reduction increases, the need for a material to replace the ITO transparent electrode is actively emerging. As a means to replace the ITO transparent electrode, a transparent electrode material using silver nanowires with good electrical and physical properties of silver is being developed.
새로운 투명전극소재로서 은 나노와이는, 금속 중에서 그 화학적 안정성이 높고, 열전도도 및 전기전도도가 매우 좋은 은의 특징과 나노와이어의 아주 작은 치수로 인해 나타나는 광학적 특성인 투명성까지 더해져 투명도전막을 제조하기 위한 전극소재이다. 이러한 은 나노와이어는 향후 PDP(플라즈마 디스플레이 판넬), 광학필터, 전자차폐제, 유기발광다이오드(OLED), 태양전지, LCD(liquid crystal display), 터치스크린, 휴대폰용 EL 키패드 등 전기, 자기, 광학 소자 및 센서 등에 광범위하게 적용할 수 있다.As a new transparent electrode material, silver nanowires have high chemical stability among metals, and the characteristics of silver with very good thermal and electrical conductivity and transparency, which is an optical characteristic due to the very small dimensions of nanowires, are added to produce a transparent conductive film. electrode material. These silver nanowires will be used in electrical, magnetic and optical devices such as PDP (plasma display panel), optical filter, electronic shielding agent, organic light emitting diode (OLED), solar cell, liquid crystal display (LCD), touch screen, and EL keypad for mobile phone in the future. and sensors, and the like.
은 나노와이어가 다양하게 응용되어 여러 분야에 활용되기 위해서는 응용되어지는 분야에서 요구하는 직경, 길이 및 장단축비를 충족시킴과 동시에 각각의 크기 편차를 작게 제어하며 완화된 조건으로 대량생산하는 기술이 가장 중요하다.In order for silver nanowires to be applied in various fields and used in various fields, it is necessary to meet the diameter, length, and length and shortening ratios required in the field to be applied, and at the same time to control the size deviation of each silver nanowire small and mass-produce it under relaxed conditions. Most important.
투명도전막은 가시광 영역(380~780㎚ 파장)에서 투명하고, 전기전도도가 우수한 전극을 의미하며 최근 투명도전막의 광투과도와 면저항에 대한 요구조건이 강화되어지고 있다. 광투과도는 90%이상, 면저항은 150Ω/□ 이하가 요구된다.The transparent conductive film is transparent in the visible light region (wavelength of 380 to 780 nm) and means an electrode with excellent electrical conductivity. Light transmittance of 90% or more and sheet resistance of 150Ω/□ or less are required.
나노와이어의 길이, 직경 및 장축단비는 전기전도도, 광투과도에 영향을 미친다. 즉, 길이가 긴 나노와이어일수록 투명도전막의 목표하는 전도성을 획득하는데 보다 적은 나노와이어가 필요하므로, 더 높은 장축단비를 갖는 나노와이어가 유리하다. 또한 직경이 작은 나노와이어일수록 더 높은 광투과도와 더 낮은 헤이즈를 제공할 수 있다.The length, diameter, and long-axis ratio of nanowires affect electrical conductivity and light transmittance. That is, the longer the nanowire, the less the nanowire is required to obtain the target conductivity of the transparent conductive film, so the nanowire having a higher major-axis ratio is advantageous. In addition, nanowires with smaller diameters can provide higher light transmittance and lower haze.
은 나노와이어를 대규모로 제조하는 종래의 일반적인 방법은 일명 '폴리올 공정 (polyol process)'이라고도 하는 액상화학법인데, 폴리올 용매에 캡핑 시약, 할로겐 촉매, AgNO3 등으로 전구체용액을 혼합 후 가열하여 제조하는 방법이다.A conventional general method for large-scale production of silver nanowires is a liquid-phase chemical method, also called a 'polyol process'. way.
폴리올 공정에 대해서는 특허문헌 0001 등이 알려져 있다.Patent document 0001 etc. are known about a polyol process.
이러한 폴리올 공정은, 폴리 비닐 피롤리돈(이하, 'PVP')의 존재하에 에틸렌 글리콜, 프로필렌글리콜 등과 같은 폴리올에 의해 은염를 환원시키는 것을 포함한다. 일반적으로, 환원 공정은 160℃ 이하의 온도에서 실시된다. 이때 폴리올은 일반적으로 용매뿐만 아니라 환원제로서의 이중 기능을 가진다.This polyol process involves the reduction of a silver salt by a polyol such as ethylene glycol, propylene glycol, etc. in the presence of polyvinyl pyrrolidone (hereinafter 'PVP'). In general, the reduction process is carried out at a temperature of 160° C. or less. In this case, the polyol generally has a dual function as a reducing agent as well as a solvent.
