WO2013133644A1 - Conductive ink composition for forming transparent electrodes - Google Patents

Conductive ink composition for forming transparent electrodes Download PDF

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Publication number
WO2013133644A1
WO2013133644A1 PCT/KR2013/001848 KR2013001848W WO2013133644A1 WO 2013133644 A1 WO2013133644 A1 WO 2013133644A1 KR 2013001848 W KR2013001848 W KR 2013001848W WO 2013133644 A1 WO2013133644 A1 WO 2013133644A1
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metal
transparent electrode
ink composition
conductive ink
acac
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PCT/KR2013/001848
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French (fr)
Korean (ko)
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이성현
김성배
김경은
이준혁
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주식회사 동진쎄미켐
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Priority to CN201380013342.0A priority Critical patent/CN104159985B/en
Publication of WO2013133644A1 publication Critical patent/WO2013133644A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates to a conductive ink composition for forming a transparent electrode.
  • the transparent electrode is a condensation of atoms, molecules or ions by a physicochemical method on a transparent glass substrate or a thin polymer substrate, and refers to an electrode that is transparent in the visible region (380-780 nm wavelength) and has high electrical conductivity. More specifically, the transparent electrode refers to a thin film having a light transmittance of about 80% or more and a sheet resistance of 500 ⁇ / ⁇ or less.
  • ITO Indium tin oxide
  • ZnO thin films have low cost materials and low electrical conductivity compared to ITO, and ATO thin films in which Sb is added to SnO 2 in a small amount do not etch and have a high firing temperature.
  • the metal nanowires form a network when forming the transparent electrode to secure electrical conductivity.
  • the metal nanowire network is densely formed, the electrical conductivity of the transparent electrode is improved, but the visible light transmittance is lowered and excessive cost is required.
  • metal nanowires are nanostructures, which are more active than conventional materials, and thus are prone to oxidation and corrosion when exposed to the atmosphere without a protective layer.
  • silver nanowires have high conductivity properties and are transparent in the visible region, but are known to increase resistance by about 15-20% due to oxidation and corrosion in the air. There was a problem to use.
  • the present invention exhibits excellent electrical conductivity and visible light transmittance, and does not require a separate antioxidant or protective layer to prevent corrosion and oxidation of the metal nanowires, and environmental resistance of the manufactured transparent electrode
  • An object of the present invention is to provide a conductive ink composition for a transparent electrode which can be secured.
  • an object of the present invention is to provide a method for forming a transparent electrode using the composition and a transparent electrode produced by the method.
  • the present invention to achieve the above object
  • It provides a conductive ink composition for forming a transparent electrode comprising a.
  • the present invention provides a method for producing a conductive transparent electrode and a conductive transparent electrode prepared by the method characterized in that the conductive ink composition for forming a transparent electrode applied to the substrate to dry and fire.
  • the conductive ink composition for forming a transparent electrode including the metal sol and the metal nanowire forms a conductive network with metal nanowires, and complements the disconnection of the network with the metal sol and fills the empty space, thereby providing excellent electrical conductivity and visible light. Permeability is shown.
  • the metal sol acts as a protective layer to prevent corrosion and oxidation of the metal nanowires, a separate antioxidant or protective layer is not required, and the environmental resistance of the manufactured transparent electrode can be guaranteed.
  • FIG. 1 is a conceptual diagram illustrating an embodiment of a transparent electrode formed according to the present invention.
  • FIG. 2 is an enlarged view of a scanning electron microscope of a transparent electrode formed according to the present invention.
  • 3 is a visible light transmittance of a transparent electrode formed according to the present invention.
  • the conductive ink composition for forming a transparent electrode of the present invention is a conductive ink composition for forming a transparent electrode of the present invention.
  • the metal sol according to the present invention can be prepared at room temperature and atmospheric pressure, and the metal content of the metal sol can be controlled within the metal precursor solubility range, so that not only the metal concentration can be adjusted but also the viscosity and the calcination temperature can be adjusted. In addition, it is not mixed with the metal nanowires, so that no strong acid or strong base is used to prepare the conductive ink composition for forming the transparent electrode, and thus does not damage the metal nanowires.
  • the metal sol usable in the present invention serves to improve the electrical conductivity of the entire coating film by supplementing the disconnection of the network without damaging the metal nanowires and filling the empty space between the networks with the conductive metal coating film. It also prevents oxidation of metal nanowires and acts as a protective layer to prevent wear. In particular, it not only prevents penetration of materials that may corrode metal nanowires such as moisture, oxygen, sulfur, etc., but also improves adhesion between the metal nanowires and the lower substrate.
  • the metal of a) metal precursor which can be used for the said metal sol is not specifically limited, Preferably, Group I, IIA, such as gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, magnesium, etc. It is preferable to use at least one metal selected from the group consisting of metals of Groups, Groups IIIA, IVA and VIII B, more preferably zinc, aluminum, tin, iron, copper and silver. It is better to use at least one kind.
  • the metal precursor may be at least one inorganic salt selected from the group consisting of nitrates, acetates, acetylacetonates, silicates, phosphates, and mixtures thereof, preferably acetate, acetylacetone salts or silicates. .
  • the metal precursor is preferably used in the range of 3 to 20% by weight based on the total weight of the metal sol.
  • the metal precursor may not form a dense metal coating film and thus may not act as a protective layer of the metal nanowires, and may not compensate for disconnection and fill empty spaces of the metal nanowire network.
  • the content is more than 20% by weight, the stability of the metal sol is deteriorated, the metal precursor is precipitated, requires a calcination temperature of 300 °C or more high temperature, and the calcination time is more than 30 minutes to oxidize the metal nanowires Will cause.
  • solvent for dissolving the metal precursor in the present invention is water, methanol, ethanol, propanol, isopropanol, isopropyl acetate, butanol, 2-butanol, octanol, 2-ethylhexanol, pentanol, benzyl alcohol, Hexanol, 2-hexanol, cyclohexanol, terpineol, nonanol, methylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 2-propane One, diace
  • the mixing ratio of the solvent mixes the subsolvent in the ratio of 0.2-0.8 weight part based on 1 weight part of main solvents.
  • the main solvent may be used by selecting one of the solvents listed above, and one or more solvents other than the solvent used as the main solvent may be used as the subsolvent.
  • terpineol or nonanol has a problem in that the baking temperature of the conductive ink is high due to its high viscosity and high boiling point.
  • the viscosity and the boiling point can be lowered to control the firing temperature of the conductive ink.
  • the viscosity and sintering temperature lowering effect cannot be expected.On the contrary, when added excessively, the proper viscosity of the conductive ink cannot be maintained or defects may occur due to rapid volatilization during application. Can be.
  • Diacetyl, acetylacetone, dimethyl carbonate, or ethylene glycol are solvents that have a relatively good solubility in metal precursors.
  • the addition of methanol, ethanol, isopropanol, and the like as a subsolvent can dramatically increase the solubility in metal precursors. It is suitable for making high concentration of metal sol, but its effect is diminished outside this range.
  • the metal sol according to the present invention may be prepared by dissolving the metal precursor in the solvent at room temperature and atmospheric pressure.
  • the method for preparing the metal sol is based on the normal temperature and normal pressure conditions by using acetylacetone or a mixed solvent containing the same as a solvent using an inorganic salt of a metal, preferably a metal acetate, an acetylacetone salt or a silicate as a metal precursor.
  • a metal sol can be prepared, and the metal precursor is prepared by simply dissolving the metal precursor in a suitable solvent, thereby making the manufacturing method simple.
  • the metal content of the metal sol can be adjusted within the metal precursor solubility range to prepare a low concentration as well as a high concentration metal sol, it is possible to form a dense metal coating film as well as to control the viscosity and firing temperature of the metal sol. There is also no damage to the metal nanowires since no strong acid or strong base is used.