은염은 폴리올 용매에 의해 용액 상에서 은 원자로 환원된다. 일반적으로, 은 원자는 초기에 균질한 핵생성 과정을 통해 시드(Seed)를 형성한다. 이 시드는 일반적으로 직경이 1~5nm인 결정체이다. 이들 시드 중 일부는 용액 상에서 성장을 계속하여 등방성 나노구조체들(나노 입자)을 형성한다. 나노입자는 모든 방향에서 동일하게 성장이 진행된 결과이다. 이와 대조적으로, 일부 시드는 이방성 나노구조체들(나노튜브, 나노로드, 나노벨트, 나노와이어 등)로 성장하고, 이는 측면 방향을 따라 우선적으로 성장한 결과이다.The silver salt is reduced to silver atoms in solution phase with a polyol solvent. In general, silver atoms initially form seeds through a homogeneous nucleation process. These seeds are usually crystals with a diameter of 1-5 nm. Some of these seeds continue to grow in solution phase, forming isotropic nanostructures (nanoparticles). Nanoparticles are the result of the same growth in all directions. In contrast, some seeds grow into anisotropic nanostructures (nanotubes, nanorods, nanobelts, nanowires, etc.), which are the result of preferential growth along the lateral direction.
은 나노와이어의 직경 및 길이는 PVP와 은염의 종류 및 상대적 양, PVP와 은염의 농도, 촉매의 종류와 농도, 반응 시간 및 반응 온도를 포함하는 여러 변수들에 의해 영향을 받는다.The diameter and length of silver nanowires are affected by several variables including the type and relative amount of PVP and silver salt, the concentration of PVP and silver salt, the type and concentration of catalyst, reaction time and reaction temperature.
한편, 평균 직경 17~25nm, 평균 길이 17~23㎛의 길이의 은 나노와이어를 제조할 수 있고, 은 나노와이어 제조를 위해 투입되는 은의 수율 80몰% 이상과, 높은 단분산도를 가진 은 나노와이어를 제조할 수 있는 은 나노와이어 제조방법이 특허문헌 0002로 제안된 바 있다.On the other hand, silver nanowires having an average diameter of 17 to 25 nm and an average length of 17 to 23 μm can be produced, and silver nanowires having a yield of 80 mol% or more and a high monodispersity of silver input for the production of silver nanowires A method of manufacturing a silver nanowire capable of manufacturing a wire has been proposed in Patent Document 0002.
특허문헌 0002는 폴리올 공정에서 염화암모늄 또는 암모늄을 포함한 촉매를 사용함으로써 작은 직경의 은 나노와이어를 높은 수율로 제조할 수 있는 이점이 있다.Patent Document 0002 has an advantage in that silver nanowires having a small diameter can be manufactured in high yield by using a catalyst including ammonium chloride or ammonium in a polyol process.
그러나, 특허문헌 0001 및 0002는 은 나노와이어가 가지고 있는 단점인 코팅 후 노란색을 띄는 현상이 있는 문제가 있다.However, Patent Documents 0001 and 0002 have a problem in that silver nanowires have a yellow color after coating, which is a disadvantage.
이와 같은 종래의 문제점을 해결하기 위한 본 발명은 은 나노와이어를 코팅 후 노란색을 띄는 현상을 극복할 수 있고 높은 수율로 은 나노와이어를 합성할 수 있는 은 나노와이어의 제조방법을 제공하는 것을 목적으로 한다.The present invention for solving the problems of the prior art is to provide a method of manufacturing silver nanowires capable of overcoming the yellowing phenomenon after coating the silver nanowires and synthesizing the silver nanowires with a high yield. do.
상기와 같은 목적을 달성하기 위한 본 발명은,The present invention for achieving the above object,
a) 은 수용액 준비단계와;a) preparing a silver aqueous solution;
b) 용매에 촉매를 첨가한 후 가열하고, 은 수용액을 투입하여 은 나노와이어 합성액을 얻는 단계와, b) adding a catalyst to the solvent, heating it, and adding an aqueous silver solution to obtain a silver nanowire synthesis solution;
c) 상기 은 나노와이어 합성액의 은 나노와이어를 정제하는 단계를 포함하고,c) purifying the silver nanowires of the silver nanowire synthesis solution,
상기 촉매는 상기 촉매는 SbCl3로 이루어지는 것을 특징으로 하는 은 나노와이어의 제조방법을 제공한다.The catalyst provides a method for producing a silver nanowire, characterized in that the catalyst consists of SbCl 3 .