  • the metal of B) metal nanowires usable in the present invention is not particularly limited, but preferably Group I, such as gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, magnesium, It is preferable to use at least one metal selected from the group consisting of Group IIA, Group IIIA, Group IVA and Group VIIIB metals, more preferably selected from the group consisting of zinc, aluminum, tin, copper, silver and gold. It is preferable to use at least one metal.
  • the metal nanowires may use a diameter of 20 to 120 nm, a length of 5 to 60 um.
  • the metal nanowires may be included in an amount of 0.25 to 4 parts by weight of the metal nanowires based on 1 part by weight of the metal precursor included in the metal sol.
  • the metal nanowires are used at less than 0.25 parts by weight, the metal nanowires are difficult to form a network properly and cannot have conductivity, and when the content is more than 4 parts by weight, the metal nanowires form a network too densely.
  • the substrate becomes cloudy, which is undesirable since it causes a decrease in visible light transmittance.
  • a conductive ink composition for forming a final transparent electrode is formed by mixing a dispersion medium-metal nanowire dispersed in a dispersion medium with the metal sol using a portion of the solvent as a dispersion medium of the metal nanowires. It can be prepared, the content of each component in the conductive ink composition for forming the final transparent electrode can be adjusted within the above-described range.
  • the conductive ink composition for forming a transparent electrode according to the present invention may include additives commonly used in the art as needed in addition to the metal sol and the metal nanowire.
  • the conductive ink composition for forming a transparent electrode according to the present invention preferably has a pH in the range of 6 to 9.
  • the metal nanowires may be oxidized in the solution by an acid atmosphere, and oxidation, cleavage, or dissolution of the metal nanowires may occur even when the pH exceeds 9.
  • the present invention provides a method for producing a conductive transparent electrode and a transparent electrode produced by the method, characterized in that the transparent ink forming conductive ink composition is applied to a substrate and baked.
  • the conductive ink composition for forming a transparent electrode according to the present invention can be used in various printing processes commonly used in the art, for example, gravure off-set printing, gravure direct printing, screens ( Transparent substrates commonly used, for example, glass substrates, polys, using screen printing, spin coating, slit coating, slot die coating, or imprinting methods. It may be printed on a mid (PI) substrate, a polyethylene terephthalate (PET) substrate, and the like, and the thickness is preferably appropriately adjusted according to the use.
  • PI mid
  • PET polyethylene terephthalate
  • the electrode prepared as described above may be fired according to a firing method commonly used in the art, the firing conditions may be appropriately adjusted according to the characteristics of the substrate and the composition, it is possible to bake at less than 300 °C film It is also applicable to the organic material base material, including, preferably firing at 80 °C to 250 °C.
  • the transparent electrode according to the present invention may be usefully used for electrodes such as liquid crystal displays, plasma displays, touch panels, electroluminescent devices, thin film solar cells, dye-sensitized solar cells, and inorganic crystalline solar cells.
  • a metal sol by mixing a metal precursor and a solvent at room temperature and normal pressure conditions according to the components and contents shown in Table 1, and then mixed with a nanowire dispersion to prepare a conductive ink for transparent electrodes.
  • silver nanowire dispersion liquid in which silver nanowires were dispersed in isopropanol at a concentration of 0.8% by weight was used as the metal nanowire dispersion liquid.
  • Zn AcAc is zinc acetylacetonate
  • Cu AcAc is copper acetylacetonate
  • Sn AcAc is acetylacetonate tin
  • Al AcAc is acetylacetonate aluminum
  • Fe AcAc is acetylacetonate iron
  • Zn Ac is zinc acetate
  • Ag Ac stands for silver acetate
  • Ag AcAc stands for acetylacetonic acid
  • AcAc stands for acetylacetone
  • IPA stands for isopropanol.
  • the environmental resistance was evaluated by measuring the visible light transmittance and conductivity of the conductive ink for transparent electrodes prepared in Examples 1 to 14.
  • the glass substrate was cleaned to remove foreign substances such as organic matter, and then the conductive inks for transparent electrodes of Examples 1 to 14 were applied to the glass substrates, respectively. After application, heat treatment was performed at 200 ° C. for 10 minutes.
  • the transparent electrode prepared by using the ink composition including the metal nanowires and the metal sol according to the present invention has an excellent light transmittance of 93% or more and a sheet resistance of 500 ⁇ / ⁇ It can be seen that the conductivity is very excellent below.
  • the metal sol acts as a protective layer of the metal nanowires and exhibits excellent environmental resistance, no separate antioxidant or protective layer is required.
  • the conductive ink composition for forming a transparent electrode including the metal sol and the metal nanowire forms a conductive network with metal nanowires, and complements the disconnection of the network with the metal sol and fills the empty space, thereby providing excellent electrical conductivity and visible light. Permeability is shown.
  • the metal sol acts as a protective layer to prevent corrosion and oxidation of the metal nanowires, a separate antioxidant or protective layer is not required, and the environmental resistance of the manufactured transparent electrode can be guaranteed.

Abstract

The present invention relates to a conductive ink composition for forming transparent electrodes. More particularly, the conductive ink composition for forming transparent electrodes according to the present invention is configured such that a conductive network is made from a metal nanowire, wherein the disconnection of the network is supplemented by metal sol and empty spaces in the network are filled with said metal sol, thus exhibiting excellent electrical conductivity and visible light transmittance. Further, the metal sol serves as a protective layer for protecting against the corrosion and oxidation of the metal nanowire, thus eliminating the necessity of a separate antioxidant or protective layer, and ensuring the environmental resistance of the produced transparent electrode.

Description

투명 전극 형성용 전도성 잉크 조성물Conductive Ink Composition for Transparent Electrode Formation
본 발명은 투명 전극 형성용 전도성 잉크 조성물에 관한 것이다.The present invention relates to a conductive ink composition for forming a transparent electrode.
투명 전극은 투명한 유리 기판 또는 얇은 고분자 기판 위에 물리화학적인 방법으로 원자, 분자 또는 이온을 응축시킨 것으로, 가시광 영역(380-780 ㎚ 파장)에서 투명하고, 전기전도도가 큰 전극을 의미한다. 보다 구체적으로, 투명 전극은 광투과도가 약 80% 이상이고, 면저항이 500 Ω/□ 이하인 박막을 의미한다.The transparent electrode is a condensation of atoms, molecules or ions by a physicochemical method on a transparent glass substrate or a thin polymer substrate, and refers to an electrode that is transparent in the visible region (380-780 nm wavelength) and has high electrical conductivity. More specifically, the transparent electrode refers to a thin film having a light transmittance of about 80% or more and a sheet resistance of 500 Ω / □ or less.
투명 전극의 재료로 사용되기 위해서는 전기적, 광학적 특성 및 에칭 특성이 우수한 재료가 필요하다. 현재까지 개발된 재료로는 가장 우수한 물성을 나타내고 있는 ITO(Indium tin oxide)가 널리 사용되고 있다. 하지만 ITO는 고가의 희소금속인 인듐을 주성분으로 하고 있기 때문에 이를 대체할만한 투명 전극 재료가 요구되고 있다.In order to be used as a material for the transparent electrode, a material having excellent electrical, optical and etching characteristics is required. Indium tin oxide (ITO), which exhibits the best physical properties, is widely used as a material developed to date. However, since ITO is based on indium, an expensive rare metal, a transparent electrode material is required to replace it.
이에 금, 은, 구리 등의 금속을 스퍼터링하여 얇은 박막으로 만들어 투명 전극으로 사용한 시도가 있었으나, 이는 전기전도도는 우수하지만 가시광 영역의 광투과도가 떨어지며, 하부 기판과의 접착력이 좋지 않다는 문제점이 있다.There has been an attempt to use a transparent electrode by sputtering a metal such as gold, silver, copper, etc., which is excellent in electrical conductivity, but has a problem in that light transmittance in the visible region is poor and adhesion to the lower substrate is not good.
또한 ZnO 박막은 저가의 재료이나 전기전도성이 ITO에 비해 낮고, SnO2에 Sb를 소량 첨가한 ATO 박막은 에칭이 되지 않고 소성 온도가 높다는 문제점이 있다.In addition, ZnO thin films have low cost materials and low electrical conductivity compared to ITO, and ATO thin films in which Sb is added to SnO 2 in a small amount do not etch and have a high firing temperature.
또한 졸-겔(Sol-Gel) 합성을 이용하여 산화막을 만드는 방법도 사용되고 있으나 여전히 전기전도성이 낮고, 소성 온도가 350 ℃를 넘는 고온 공정을 필요로 한다는 문제점이 있다.In addition, a method of making an oxide film by using a sol-gel synthesis is also used, but there is a problem in that the electrical conductivity is low and the firing temperature requires a high temperature process over 350 ° C.
또한 ZnO, ITO, IZO 등의 산화물을 나노 크기의 입자로 제조하고 이를 이용하여 잉크나 페이스트를 제조하여 투명 전극을 제조하는 방법도 있으나, 나노 크기의 산화물 제조가 어렵고 250 ℃ 이상의 비교적 고온 공정이 필요하다는 문제점이 있다.In addition, there is a method for preparing a transparent electrode by preparing oxides such as ZnO, ITO, IZO, etc. using nano-sized particles and preparing ink or paste, but it is difficult to manufacture nano-sized oxides and requires a relatively high temperature process of 250 ° C. or more. There is a problem.
이에 최근에는 금속 나노와이어를 투명 전극에 적용하는 시도가 이루어지고 있다.In recent years, attempts have been made to apply metal nanowires to transparent electrodes.
투명 전극용 전도성 잉크에서 금속 나노와이어는 투명 전극 형성시 네트워크를 형성하여 전기전도성을 확보하는 역할을 한다. 금속 나노와이어 네트워크가 촘촘히 형성될수록 투명 전극의 전기전도도는 향상되나 가시광 투과율이 떨어지고 과다한 비용이 소요되는 문제점이 있다. 또한 금속 나노와이어로 전도성 네트워크를 형성하더라도 네트워크의 단선이 필연적으로 발생하게 될 뿐 아니라 네트워크 사이의 빈공간은 전도성을 가지지 못하는 부도체 영역으로 남게 된다. 또한 금속 나노와이어는 나노 구조체로서 활성이 기존 물질보다 강해서 보호층 없이 대기에 노출될 경우 산화 및 부식 경향이 강하다. 특히 은 나노와이어는 고전도 특성을 가지며 가시광 영역에서 투명하지만, 대기 중에서 산화 및 부식에 의해 약 15-20% 정도 저항이 상승하는 것으로 알려져 있으며, 이를 방지하기 위해서는 별도의 산화방지제 또는 다수의 보호층을 사용해야 하는 문제점이 있었다.In the conductive ink for the transparent electrode, the metal nanowires form a network when forming the transparent electrode to secure electrical conductivity. As the metal nanowire network is densely formed, the electrical conductivity of the transparent electrode is improved, but the visible light transmittance is lowered and excessive cost is required. In addition, even if a conductive network is formed with metal nanowires, disconnection of the network will inevitably occur, and the void space between the networks will remain as a non-conductive area having no conductivity. In addition, metal nanowires are nanostructures, which are more active than conventional materials, and thus are prone to oxidation and corrosion when exposed to the atmosphere without a protective layer. In particular, silver nanowires have high conductivity properties and are transparent in the visible region, but are known to increase resistance by about 15-20% due to oxidation and corrosion in the air. There was a problem to use.
상기와 같은 문제점을 해결하기 위해, 본 발명은 우수한 전기전도성 및 가시광 투과도를 나타내며, 금속 나노와이어의 부식 및 산화를 방지하는 별도의 산화방지제 또는 보호층이 필요하지 않고, 제조되는 투명 전극의 내환경성을 담보할 수 있는 투명 전극용 전도성 잉크 조성물을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention exhibits excellent electrical conductivity and visible light transmittance, and does not require a separate antioxidant or protective layer to prevent corrosion and oxidation of the metal nanowires, and environmental resistance of the manufactured transparent electrode An object of the present invention is to provide a conductive ink composition for a transparent electrode which can be secured.
또한 본 발명은 상기 조성물을 이용하는 투명전극의 형성방법 및 상기 방법에 의하여 제조된 투명 전극을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a method for forming a transparent electrode using the composition and a transparent electrode produced by the method.
상기 목적을 달성하기 위해 본 발명은 The present invention to achieve the above object
A)a) 금속 전구체; b) 용매를 포함하는 금속 졸; 및 A) a) a metal precursor; b) a metal sol comprising a solvent; And
B) 금속와이어B) metal wire
를 포함하는 것을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물을 제공한다.It provides a conductive ink composition for forming a transparent electrode comprising a.
또한 본 발명은 상기 투명 전극 형성용 전도성 잉크 조성물을 기재에 도포하여 건조 및 소성하는 것을 특징으로 하는 전도성 투명 전극의 제조방법 및 상기 방법에 의하여 제조된 전도성 투명전극을 제공한다.In another aspect, the present invention provides a method for producing a conductive transparent electrode and a conductive transparent electrode prepared by the method characterized in that the conductive ink composition for forming a transparent electrode applied to the substrate to dry and fire.
본 발명에 따라 상기 금속 졸 및 금속 나노와이어를 포함하는 투명 전극 형성용 전도성 잉크 조성물은 금속 나노와이어로 전도성 네트워크를 형성하고 금속 졸로 네트워크의 단선을 보완하고 빈 공간을 채우므로, 우수한 전기전도성 및 가시광 투과도를 나타낸다. 또한 금속 졸이 금속 나노와이어의 부식 및 산화를 방지하는 보호층으로 작용하므로 별도의 산화방지제 또는 보호층이 필요하지 않고, 제조되는 투명 전극의 내환경성을 보장할 수 있다.According to the present invention, the conductive ink composition for forming a transparent electrode including the metal sol and the metal nanowire forms a conductive network with metal nanowires, and complements the disconnection of the network with the metal sol and fills the empty space, thereby providing excellent electrical conductivity and visible light. Permeability is shown. In addition, since the metal sol acts as a protective layer to prevent corrosion and oxidation of the metal nanowires, a separate antioxidant or protective layer is not required, and the environmental resistance of the manufactured transparent electrode can be guaranteed.
도 1은 본 발명에 따라 형성된 투명 전극의 일 실시예를 나타내는 개념도이다.1 is a conceptual diagram illustrating an embodiment of a transparent electrode formed according to the present invention.
도 2는 본 발명에 따라 형성된 투명 전극의 주사전자현미경 확대도이다.2 is an enlarged view of a scanning electron microscope of a transparent electrode formed according to the present invention.
도 3은 본 발명에 따라 형성된 투명 전극의 가시광 투과도이다.3 is a visible light transmittance of a transparent electrode formed according to the present invention.
본 발명의 투명 전극 형성용 전도성 잉크 조성물은The conductive ink composition for forming a transparent electrode of the present invention
A)a) 금속 전구체; b) 용매를 포함하는 금속 졸; 및 A) a) a metal precursor; b) a metal sol comprising a solvent; And
B) 금속와이어B) metal wire
를 포함하는 것을 특징으로 한다.Characterized in that it comprises a.
본 발명에 따른 상기 금속 졸은 상온 및 상압 조건에서 제조될 수 있고, 금속 졸의 금속 함량을 금속 전구체 용해도 범위 내에서 조절 가능하므로 금속 농도 조절이 가능할 뿐 아니라 점도 조절 및 소성 온도 조절도 가능하다. 또한 금속 나노와이어와 함께 혼합하여 투명 전극 형성용 전도성 잉크 조성물을 제조시 강산 또는 강염기를 사용하지 않으므로 금속 나노와이어에 손상을 주지 않는다.The metal sol according to the present invention can be prepared at room temperature and atmospheric pressure, and the metal content of the metal sol can be controlled within the metal precursor solubility range, so that not only the metal concentration can be adjusted but also the viscosity and the calcination temperature can be adjusted. In addition, it is not mixed with the metal nanowires, so that no strong acid or strong base is used to prepare the conductive ink composition for forming the transparent electrode, and thus does not damage the metal nanowires.