상기 a)단계의 상기 은 수용액은 용매에 은 전구체를 투입하여 제조할 수 있다. 상기 용매는 증류수에 펜타에리트리톨을 혼합한 혼합용액으로 이루어질 수 있으나, 글리세린에 펜타에리트리톨을 혼합한 혼합용액으로 이루어지는 것이 바람직하다.The silver aqueous solution of step a) may be prepared by adding a silver precursor to a solvent. The solvent may be a mixed solution of distilled water mixed with pentaerythritol, but preferably a mixed solution of glycerin mixed with pentaerythritol.
상기 은 수용액의 은 전구체는 AgNO3, KagCN2 중 선택된 1종으로 이루어질 수 있다.The silver precursor of the silver aqueous solution may be formed of one selected from AgNO3 and KagCN2.
그리고, 상기 b)단계의 용매는 증류수에 펜타에리트리톨을 혼합한 혼합용액으로 이루어진다. 상기 용매는 증류수에 펜타에리트리톨을 혼합한 혼합용액으로 이루어질 수 있으나, 글리세린에 펜타에리트리톨을 혼합한 혼합용액으로 이루어지는 것이 바람직하다.And, the solvent of step b) consists of a mixed solution in which pentaerythritol is mixed with distilled water. The solvent may be a mixed solution of distilled water mixed with pentaerythritol, but preferably a mixed solution of glycerin mixed with pentaerythritol.
특히, 상기 b)단계는 상기 용매에 SbCl3 촉매, 폴리비닐피롤리돈 K30을 투입하여 용해시킨 다음, 폴리비닐피롤리돈 K90을 혼합 후 120℃ 내지 180℃로 가열하고, 상기 은 수용액을 투입한 후 150℃의 온도로 4시간 동안 유지하여 나노와이어를 형성하는 것이 좋다.In particular, in step b), the SbCl 3 catalyst and polyvinylpyrrolidone K30 are added and dissolved in the solvent, and then polyvinylpyrrolidone K90 is mixed and heated to 120° C. to 180° C., and the silver aqueous solution is added. After that, it is good to form a nanowire by maintaining it at a temperature of 150° C. for 4 hours.
그리고 상기 c)단계는 상기 은 나노와이어 합성액에 증류수 및 이소프로필알코올을 투입하여 은 나노와이어를 분산시킨 후 아세톤을 투입하여 응집된 은 나노와이어를 수득하고, 수득된 은 나노와이어를 증류수에 분산시킨 후 아세톤을 투입하여 응집된 은 나노와이어를 수득하는 공정을 포함하여 이루어지는 것이 바람직하다.And in step c), distilled water and isopropyl alcohol were added to the silver nanowire synthesis solution to disperse silver nanowires, and acetone was added to obtain agglomerated silver nanowires, and the obtained silver nanowires were dispersed in distilled water. It is preferable to include a step of obtaining agglomerated silver nanowires by adding acetone after the process.
아울러, 본 발명은 상기 은 나노와이어의 제조방법에 의해 제조된 것을 특징으로 하는 은 나노와이어를 제공한다.In addition, the present invention provides a silver nanowire, characterized in that produced by the method for producing the silver nanowire.
본 발명의 은 나노와이어의 제조방법은 은 나노와이어를 코팅 후 노란색을 띄는 현상을 극복할 수 있고 높은 수율로 은 나노와이어를 합성할 수 있는 효과가 있다.The method for manufacturing silver nanowires of the present invention has the effect of overcoming the yellowing phenomenon after coating the silver nanowires and synthesizing the silver nanowires with a high yield.
이하, 본 발명의 은 나노와이어의 제조방법에 대해 상세히 설명하면 다음과 같다.Hereinafter, the manufacturing method of the silver nanowire of the present invention will be described in detail as follows.
본 발명의 은 나노와이어의 제조방법은 크게, 은 수용액 준비단계, 은 나노와이어 합성단계 및 은 나노와이어 정제단계를 포함하여 이루어진다.The method for producing a silver nanowire of the present invention largely includes a silver aqueous solution preparation step, a silver nanowire synthesis step, and a silver nanowire purification step.
먼저, 상기 은 수용액 준비단계는 용매에 은 전구체를 투입하여 제조된다. First, the silver aqueous solution preparation step is prepared by adding a silver precursor to a solvent.