본 발명에서 사용가능한 금속 졸은 금속 나노와이어에 손상을 주지 않고 네트워크의 단선을 보완하고 네트워크 사이의 빈 공간을 전도성의 금속 도막으로 채워 도막 전체의 전기전도도를 향상시키는 역할을 한다. 또한 금속 나노와이어의 산화를 방지하며, 마모를 방지하는 보호층의 역할을 한다. 특히, 습기, 산소, 황 등과 같은 금속 나노와이어를 부식시킬 수 있는 물질의 투과를 방지할 뿐 아니라, 금속 나노와이어와 하부 기판과의 접착력도 향상시킨다.The metal sol usable in the present invention serves to improve the electrical conductivity of the entire coating film by supplementing the disconnection of the network without damaging the metal nanowires and filling the empty space between the networks with the conductive metal coating film. It also prevents oxidation of metal nanowires and acts as a protective layer to prevent wear. In particular, it not only prevents penetration of materials that may corrode metal nanowires such as moisture, oxygen, sulfur, etc., but also improves adhesion between the metal nanowires and the lower substrate.
상기 금속 졸에 사용 가능한 a) 금속 전구체의 금속은 특별히 한정되지 않으나, 바람직하게는 금, 은, 구리, 알루미늄, 니켈, 주석, 팔라듐, 백금, 아연, 철, 인듐, 마그네슘 등의 Ⅰ족, ⅡA족, ⅢA족, ⅣA족 및 ⅤⅢ B족의 금속으로 이루어진 군에서 선택되는 1종 이상의 금속을 사용하는 것이 좋으며, 더욱 바람직하게는 아연, 알루미늄, 주석, 철, 구리 및 은으로 이루어진 군에서 선택되는 1종 이상을 사용하는 것이 좋다.The metal of a) metal precursor which can be used for the said metal sol is not specifically limited, Preferably, Group I, IIA, such as gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, magnesium, etc. It is preferable to use at least one metal selected from the group consisting of metals of Groups, Groups IIIA, IVA and VIII B, more preferably zinc, aluminum, tin, iron, copper and silver. It is better to use at least one kind.
상기 금속 전구체는 질산염, 아세트산염, 아세틸아세톤산염, 규산염, 인산염 및 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상의 무기염일 수 있으며, 바람직하게는 아세트산염, 아세틸아세톤염 또는 규산염을 사용하는 것이 좋다.The metal precursor may be at least one inorganic salt selected from the group consisting of nitrates, acetates, acetylacetonates, silicates, phosphates, and mixtures thereof, preferably acetate, acetylacetone salts or silicates. .
상기 금속 전구체는 금속 졸 총중량을 기준으로 3 내지 20 중량%의 범위에서 사용하는 것이 좋다. 상기 금속 전구체를 3 중량% 미만으로 사용할 경우, 치밀한 금속 도막을 형성하지 못하여 금속 나노와이어의 보호층으로 작용할 수 없으며, 금속 나노와이어 네트워크의 단선 보완과 빈 공간을 채울 수 없게 된다. 또한 상기 함량이 20 중량%를 초과하는 경우, 금속 졸의 안정성이 떨어져 금속 전구체가 석출되거나, 300 ℃ 이상 고온의 소성 온도를 필요로 하고, 소성시간도 30분 이상 소요되어 금속 나노와이어의 산화를 유발하게 된다.The metal precursor is preferably used in the range of 3 to 20% by weight based on the total weight of the metal sol. When the metal precursor is used at less than 3% by weight, it may not form a dense metal coating film and thus may not act as a protective layer of the metal nanowires, and may not compensate for disconnection and fill empty spaces of the metal nanowire network. In addition, when the content is more than 20% by weight, the stability of the metal sol is deteriorated, the metal precursor is precipitated, requires a calcination temperature of 300 ℃ or more high temperature, and the calcination time is more than 30 minutes to oxidize the metal nanowires Will cause.
본 발명에서 상기 금속 전구체를 용해시키기 위한 b) 용매로는 물, 메탄올, 에탄올, 프로판올, 이소프로판올, 이소프로필아세테이트, 부탄올, 2-부탄올, 옥탄올, 2-에틸헥사놀, 펜탄올, 벤질알콜, 헥산올, 2-헥산올, 사이클로헥산올, 테르피네올, 노나놀, 메틸렌 글리콜, 에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 테트라에틸렌 글리콜, 에틸렌 글리콜 모노메틸에테르, 에틸렌 글리콜 모노에틸에테르, 에틸렌 글리콜 모노부틸에테르, 디에틸렌 글리콜 모노메틸에테르, 디에틸렌 글리콜 모노에틸에테르, 디에틸렌 글리콜 모노부틸에테르, 트리에틸렌 글리콜 모노메틸에테르, 트리에틸렌 글리콜 모노에틸에테르, 트리에틸렌 글리콜 모노부틸에테르, 2-프로판온, 디아세틸, 아세틸아세톤, 1,2-디아세틸에탄, 디메틸카보네이트, 디에틸카보네이트, 프로필렌글리콜메틸에테르아세테이트, 2-메톡시에틸아세테이트, 프로필렌글리콜모노메틸에테르, N-메틸-2-피롤리돈, N-메틸아세트아마이드 및 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상의 용매를 사용할 수 있고, 바람직하게는 아세틸아세톤 단독 또는 이를 포함하는 혼합용매를 사용할 수 있으며, 금속 전구체에 대한 용해력, 잉크의 점도 조절, 원활한 박막 형성, 금속 나노와이어와의 혼합성 등을 고려하여 선정하는 것이 바람직하며, 더욱 바람직하기로 본 발명의 금속 졸에서 용매의 함량은 80-97 중량%이다. B) solvent for dissolving the metal precursor in the present invention is water, methanol, ethanol, propanol, isopropanol, isopropyl acetate, butanol, 2-butanol, octanol, 2-ethylhexanol, pentanol, benzyl alcohol, Hexanol, 2-hexanol, cyclohexanol, terpineol, nonanol, methylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 2-propane One, diacetyl, acetylacetone, 1,2-diacetylethane, dimethyl carbonate, diethyl carbonate, pro At least one solvent selected from the group consisting of len glycol methyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, N-methyl-2-pyrrolidone, N-methylacetamide and mixtures thereof Preferably, acetylacetone alone or a mixed solvent including the same may be used, and the solvent may be selected in consideration of the solvent power to the metal precursor, the viscosity control of the ink, the formation of a smooth thin film, and the compatibility with the metal nanowires. More preferably, the content of the solvent in the metal sol of the present invention is 80-97% by weight.
또한 2 종류 이상의 용매를 혼합하여 사용하는 경우, 용매의 혼합 비율은 주용매 1 중량부를 기준으로 부용매를 0.2 내지 0.8 중량부의 비율로 혼합하는 것이 바람직하다. 상기 주용매는 상기 열거된 용매 중 1종을 선택하여 사용할 수 있으며, 주용매로 사용한 용매를 제외한 1종 이상의 용매를 부용매로 사용할 수 있다. 용매 혼합 비율 상기 범위 내 있는 경우에는 점도 조절의 용이성, 금속 전구체의 용해도 상승, 전도성 잉크의 소성 온도 조절 등의 효과를 얻게 된다.In addition, when mixing two or more types of solvents, it is preferable that the mixing ratio of the solvent mixes the subsolvent in the ratio of 0.2-0.8 weight part based on 1 weight part of main solvents. The main solvent may be used by selecting one of the solvents listed above, and one or more solvents other than the solvent used as the main solvent may be used as the subsolvent. When the solvent mixing ratio is in the above range, effects such as ease of viscosity adjustment, increase in solubility of the metal precursor, and control of the firing temperature of the conductive ink are obtained.