상기 용매로서 증류수에 펜타에리트리톨을 혼합한 용매를 사용하는 것이 좋다. 이때 상기 증류수 100중량부에 펜타에리트리톨 5 내지 15중량부를 혼합하는 것이 좋다. 상기 펜타에리트리톨을 5중량부 미만으로 혼합하면 수분증발이 많아 좋지 못하고, 15중량부 초과로 혼합하면 와이어생성에 좋지 못하다.It is preferable to use a solvent in which pentaerythritol is mixed with distilled water as the solvent. At this time, it is preferable to mix 5 to 15 parts by weight of pentaerythritol in 100 parts by weight of the distilled water. When the pentaerythritol is mixed in less than 5 parts by weight, it is not good because there is a lot of moisture evaporation, and when mixed in more than 15 parts by weight, it is not good to produce a wire.
그리고 상기 은 전구체로서 AgNO3, KagCN2 중 선택된 1종을 사용할 수 있다.In addition, one selected from AgNO3 and KagCN2 may be used as the silver precursor.
상기 은 전구체는 상기 용매 100중량부에 0.8g 내지 3g 중량부를 투입하는 것이 좋다. 상기 은 전구체를 0.8g 중량부 미만으로 혼합하면 수율에 좋지 못하고, 3g 중량부 초과로 혼합하면 와이어의 두께를 얇게 하는 것에 좋지 못하다.It is preferable that 0.8 g to 3 g parts by weight of the silver precursor be added to 100 parts by weight of the solvent. When the silver precursor is mixed in less than 0.8 g parts by weight, the yield is not good, and when the silver precursor is mixed in more than 3 g parts by weight, it is not good to thin the thickness of the wire.
다음으로, 상기 은 나노와이어 합성단계는 용매에 촉매를 첨가한 후 가열하고, 상기 은 수용액을 투입하여 은 나노와이어 합성액을 얻는 단계이다.Next, the silver nanowire synthesis step is a step to obtain a silver nanowire synthesis solution by adding a catalyst to a solvent, heating, and then adding the silver aqueous solution.
상기 용매는 은 나노와이어의 수율을 향상시키기 위해 증류수에 펜타에리트리톨을 혼합한 환원용매를 사용하는 것이 좋다. 상기 증류수 100중량부에 펜타에리트리톨 5 내지 15중량부를 혼합하는 것이 좋다. 상기 펜타에리트리톨을 5중량부 미만으로 혼합하면 수분증발량이 많아 좋지 못하고, 15중량부 초과로 혼합하면 와이어 생성의 방해가 되어 좋지 못하다.As the solvent, it is preferable to use a reducing solvent in which pentaerythritol is mixed with distilled water in order to improve the yield of silver nanowires. It is preferable to mix 5 to 15 parts by weight of pentaerythritol in 100 parts by weight of the distilled water. When the pentaerythritol is mixed in less than 5 parts by weight, the amount of water evaporated is not good, and when mixed in more than 15 parts by weight, it is not good because it interferes with wire generation.
특히, 상기 용매는 수분의 증발량을 막기 위하여, 글리세린에 펜타에리트리톨을 혼합한 환원용매를 사용하는 것이 좋다. 상기 펜타에리트리톨을 5중량부 미만으로 혼합하면 글리세린의 점성 때문에 교반에 좋지 못하고, 15중량부 초과로 혼합하면 와이어 생성의 방해가 되어 좋지 못하다. In particular, as the solvent, it is preferable to use a reducing solvent in which pentaerythritol is mixed with glycerin in order to prevent the evaporation of moisture. When the pentaerythritol is mixed in less than 5 parts by weight, it is not good for stirring because of the viscosity of glycerin, and when mixed in more than 15 parts by weight, it is not good because it interferes with the production of the wire.
그리고 상기 촉매는 은 나노와이어의 형성반응을 촉진시키기 위한 것으로서, 특히 은 나노와이어가 노란색을 띄는 현상을 극복하고 백색을 나타내도록 하기 위하여 촉매로서 SbCl3를 사용한다. In addition, the catalyst is to promote the formation of silver nanowires, and in particular, SbCl 3 is used as a catalyst in order to overcome a phenomenon in which the silver nanowires are yellow and exhibit a white color.
상기 SbCl3는 상기 은 수용액의 은 전구체 100중량부에 대해 0.03g 내지 1g 중량부를 사용하는 것이 바람직하다. 0.03g 중량부 미만으로 혼합하면 은 나노와이어의 합성 반응을 충분히 촉진할 수 없고, 노란색을 띄는 현상을 효과적으로 방지할 수 없고, 1g 중량부 초과로 혼합하면 과응집을 발생시켜서 좋지 못하다.The SbCl 3 is preferably used in an amount of 0.03 g to 1 g by weight based on 100 parts by weight of the silver precursor in the silver aqueous solution. When mixed in less than 0.03 g parts by weight, the synthesis reaction of silver nanowires cannot be sufficiently promoted, and the yellowing phenomenon cannot be effectively prevented, and when mixed in excess of 1 g parts by weight, over-agglomeration occurs, which is not good.
상기 은 나노와이어 합성단계는 상기 용매에 SbCl3 촉매를 첨가한 후 가열하면서 캡핑제를 첨가하고, 상기 캡핑제가 완전 용해된 후 온도를 유지한 상태에서 상기 은 수용액을 투입하여 은 나노와이어 합성액을 얻는다.In the silver nanowire synthesis step , after adding the SbCl 3 catalyst to the solvent, a capping agent is added while heating, and after the capping agent is completely dissolved, the silver aqueous solution is added while maintaining the temperature to obtain a silver nanowire synthesis solution. get
특히, 상기 캡핑제로서 PVP(Polyvinylpyrrolidone)를 사용하는 것이 좋다. 상기 캡핑제의 용해 시간을 단축하기 위해, 상기 용매에 촉매를 첨가한 후 승온 중 80 내지 120℃에서 PVP K30을 투입하고, 상기 PVP K30이 용해된 후 PVP K90을 투입하는 것이 좋다.In particular, it is preferable to use polyvinylpyrrolidone (PVP) as the capping agent. In order to shorten the dissolution time of the capping agent, it is preferable to add PVP K30 at 80 to 120° C. during temperature rise after adding the catalyst to the solvent, and then add PVP K90 after the PVP K30 is dissolved.
다음으로 상기 은 나노와이어 정제단계는 은 나노와이어의 합성 후 잔존하는 캡핑제, 은 전구체 등을 분리하여 은 나노와어를 정제 및 수거하기 위한 단계이다.Next, the silver nanowire purification step is a step for purifying and collecting the silver nanowires by separating the capping agent, the silver precursor, etc. remaining after the synthesis of the silver nanowires.
상기 은 나노와이어 정제단계는 상기 은 나노와이어 합성액에 증류수 및 이소프로필알코올을 투입하여 은 나노와이어를 분산시킨 후 아세톤을 투입한 후 응집된 은 나노와이어를 수득하는 단계와, 수득된 은 노나와이어를 증류수에 분산시킨 후 아세톤을 투입하여 응집된 은 나노와이어를 수득하는 단계를 포함하여 이루어지는 것이 좋다.In the silver nanowire purification step, distilled water and isopropyl alcohol were added to the silver nanowire synthesis solution to disperse the silver nanowires, and then acetone was added to obtain agglomerated silver nanowires; After dispersing in distilled water, acetone is preferably added to obtain agglomerated silver nanowires.
이때 상기 은 나노와이어 합성액에 증류수 뿐만 아니라 이소프로필알코올을 투입함으로서, 아세톤 투입시 층분리가 일어나지 않고, 은 나노와이어가 효과적으로 응집되어 은 나노와이어를 효과적으로 정제할 수 있는 이점이 있다. 특히, 증류수와 이소프로필알코올을 1:1의 부피비로 상기 은 나노와이어 합성액에 투입하는 것이 좋다.At this time, by adding isopropyl alcohol as well as distilled water to the silver nanowire synthesis solution, layer separation does not occur when acetone is added, and the silver nanowires are effectively aggregated to effectively purify the silver nanowires. In particular, it is preferable to add distilled water and isopropyl alcohol to the silver nanowire synthesis solution in a volume ratio of 1:1.
이와 같이 정제된 은 나노와이어는 노란색을 띄지 않고 백색을 나타내는 특성을 가지는 등 색특성이 크게 개선된 이점이 있다.The silver nanowires purified in this way have the advantage of greatly improved color characteristics, such as having a white characteristic without showing a yellow color.
다음으로, 본 발명의 은 나노와이어의 제조방법을 실시예를 들어 상세히 설명하면 다음과 같고, 본 발명의 권리범위는 하기의 실시예에 한정되는 것은 아니다.Next, the manufacturing method of the silver nanowire of the present invention will be described in detail with reference to examples, and the scope of the present invention is not limited to the following examples.
[실시예 1][Example 1]
DIW 100ml에 펜타에리트리톨(대정화금) 10g을 혼합하였고, 여기에 질산은(삼전화학)1.6g을 투입하여 질산은 수용액을 제조하였다. 10 g of pentaerythritol (Daejeong Hwageum) was mixed with 100 ml of DIW, and 1.6 g of silver nitrate (Samjeon Chemical) was added thereto to prepare an aqueous solution of silver nitrate.