예를 들면, 테르피네올 또는 노나놀은 점도가 높고 끓는점이 높아 전도성 잉크의 소성 온도가 높아지는 문제점이 존재한다. 이때 메탄올, 에탄올 등을 부용매로서 상기 범위 내에서 사용하면 점도를 떨어뜨리고 끓는점을 떨어뜨려 전도성 잉크의 소성 온도를 조절할 수 있게 된다. 하지만 메탄올, 에탄올의 함량이 상기 범위를 벗어나 부족하면 점도 및 소성 온도 하강 효과를 기대할 수 없고, 반대로 과다하게 첨가되면 전도성 잉크의 적정 점도를 유지할 수 없거나 도포 시 빠른 휘발로 인해 도막에 결점이 발생 할 수 있다. 또한 디아세틸, 아세틸아세톤, 디메틸 카보네이트 또는 에틸렌 글리콜은 금속 전구체에 대해 용해도가 비교적 좋은 용매인데, 여기에 메탄올, 에탄올, 이소프로판올 등을 부용매로 첨가하면 금속 전구체에 대한 용해도를 급격히 상승시키는 효과가 있어 고농도의 금속 졸을 만드는데 적합하지만 상기 범위를 벗어나면 그 효과는 줄어들게 된다.For example, terpineol or nonanol has a problem in that the baking temperature of the conductive ink is high due to its high viscosity and high boiling point. In this case, when methanol, ethanol, or the like is used within the above range as a sub-solvent, the viscosity and the boiling point can be lowered to control the firing temperature of the conductive ink. However, if the content of methanol and ethanol is out of the above range, the viscosity and sintering temperature lowering effect cannot be expected.On the contrary, when added excessively, the proper viscosity of the conductive ink cannot be maintained or defects may occur due to rapid volatilization during application. Can be. Diacetyl, acetylacetone, dimethyl carbonate, or ethylene glycol are solvents that have a relatively good solubility in metal precursors. The addition of methanol, ethanol, isopropanol, and the like as a subsolvent can dramatically increase the solubility in metal precursors. It is suitable for making high concentration of metal sol, but its effect is diminished outside this range.
본 발명에 따른 상기 금속 졸은 상온 및 상압 조건에서 상기 금속 전구체를 상기 용매에 용해시켜 제조될 수 있다.The metal sol according to the present invention may be prepared by dissolving the metal precursor in the solvent at room temperature and atmospheric pressure.
보다 구체적으로 상기 금속 졸의 제조방법은 금속 전구체로서 금속의 무기염, 바람직하게는 금속의 아세트산염, 아세틸아세톤염 또는 규산염을 사용하여 용매로서 아세틸아세톤 또는 이를 포함하는 혼합용매를 사용함으로써 상온 상압 조건에서 금속 졸을 제조할 수 있으며, 금속 전구체를 적절한 용매에 단순히 용해하여 제조하므로, 제조 방법이 간단하다. 또한 금속 졸의 금속 함량을 금속 전구체 용해도 범위 내에서 조절 가능하여 저농도는 물론 고농도의 금속 졸을 제조할 수 있으므로, 치밀한 금속 도막 형성이 가능할 뿐 아니라 금속 졸의 점도 및 소성 온도도 조절이 가능하다. 또한 강산 또는 강염기를 사용하지 않기 때문에 금속 나노와이어에 대한 손상도 없다.More specifically, the method for preparing the metal sol is based on the normal temperature and normal pressure conditions by using acetylacetone or a mixed solvent containing the same as a solvent using an inorganic salt of a metal, preferably a metal acetate, an acetylacetone salt or a silicate as a metal precursor. A metal sol can be prepared, and the metal precursor is prepared by simply dissolving the metal precursor in a suitable solvent, thereby making the manufacturing method simple. In addition, the metal content of the metal sol can be adjusted within the metal precursor solubility range to prepare a low concentration as well as a high concentration metal sol, it is possible to form a dense metal coating film as well as to control the viscosity and firing temperature of the metal sol. There is also no damage to the metal nanowires since no strong acid or strong base is used.
또한 본 발명에서 사용가능한 B) 금속 나노와이어의 금속은 특별히 한정되지 않으나, 바람직하게는 금, 은, 구리, 알루미늄, 니켈, 주석, 팔라듐, 백금, 아연, 철, 인듐, 마그네슘 등의 Ⅰ족, ⅡA족, ⅢA족, ⅣA족 및 ⅤⅢ B족 금속으로 이루어진 군에서 선택되는 1종 이상의 금속을 사용하는 것이 좋으며, 더욱 바람직하게는 아연, 알루미늄, 주석, 구리, 은 및 금으로 이루어진 군에서 선택되는 1종 이상의 금속을 사용하는 것이 좋다. 또한 상기 금속 나노와이어는 직경이 20 내지 120 nm, 길이가 5 내지 60 um인 것을 사용하는 것이 좋다.In addition, the metal of B) metal nanowires usable in the present invention is not particularly limited, but preferably Group I, such as gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, magnesium, It is preferable to use at least one metal selected from the group consisting of Group IIA, Group IIIA, Group IVA and Group VIIIB metals, more preferably selected from the group consisting of zinc, aluminum, tin, copper, silver and gold. It is preferable to use at least one metal. In addition, the metal nanowires may use a diameter of 20 to 120 nm, a length of 5 to 60 um.
상기 금속 나노와이어는 상기 금속 졸에 포함된 금속 전구체 1 중량부를 기준으로 금속 나노와이어 0.25 내지 4 중량부로 포함되는 것이 바람직하다. 상기 금속 나노와이어를 0.25 중량부 미만으로 사용하면, 금속 나노와이어가 네트워크를 제대로 형성하기 어려워 전도성을 가질 수 없게 되며, 상기 함량이 4 중량부를 초과하면, 금속 나노와이어가 너무 치밀하게 네트워크를 형성하여 기판이 흐려지게 되며, 이는 가시광 투과율 저하를 야기하므로 바람직하지 않다.The metal nanowires may be included in an amount of 0.25 to 4 parts by weight of the metal nanowires based on 1 part by weight of the metal precursor included in the metal sol. When the metal nanowires are used at less than 0.25 parts by weight, the metal nanowires are difficult to form a network properly and cannot have conductivity, and when the content is more than 4 parts by weight, the metal nanowires form a network too densely. The substrate becomes cloudy, which is undesirable since it causes a decrease in visible light transmittance.
상기 금속 나노와이어는 통상적으로 분산액에 분산시켜 사용하는 것이 바람직하며, 상기 분산액으로는 상기 금속 졸을 제조할 때 사용한 용매를 사용할 수 있다. 일예로 금속전구체와 용매를 혼합하여 금속졸의 제조시 용매의 일부를 금속 나노와이어의 분산매로 사용하여 분산매에 분산된 분산매-금속 나노와이어를 상기 금속졸과 혼합하여 최종 투명 전극 형성용 전도성 잉크 조성물을 제조할 수 있으며, 최종 투명 전극 형성용 전도성 잉크 조성물에서 각 성분의 함량은 상기 기재한 범위 내로 조절할 수 있다.It is preferable to disperse | distribute the said metal nanowire normally in a dispersion liquid, and the solvent used when manufacturing the said metal sol can be used as said dispersion liquid. For example, when preparing a metal sol by mixing a metal precursor and a solvent, a conductive ink composition for forming a final transparent electrode is formed by mixing a dispersion medium-metal nanowire dispersed in a dispersion medium with the metal sol using a portion of the solvent as a dispersion medium of the metal nanowires. It can be prepared, the content of each component in the conductive ink composition for forming the final transparent electrode can be adjusted within the above-described range.
본 발명에 따른 투명 전극 형성용 전도성 잉크 조성물은 상기 금속 졸, 금속 나노와이어 이외에 필요에 따라 당업계에서 통상적으로 사용되는 첨가제를 포함할 수 있다.The conductive ink composition for forming a transparent electrode according to the present invention may include additives commonly used in the art as needed in addition to the metal sol and the metal nanowire.