DIW 300ml에 펜타에리트리톨(대정화금) 30g을 혼합하였고, 여기에 촉매로서 SbCl3(삼염화안티몬/대정화금) 0.03g을 투입하여 마그네틱바를 이용하여 RPM 약 30으로 저속으로 교반하였고, 온도 상승 중에 PVP K30(아크로스)을 0.3g투입 후 완전히 용해시킨 다음 PVP K90(바스프)을 2.3g을 투입하였다. 150℃까지 가열 후 PVP K90이 완전히 용해된 다음, 질산은 수용액을 드랍핑하여 투입하였다. 이후 150℃를 유지하였으며 약 4시간 반응하여 은 나노와이어 합성을 완료했다. 이때 PVP K30의 완전 용해시간은 25분 소요됐고, PVP K90의 완전 용해시간은 90분 소요됐다.30 g of pentaerythritol (Daejeong Hwageum) was mixed with 300 ml of DIW, and 0.03 g of SbCl3 (antimony trichloride/Daejeong Hwageum) as a catalyst was added thereto. Using a magnetic bar, the mixture was stirred at a low speed at about 30 RPM and while the temperature was rising. After 0.3 g of PVP K30 (Across) was added and completely dissolved, 2.3 g of PVP K90 (BASF) was added. After heating to 150° C., PVP K90 was completely dissolved, and then an aqueous silver nitrate solution was added by dropping. Thereafter, the temperature was maintained at 150° C. and the reaction was completed for about 4 hours to complete the synthesis of silver nanowires. At this time, the complete dissolution time of PVP K30 was 25 minutes, and the complete dissolution time of PVP K90 was 90 minutes.
수득한 은 나노와이어 합성액에 DIW 40ml, IPA 40ml을 투입후 분산하였고, 분산이 완료된 후 아세톤 약 2L를 투입하여 은 나노와이어를 수득하였다. 그리고 수득된 은 나노와이어를 DIW 300ml에 분산하였고, 2차적으로 분산액에 아세톤 1.2L를 투입하여 정제를 하였고, 본 과정을 두차례 더 반복하여 은 나노와이어를 정제한 후 DIW에 보관하였다.40ml of DIW and 40ml of IPA were added to the obtained silver nanowire synthesis solution and then dispersed, and after dispersion was completed, about 2L of acetone was added to obtain silver nanowires. Then, the obtained silver nanowires were dispersed in 300ml of DIW, and secondarily, 1.2L of acetone was added to the dispersion for purification, and this process was repeated two more times to purify the silver nanowires and stored in DIW.
[실시예 2][Example 2]
글리세린 100ml에 펜타에리트리톨(대정화금) 10g을 혼합하였고, 여기에 질산은(삼전화학)1.6g을 투입하여 질산은 수용액을 제조하였다. 이때 글리세린의 점성 때문에 약 100℃로 가열한 상태에서 교반하여 혼합했다.10 g of pentaerythritol (Daejeong Hwageum) was mixed with 100 ml of glycerin, and 1.6 g of silver nitrate (Samjeon Chemical) was added thereto to prepare an aqueous silver nitrate solution. At this time, due to the viscosity of glycerin, the mixture was stirred and mixed while heated to about 100°C.
글리세린 300ml에 펜타에리트리톨(대정화금) 30g을 혼합하였고, 여기에 SbCl3(삼염화안티몬/대정화금) 0.03g을 투입하여 마그네틱바를 이용하여 RPM 약 30으로 저속으로 교반하였고, 온도 상승 중에 PVP K30(아크로스)을 0.3g 투입한 후 완전히 용해시킨 다음 PVP K90(바스프)을 2.3g 투입하였다. 150℃ 까지 가열하여 완전히 용해시킨 다음 질산은 수용액을 드랍핑하여 투입하였다. 이후 150℃를 유지하였으며 약 4시간 반응하여 은 나노와이어의 합성을 완료했다. 이때 PVP K30의 완전 용해시간은 8분 소요됐고, PVP K90의 완전 용해시간은 70분 소요됐다.30 g of pentaerythritol (Daejeong Hwageum) was mixed with 300 ml of glycerin, and 0.03 g of SbCl3 (antimony trichloride/Daejeong Hwageum) was added thereto and stirred at low speed at about 30 RPM using a magnetic bar, and PVP K30 while the temperature was rising (Acros) was added to 0.3 g, completely dissolved, and then 2.3 g of PVP K90 (BASF) was added. It was completely dissolved by heating to 150° C., and then added by dropping an aqueous solution of silver nitrate. Thereafter, the temperature was maintained at 150° C. and the reaction was completed for about 4 hours to complete the synthesis of silver nanowires. At this time, the complete dissolution time of PVP K30 was 8 minutes, and the complete dissolution time of PVP K90 was 70 minutes.
수득한 은 나노와이어 합성액에 DIW 40ml, IPA 40ml을 투입후 분산하였고 분산이 완료된 후 아세톤 약 2L를 투입하여 와이어를 수득하였다. 수득한 은 나노와이어를 회수후 DIW 300ml에 분산하였고, 2차적으로 분산액에 아세톤 1.2L를 투입하여 정제를 하였고, 본 과정을 두차례 더 반복하여 은 나노와이어를 정제한 후 DIW에 보관하였다.40ml of DIW and 40ml of IPA were added to the obtained silver nanowire synthesis solution, and then dispersed. After dispersion was completed, about 2L of acetone was added to obtain a wire. The obtained silver nanowires were recovered and dispersed in 300ml of DIW, and secondarily, 1.2L of acetone was added to the dispersion for purification, and this process was repeated two more times to purify the silver nanowires and stored in DIW.
[비교예 1][Comparative Example 1]
실시예 1과 달리 촉매로서 KBr 0.02g, AgCl 0.01g을 첨가하여 은 나노와이어를 합성하였다. 그리고 실시예 1과 동일한 방법으로 은 나노와이어를 정제한 후 DIW에 보관하였다.Unlike Example 1, 0.02 g of KBr and 0.01 g of AgCl were added as catalysts to synthesize silver nanowires. Then, silver nanowires were purified in the same manner as in Example 1 and stored in DIW.
[비교예 2][Comparative Example 2]
프로필렌글라이콜 100ml에 질산은(삼전화학) 1.6g을 투입하여 질산은 수용액을 제조하였다. An aqueous silver nitrate solution was prepared by adding 1.6 g of silver nitrate (Samjeon Chemical) to 100 ml of propylene glycol.
프로필렌글라이콜 300ml에 촉매로서 KBr 0.02g, AgCl 0.01g을 첨가한 후 마그네틱바를 이용하여 RPM 약 30으로 저속으로 교반하였고, 온도 상승 중에 PVP K90(아크로스)을 2.6g을 투입하였다. 150℃까지 가열 후 PVP K90이 완전히 용해된 다음, 질산은 수용액을 드랍핑하여 투입하였다. 이후 150℃를 유지하였으며 약 4시간 반응하여 은 나노와이어 합성을 완료했다. 이때 PVP K90의 완전 용해시간은 90분 소요됐다.After adding 0.02 g of KBr and 0.01 g of AgCl as catalysts to 300 ml of propylene glycol, the mixture was stirred at a low speed at about 30 RPM using a magnetic bar, and 2.6 g of PVP K90 (Across) was added while the temperature was rising. After heating to 150° C., PVP K90 was completely dissolved, and then an aqueous silver nitrate solution was added by dropping. Thereafter, the temperature was maintained at 150° C. and the reaction was completed for about 4 hours to complete the synthesis of silver nanowires. At this time, the complete dissolution time of PVP K90 took 90 minutes.
그리고 수득한 은 나노와이어 합성액을 실시예 1의 정제방법과 동일한 방법으로 은 나노와이어를 정제한 후 DIW에 보관하였다.Then, the silver nanowire synthesis solution obtained was purified by the same method as the purification method of Example 1, and then stored in DIW.
[비교예 3][Comparative Example 3]
실시예 1과 동일한 방법으로 은 나노와이어의 합성을 완료하였다. The synthesis of silver nanowires was completed in the same manner as in Example 1.
수득한 은 나노와이어 합성액에 DIW 40ml을 투입후 분산하였고, 분산이 완료된 후 아세톤 약 2L를 투입하여 정제를 시도하였으나, 층분리가 일어나 은 나노와이어의 정제가 불가능하였다40ml of DIW was added to the obtained silver nanowire synthesis solution and dispersed, and after dispersion was completed, about 2L of acetone was added to attempt purification, but layer separation occurred and purification of the silver nanowire was impossible.
실시예 1 및 2, 비교예 1 및 2에 의해 제조된 은 나노와이어의 평균 직경, 평균 길이및 생산 수율에 대해 실험하였고, 그 결과를 표 1로 나타냈다.Examples 1 and 2 and Comparative Examples 1 and 2 were tested for the average diameter, average length, and production yield of the silver nanowires, the results are shown in Table 1.