본 발명에 따른 투명 전극 형성용 전도성 잉크 조성물은 pH 범위가 6 내지 9 범위 내인 것이 좋다. 상기 pH가 6 미만 일 경우, 산 분위기에 의해 금속 나노와이어가 용액 내에서 산화될 수 있으며, 또한 pH가 9를 초과 할 경우에도 금속 나노와이어의 산화, 절단 또는 용해 현상이 발생할 수 있다.The conductive ink composition for forming a transparent electrode according to the present invention preferably has a pH in the range of 6 to 9. When the pH is less than 6, the metal nanowires may be oxidized in the solution by an acid atmosphere, and oxidation, cleavage, or dissolution of the metal nanowires may occur even when the pH exceeds 9.
또한 본 발명은 상기 투명 전극 형성용 전도성 잉크 조성물을 기재에 도포하고 소성하는 것을 특징으로 하는 전도성 투명 전극의 제조방법 및 상기 방법에 의하여 제조된 투명 전극을 제공한다.In another aspect, the present invention provides a method for producing a conductive transparent electrode and a transparent electrode produced by the method, characterized in that the transparent ink forming conductive ink composition is applied to a substrate and baked.
본 발명에 따른 투명 전극 형성용 전도성 잉크 조성물은 당분야에서 통상적으로 사용하는 다양한 인쇄공정, 예를 들어, 그라비아 옵-셋 (Gravure off-set) 인쇄, 그라비아 다이렉스(Gravure direct) 인쇄, 스크린 (Screen)인쇄, 스핀코팅(spin coating), 슬릿 코팅(slit coating), 슬롯 다이 코팅(slot die coating), 또는 임프린팅 방법 등을 이용하여 통상적으로 사용되는 투명 기판, 예를 들어, 유리 기판, 폴리이미드(PI) 기판, 폴리에틸렌테레프탈레이트(PET) 기판 등에 인쇄될 수 있으며, 두께는 용도에 따라 적절히 조절되는 것이 바람직하다.The conductive ink composition for forming a transparent electrode according to the present invention can be used in various printing processes commonly used in the art, for example, gravure off-set printing, gravure direct printing, screens ( Transparent substrates commonly used, for example, glass substrates, polys, using screen printing, spin coating, slit coating, slot die coating, or imprinting methods. It may be printed on a mid (PI) substrate, a polyethylene terephthalate (PET) substrate, and the like, and the thickness is preferably appropriately adjusted according to the use.
상기와 같이 제조된 전극은 당분야에서 통상적으로 사용되는 소성 방법에 따라 소성될 수 있으며, 상기 소성 조건은 기판 및 조성물의 특성에 따라 적절히 조절될 수 있으며, 300 ℃ 미만에서의 소성이 가능하여 필름을 포함한 유기물질 기재에도 적용이 가능하며, 바람직하게는 80℃ 내지 250℃에서 소성하는 것이 좋다.The electrode prepared as described above may be fired according to a firing method commonly used in the art, the firing conditions may be appropriately adjusted according to the characteristics of the substrate and the composition, it is possible to bake at less than 300 ℃ film It is also applicable to the organic material base material, including, preferably firing at 80 ℃ to 250 ℃.
본 발명에 따른 상기 투명 전극은 액정 표시장치, 플라즈마 표시장치, 터치패널, 전계발광 장치, 박막태양전지, 염료감응태양전지, 무기물 결정질 태양전지 등의 전극에 유용하게 활용될 수 있다.The transparent electrode according to the present invention may be usefully used for electrodes such as liquid crystal displays, plasma displays, touch panels, electroluminescent devices, thin film solar cells, dye-sensitized solar cells, and inorganic crystalline solar cells.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
실시예 1 내지 14: 투명 전극용 전도성 잉크 제조Examples 1 to 14 Preparation of conductive ink for transparent electrodes
하기 표 1에 기재된 성분과 함량에 따라 금속 전구체와 용매를 상온상압 조건에서 혼합하여 금속 졸을 제조한 다음, 나노와이어 분산액을 혼합하여 투명 전극용 전도성 잉크를 제조하였다. 이 때, 금속 나노와이어 분산액으로는 은 나노와이어가 이소프로판올에 0.8 중량% 농도로 분산된 은 나노와이어 분산액을 사용하였다.To prepare a metal sol by mixing a metal precursor and a solvent at room temperature and normal pressure conditions according to the components and contents shown in Table 1, and then mixed with a nanowire dispersion to prepare a conductive ink for transparent electrodes. At this time, silver nanowire dispersion liquid in which silver nanowires were dispersed in isopropanol at a concentration of 0.8% by weight was used as the metal nanowire dispersion liquid.
표 1
단위(g) 금속전구체 1 금속전구체 2 금속전구체 3 주 용매 부 용매 1 부 용매 2
실시예 1 Zn AcAc 0.3 　 　 　 　 AcAc 6 　 　 　 　
실시예 2 Zn AcAc 2 　 　 　 　 AcAc 6 EtOH 3 　 　
실시예 3 Zn AcAc 1.5 　 　 　 　 AcAc 5 MtOH 2 　 　
실시예 4 Zn AcAc 0.8 　 　 　 　 EtOH 5 AcAc 2 　 　
실시예 5 Zn AcAc 0.8 　 　 　 　 EtOH 5 AcAc 1 IPAC 1
실시예 6 Zn AcAc 0.8 Fe AcAc 0.01 　 　 EtOH 5 AcAc 1 IPAC 1
실시예 7 Zn AcAc 0.8 Cu AcAc 0.05 　 　 EtOH 5 AcAc 1 IPAC 1
실시예 8 Zn AcAc 0.8 Cu AcAc 0.05 Fe AcAc 0.01 EtOH 5 AcAc 1 IPAC 1
실시예 9 Zn AcAc 0.8 　 　 　 　 EtOH 5 AcAc 1 IPA 1
실시예 10 Zn AcAc 0.8 Fe AcAc 0.01 　 　 EtOH 5 AcAc 1 IPA 1
실시예 11 Zn AcAc 0.8 Cu AcAc 0.05 　 　 EtOH 5 AcAc 1 IPA 1
실시예 12 Zn AcAc 0.8 Cu AcAc 0.05 Fe AcAc 0.01 EtOH 5 AcAc 1 IPA 1
실시예 13 Zn AcAc 1.8 　 　 　 　 AcAc 6 IPA 2 　 　
실시예 14 Zn Ac 0.5 　 　 　 　 AcAc 6 　 　 　 　
실시예 15 Zn Ac 0.5 　 　 　 　 MtOH 6 　 　 　 　
실시예 16 Zn Ac 1.5 　 　 　 　 MtOH 12 AcAc 4 　 　
실시예 17 Zn Ac 1 　 　 　 　 EtOH 10 IPA 2 MtOH 1
실시예 18 Zn AcAc 1.5 Cu AcAc 0.05 　 　 AcAc 6 EtOH 4 　 　
실시예 19 Zn AcAc 1.5 Cu AcAc 0.05 Sn AcAc 0.05 AcAc 6 EtOH 4 　 　
실시예 20 Zn AcAc 1.5 Cu AcAc 0.05 Fe AcAc 0.01 AcAc 6 EtOH 4 　 　
실시예 21 Zn AcAc 1.5 Cu AcAc 0.05 　 　 AcAc 6 MtOH 3 　 　
실시예 22 Zn AcAc 1.5 Cu AcAc 0.05 　 　 AcAc 15 IPA 4 　 　
실시예 23 Zn AcAc 1 Sn AcAc 0.1 　 　 EtOH 12 AcAc 4 　 　
실시예 24 Zn AcAc 1 Al AcAc 0.01 　 　 AcAc 11 IPA 2.4 　 　
실시예 25 Zn AcAc 1.5 Fe AcAc 0.02 　 　 AcAc 5 MtOH 3 　 　
실시예 26 Zn AcAc 1 Zn Ac 0.1 　 　 AcAc 5 MtOH 3 　 　
실시예 27 Zn AcAc 1 Zn Ac 0.1 　 　 AcAc 5 EtOH 3 　 　
실시예 28 Zn AcAc 1.5 Ag Ac 0.01 　 　 AcAc 15 MtOH 10 　 　
실시예 29 Zn AcAc 1.5 Ag AcAc 0.01 　 　 AcAc 5 EtOH 3.5 　 　
Table 1
Unit (g) Metal precursor 1 Metal precursor 2 Metal precursor 3 Main solvent Minor solvent 1 Minor solvent 2