표 1에서 확인되는 바와 같이 실시예 1 및 2, 비교예 1 및 2의 은 나노와이어의 평균 직경은 27nm 이하이고, 평균 길이는 16㎛~19㎛ 이며, 특히 실시예 1 및 2의 생산수율은 75~80wt%로서 비교예 2에 비하여 높게 측정되었다.As confirmed in Table 1, the average diameter of the silver nanowires of Examples 1 and 2 and Comparative Examples 1 and 2 is 27 nm or less, and the average length is 16 µm to 19 µm, and in particular, the production yields of Examples 1 and 2 are It was measured as 75-80 wt%, which was higher than Comparative Example 2.
그리고, 실시예 1 및 2, 비교예 1 및 2에 의해 제조된 은 나노와이어를 이용하여 은 나노와이어 잉크를 제조한 다음 PET 필름에 각각 코팅하여 투명전극을 형성하였다. 각 PET 필름 상에 형성된 투명전극에 대하여 투과도, 헤이즈 및 색차계를 측정하였고, 그 결과를 표 2로 나타냈다.Then, silver nanowire inks were prepared using the silver nanowires prepared in Examples 1 and 2 and Comparative Examples 1 and 2, and then each coated on a PET film to form a transparent electrode. Transmittance, haze, and colorimetry were measured for the transparent electrodes formed on each PET film, and the results are shown in Table 2.
표 2에서 확인되는 바와 같이 실시예 1 및 2의 투과도는 88.87% 이상으로 우수하였다. 특히, 색차계의 b*의 값의 경우 비교예 1, 2의 경우 1.19 이상으로 노란색을 띄었으나, 실시예 1 및 2는 0.52 이하로서 노란색을 띄는 현상이 많이 극복된 사실을 확인할 수 있다.As confirmed in Table 2, the transmittance of Examples 1 and 2 was excellent at 88.87% or more. In particular, in the case of the b* value of the color-difference meter, Comparative Examples 1 and 2 showed a yellow color of 1.19 or more, but Examples 1 and 2 showed a value of 0.52 or less, confirming the fact that the yellow phenomenon was largely overcome.
Claims (10)
b) 증류수 또는 글리세린에 펜타에리트리톨을 혼합한 혼합용액에 촉매로서 SbCl3를 첨가한 후 가열하고, 상기 은 수용액을 투입하여 은 나노와이어 합성액을 얻는 단계와,
c) 상기 은 나노와이어 합성액의 은 나노와이어를 정제하는 단계를 포함하는 것을 특징으로 하는 은 나노와이어의 제조방법.
a) preparing a silver aqueous solution by adding a silver precursor to a mixed solution of distilled water or glycerin and pentaerythritol;
b) adding SbCl 3 as a catalyst to a mixed solution of distilled water or glycerin mixed with pentaerythritol, heating, and adding the silver aqueous solution to obtain a silver nanowire synthesis solution;
c) A method of producing a silver nanowire comprising the step of purifying the silver nanowire of the silver nanowire synthesis solution.
상기 b)단계는 상기 혼합용액에 SbCl3 촉매, 폴리비닐피롤리돈 K30을 투입하여 용해시킨 다음, 폴리비닐피롤리돈 K90을 혼합 후 120℃ 내지 180℃로 가열하고, 상기 은 수용액을 투입한 후 150℃의 온도로 4시간 동안 유지하여 나노와이어를 형성하는 것을 특징으로 하는 은 나노와이어의 제조방법.
According to claim 1,
In step b), the SbCl 3 catalyst and polyvinylpyrrolidone K30 were added to the mixed solution and dissolved, and then polyvinylpyrrolidone K90 was mixed and heated to 120° C. to 180° C., and the silver aqueous solution was added. A method of manufacturing a silver nanowire, characterized in that the nanowire is formed by maintaining it at a temperature of 150° C. for 4 hours.
상기 c)단계는 상기 은 나노와이어 합성액에 증류수 및 이소프로필알코올을 투입하여 은 나노와이어를 분산시킨 후 아세톤을 투입하여 응집된 은 나노와이어를 수득하고, 수득된 은 나노와이어를 증류수에 분산시킨 후 아세톤을 투입하여 응집된 은 나노와이어를 수득하는 공정을 포함하여 이루어지는 것을 특징으로 하는 은 나노와이어의 제조방법.
3. The method of claim 2,
In step c), distilled water and isopropyl alcohol were added to the silver nanowire synthesis solution to disperse silver nanowires, and acetone was added to obtain agglomerated silver nanowires, and the obtained silver nanowires were dispersed in distilled water. A method for producing silver nanowires, comprising a step of obtaining agglomerated silver nanowires by adding acetone afterward.
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