Example 1 Zn AcAc 0.3 AcAc 6
Example 2 Zn AcAc 2 AcAc 6 EtOH 3
Example 3 Zn AcAc 1.5 AcAc 5 MtOH 2
Example 4 Zn AcAc 0.8 EtOH 5 AcAc 2
Example 5 Zn AcAc 0.8 EtOH 5 AcAc One IPAC One
Example 6 Zn AcAc 0.8 Fe acac 0.01 EtOH 5 AcAc One IPAC One
Example 7 Zn AcAc 0.8 Cu AcAc 0.05 EtOH 5 AcAc One IPAC One
Example 8 Zn AcAc 0.8 Cu AcAc 0.05 Fe acac 0.01 EtOH 5 AcAc One IPAC One
Example 9 Zn AcAc 0.8 EtOH 5 AcAc One IPA One
Example 10 Zn AcAc 0.8 Fe acac 0.01 EtOH 5 AcAc One IPA One
Example 11 Zn AcAc 0.8 Cu AcAc 0.05 EtOH 5 AcAc One IPA One
Example 12 Zn AcAc 0.8 Cu AcAc 0.05 Fe acac 0.01 EtOH 5 AcAc One IPA One
Example 13 Zn AcAc 1.8 AcAc 6 IPA 2
Example 14 Zn Ac 0.5 AcAc 6
Example 15 Zn Ac 0.5 MtOH 6
Example 16 Zn Ac 1.5 MtOH 12 AcAc 4
Example 17 Zn Ac One EtOH 10 IPA 2 MtOH One
Example 18 Zn AcAc 1.5 Cu AcAc 0.05 AcAc 6 EtOH 4
Example 19 Zn AcAc 1.5 Cu AcAc 0.05 Sn AcAc 0.05 AcAc 6 EtOH 4
Example 20 Zn AcAc 1.5 Cu AcAc 0.05 Fe acac 0.01 AcAc 6 EtOH 4
Example 21 Zn AcAc 1.5 Cu AcAc 0.05 AcAc 6 MtOH 3
Example 22 Zn AcAc 1.5 Cu AcAc 0.05 AcAc 15 IPA 4
Example 23 Zn AcAc One Sn AcAc 0.1 EtOH 12 AcAc 4
Example 24 Zn AcAc One Al AcAc 0.01 AcAc 11 IPA 2.4
Example 25 Zn AcAc 1.5 Fe acac 0.02 AcAc 5 MtOH 3
Example 26 Zn AcAc One Zn Ac 0.1 AcAc 5 MtOH 3
Example 27 Zn AcAc One Zn Ac 0.1 AcAc 5 EtOH 3
Example 28 Zn AcAc 1.5 Ag Ac 0.01 AcAc 15 MtOH 10
Example 29 Zn AcAc 1.5 Ag AcAc 0.01 AcAc 5 EtOH 3.5
상기 표 1에서 Zn AcAc는 아세틸아세톤산 아연, Cu AcAc는 아세틸아세톤산 구리, Sn AcAc는 아세틸아세톤산 주석, Al AcAc는 아세틸아세톤산 알루미늄, Fe AcAc는 아세틸아세톤산 철, Zn Ac는 아세트산 아연, Ag Ac는 아세트산 은, Ag AcAc는 아세틸아세톤산 은, AcAc는 아세틸아세톤, IPA는 이소프로판올을 나타낸다. In Table 1, Zn AcAc is zinc acetylacetonate, Cu AcAc is copper acetylacetonate, Sn AcAc is acetylacetonate tin, Al AcAc is acetylacetonate aluminum, Fe AcAc is acetylacetonate iron, Zn Ac is zinc acetate, Ag Ac stands for silver acetate, Ag AcAc stands for acetylacetonic acid, AcAc stands for acetylacetone, and IPA stands for isopropanol.
시험예 1Test Example 1
상기 실시예 1 내지 14에서 제조한 투명 전극용 전도성 잉크의 가시광 투과도와 전도성을 측정하여 내환경성 평가를 실시하였다.The environmental resistance was evaluated by measuring the visible light transmittance and conductivity of the conductive ink for transparent electrodes prepared in Examples 1 to 14.
구체적으로, 유리 기판을 유기물 등 이물질을 제거하기 위하여 세정한 후, 상기 실시예 1 내지 14의 투명 전극용 전도성 잉크를 유리 기판에 각각 도포하였다. 도포 후, 200 ℃에서 10분간 열처리하였다.Specifically, the glass substrate was cleaned to remove foreign substances such as organic matter, and then the conductive inks for transparent electrodes of Examples 1 to 14 were applied to the glass substrates, respectively. After application, heat treatment was performed at 200 ° C. for 10 minutes.
400 nm 내지 800 nm 파장 영역에서 Agilent사의 Cary 4000 UV-Visible Spectrophotometer를 이용하여 가시광 투과도를 측정하고, 전도성 4-point 측정 기기로 면저항을 측정함으로써 전도성을 측정하였으며, 온도 85 ℃ 및 습도 85% 조건에서 면저항이 변하지 않는 시간을 측정함으로써 내환경성을 평가하였다. 그 결과를 하기 표 2 및 도 3에 나타내었다.In the 400 nm to 800 nm wavelength range, visible light transmittance was measured using Agilent's Cary 4000 UV-Visible Spectrophotometer, and the surface resistance was measured using a conductive 4-point measuring device. Environmental resistance was evaluated by measuring the time that sheet resistance does not change. The results are shown in Table 2 and FIG. 3.
표 2
　 광투과도(%) 면저항(Ω/□) 내환경성 평가(hr)
실시예 1 97.51 187 240
실시예 2 98.85 255 360
실시예 3 97.37 242 360
실시예 4 98.54 210 360
실시예 5 98.07 195 320
실시예 6 97.15 182 296
실시예 7 97.59 157 344
실시예 8 97.37 175 344
실시예 9 98.72 207 380
실시예 10 96.42 215 296
실시예 11 97.47 190 320
실시예 12 98.02 205 320
실시예 13 98.46 250 360
실시예 14 97.91 196 264
실시예 15 98.11 198 216
실시예 16 97.67 220 216
실시예 17 97.88 205 320
실시예 18 96.79 237 192
실시예 19 97.63 245 264
실시예 20 96.27 200 288
실시예 21 96.25 225 192
실시예 22 97.14 230 192
실시예 23 96.24 478 240
실시예 24 96.79 493 240
실시예 25 96.33 250 144
실시예 26 96.53 395 192
실시예 27 97.26 403 192
실시예 28 94.34 207 216
실시예 29 93.77 264 216
TABLE 2
Light transmittance (%) Sheet resistance (Ω / □) Environmental resistance evaluation (hr)
Example 1 97.51 187 240
Example 2 98.85 255 360
Example 3 97.37 242 360
Example 4 98.54 210 360
Example 5 98.07 195 320
Example 6 97.15 182 296
Example 7 97.59 157 344
Example 8 97.37 175 344
Example 9 98.72 207 380
Example 10 96.42 215 296
Example 11 97.47 190 320
Example 12 98.02 205 320
Example 13 98.46 250 360
Example 14 97.91 196 264
Example 15 98.11 198 216
Example 16 97.67 220 216
Example 17 97.88 205 320
Example 18 96.79 237 192
Example 19 97.63 245 264
Example 20 96.27 200 288
Example 21 96.25 225 192
Example 22 97.14 230 192
Example 23 96.24 478 240
Example 24 96.79 493 240
Example 25 96.33 250 144
Example 26 96.53 395 192
Example 27 97.26 403 192
Example 28 94.34 207 216
Example 29 93.77 264 216
상기 표 2 및 도 3에 나타난 바와 같이, 본 발명에 따라 금속 나노와이어 및 금속 졸을 포함하는 잉크 조성물을 이용하여 제조된 투명 전극은 광투과도가 93% 이상으로 매우 우수하고, 면저항이 500 Ω/□ 이하로 전도성이 매우 우수함을 알 수 있다.As shown in Table 2 and FIG. 3, the transparent electrode prepared by using the ink composition including the metal nanowires and the metal sol according to the present invention has an excellent light transmittance of 93% or more and a sheet resistance of 500 Ω / □ It can be seen that the conductivity is very excellent below.
또한 금속 졸이 금속 나노와이어의 보호층으로 작용하여 우수한 내환경성을 나타내므로, 별도의 산화방지제 또는 보호층이 필요하지 않다.In addition, since the metal sol acts as a protective layer of the metal nanowires and exhibits excellent environmental resistance, no separate antioxidant or protective layer is required.
본 발명에 따라 상기 금속 졸 및 금속 나노와이어를 포함하는 투명 전극 형성용 전도성 잉크 조성물은 금속 나노와이어로 전도성 네트워크를 형성하고 금속 졸로 네트워크의 단선을 보완하고 빈 공간을 채우므로, 우수한 전기전도성 및 가시광 투과도를 나타낸다. 또한 금속 졸이 금속 나노와이어의 부식 및 산화를 방지하는 보호층으로 작용하므로 별도의 산화방지제 또는 보호층이 필요하지 않고, 제조되는 투명 전극의 내환경성을 보장할 수 있다.According to the present invention, the conductive ink composition for forming a transparent electrode including the metal sol and the metal nanowire forms a conductive network with metal nanowires, and complements the disconnection of the network with the metal sol and fills the empty space, thereby providing excellent electrical conductivity and visible light. Permeability is shown. In addition, since the metal sol acts as a protective layer to prevent corrosion and oxidation of the metal nanowires, a separate antioxidant or protective layer is not required, and the environmental resistance of the manufactured transparent electrode can be guaranteed.

Claims (12)

  1. A)a) 금속 전구체; 및 b) 용매를 포함하는 금속 졸; 및A) a) a metal precursor; And b) a metal sol comprising a solvent; And
    B) 금속 나노와이어;B) metal nanowires;
    를 포함하는 것을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.Conductive ink composition for forming a transparent electrode comprising a.
  2. 제1항에 있어서,The method of claim 1,
    A)a) 금속 전구체 3 내지 20 중량%; 및 b) 용매 80 내지 97 중량%를 포함하는 금속 졸; 및A) a) 3 to 20% by weight of the metal precursor; And b) 80-97 wt% of a solvent; And
    B) 상기 금속 졸에 포함된 금속 전구체 1 중량부에 대하여 기준으로 금속 나노와이어 0.25 내지 4 중량부;B) 0.25 to 4 parts by weight of the metal nanowires based on 1 part by weight of the metal precursor contained in the metal sol;
    를 포함하는 것을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.Conductive ink composition for forming a transparent electrode comprising a.
  3. 제1항에 있어서,The method of claim 1,
    상기 금속 전구체의 금속이 Ⅰ족, ⅡA족, ⅢA족, ⅣA족 및 ⅤⅢ B족 금속으로 이루어진 군에서 선택되는 1종 이상의 금속임을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.A conductive ink composition for forming a transparent electrode, wherein the metal of the metal precursor is at least one metal selected from the group consisting of Group I, IIA, IIIA, IVA, and VIII B metals.
  4. 제3항에 있어서,The method of claim 3,
    상기 금속이 아연, 알루미늄, 주석, 철, 구리 및 은으로 이루어진 군에서 선택되는 1종 이상의 금속임을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.Conductive ink composition for forming a transparent electrode, characterized in that the metal is at least one metal selected from the group consisting of zinc, aluminum, tin, iron, copper and silver.
  5. 제1항에 있어서,The method of claim 1,
    상기 금속 전구체가 질산염, 아세트산염, 아세틸아세톤산염, 규산염, 인산염 및 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상의 무기염임을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.And the metal precursor is at least one inorganic salt selected from the group consisting of nitrates, acetates, acetylacetonates, silicates, phosphates and mixtures thereof.
  6. 제5항에 있어서,The method of claim 5,
    상기 금속 전구체가 아세트산염, 아세틸아세톤염 또는 규산염임을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.The conductive ink composition for forming a transparent electrode, wherein the metal precursor is acetate, acetylacetone salt or silicate.
  7. 제1항에 있어서,The method of claim 1,
    상기 용매가 물, 메탄올, 에탄올, 프로판올, 이소프로판올, 이소프로필아세테이트, 부탄올, 2-부탄올, 옥탄올, 2-에틸헥사놀, 펜탄올, 벤질알콜, 헥산올, 2-헥산올, 사이클로헥산올, 테르피네올, 노나놀, 메틸렌 글리콜, 에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 테트라에틸렌 글리콜, 에틸렌 글리콜 모노메틸에테르, 에틸렌 글리콜 모노에틸에테르, 에틸렌 글리콜 모노부틸에테르, 디에틸렌 글리콜 모노메틸에테르, 디에틸렌 글리콜 모노에틸에테르, 디에틸렌 글리콜 모노부틸에테르, 트리에틸렌 글리콜 모노메틸에테르, 트리에틸렌 글리콜 모노에틸에테르, 트리에틸렌 글리콜 모노부틸에테르, 2-프로판온, 디아세틸, 아세틸아세톤, 1,2-디아세틸에탄, 디메틸카보네이트, 디에틸카보네이트, 프로필렌글리콜메틸에테르아세테이트, 2-메톡시에틸아세테이트, 프로필렌글리콜모노메틸에테르, N-메틸-2-피롤리돈, N-메틸아세트아마이드 및 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상의 용매임을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.The solvent includes water, methanol, ethanol, propanol, isopropanol, isopropyl acetate, butanol, 2-butanol, octanol, 2-ethylhexanol, pentanol, benzyl alcohol, hexanol, 2-hexanol, cyclohexanol, Terpineol, nonanol, methylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 2-propanone, diacetyl, acetylacetone, 1,2- Diacetyl ethane, dimethyl carbonate, diethyl carbonate, propylene glycol methyl ether acetate, 2-methoxyethylacea A conductive ink composition for forming a transparent electrode, characterized in that at least one solvent selected from the group consisting of cetate, propylene glycol monomethyl ether, N-methyl-2-pyrrolidone, N-methylacetamide and mixtures thereof.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 용매가 2종 이상의 혼합용매이고, 주용매 1 중량부를 기준으로 0.2 내지 0.8 중량부의 부용매를 혼합되어 있는 것을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.The solvent is two or more mixed solvents, 0.2 to 0.8 parts by weight of the sub-solvent based on 1 part by weight of the main solvent is mixed conductive ink composition for forming a transparent electrode.
  9. 제1항에 있어서,The method of claim 1,
    pH가 6 내지 9인 것을 특징으로 하는 투명 전극 형성용 전도성 잉크 조성물.Conductive ink composition for forming a transparent electrode, characterized in that the pH of 6 to 9.
  10. 제1항 내지 제9항 중 어느 한 항 기재의 투명 전극 형성용 전도성 잉크 조성물을 기재에 도포하여 건조 및 소성하는 것을 특징으로 하는 전도성 투명전극의 제조방법.A method for manufacturing a conductive transparent electrode, characterized in that the conductive ink composition for forming a transparent electrode according to any one of claims 1 to 9 is applied to a substrate, followed by drying and baking.
  11. 제10항에 있어서,The method of claim 10,
    상기 소성은 80 내지 250 ℃에서 이루어지는 것을 특징으로 하는 전도성 투명전극의 제조방법.The firing is a method for producing a conductive transparent electrode, characterized in that at 80 to 250 ℃.
  12. 제10항 기재의 제조방법에 의하여 제조된 전도성 투명전극.A conductive transparent electrode prepared by the manufacturing method of claim 10.
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