KR20030047275A - Transparent conductive compound and printing method of forming transparent conductive electrode for display panel - Google Patents
Transparent conductive compound and printing method of forming transparent conductive electrode for display panel Download PDFInfo
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- KR20030047275A KR20030047275A KR1020010077725A KR20010077725A KR20030047275A KR 20030047275 A KR20030047275 A KR 20030047275A KR 1020010077725 A KR1020010077725 A KR 1020010077725A KR 20010077725 A KR20010077725 A KR 20010077725A KR 20030047275 A KR20030047275 A KR 20030047275A
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
Description
본 발명은 액정 표시소자, 전계 발광(EL; Electroluminescence) 표시소자나 플라즈마디스플레이패널(PDP; Plasma Display Panel) 표시소자 등에 사용하는 저 저항 투명성 도전 전극막(低抵抗 透明性 導電 電極膜) 회로를 유리 및 플라스틱필름 등의 기판에 스크린 인쇄법으로 형성할 수 있도록 하는 투명전도막 회로 조성물 및 그를 이용한 표시소자 기판 투명전도막 회로 형성방법에 관한 것으로, 더 자세하게는 전자제품분야, 자동차 및 항공기 표시기기분야, 자외선, 적외선 방지나 조광(調光)을 필요로 하는 프론트 글라스 등에 다용도로 이용할 수 있는 표시소자 기판의 투명전도막 회로 형성을 위한 조성물 및 그를 이용한 형성방법에 관한 것이다.The present invention provides a low resistance transparent conductive electrode film circuit for use in liquid crystal display devices, electroluminescence (EL) display devices, plasma display panel (PDP) display devices, and the like. And a method for forming a transparent conductive film circuit composition and a display device substrate transparent conductive film circuit using the same, which can be formed on a substrate such as a plastic film by screen printing, and more specifically, in the field of electronic products, automotive and aircraft display devices. The present invention relates to a composition for forming a transparent conductive film circuit of a display element substrate that can be used for a variety of purposes, such as a front glass requiring ultraviolet light, infrared ray prevention, or dimming, and a forming method using the same.
일반적으로 액정, 유기EL, PDP 등 영상 표시 소자류에는 저저항 투명 전극 막 회로의 형성이 필요하게 되는 바, 종래에 있어서 이러한 표시 소자류의 유리기판면에 투명도전막을 형성할 때에는 파우더(Powder)상의 인듐-주석 산화물(ITO;Indium Tin Oxide) 전구체를 이용한 이온 스퍼터링법(Spattering; 분산, 뿌리기)이나 진공증착법을 주로 사용하였고, 투명도전막을 형성한 후 전극패턴회로를 에칭처리로 형성하였다.In general, low-resistance transparent electrode film circuits are required for image display devices such as liquid crystal, organic EL, and PDP. In the past, when a transparent conductive film is formed on a glass substrate surface of such display devices, a powder is used. Ion sputtering (dispersing, spraying) or vacuum deposition using an indium tin oxide (ITO) precursor on the phase was mainly used. After forming a transparent conductive film, an electrode pattern circuit was formed by etching.
그러나 상기 종래의 스퍼터링법 및 저온진공증착법은 챔버실의 용량과 기판치수가 제한되므로 대형 표시소자 전극회로 등의 형성에 1000mm2이상의 장치와 고가의 비용이 들게 되어 비용면이나 양산성에서 큰 문제가 있었다.However, the conventional sputtering method and the low temperature vacuum deposition method are limited in the capacity of the chamber chamber and the size of the substrate, so that the formation of a large display device electrode circuit, etc., requires a device of 1000 mm 2 or more and a high cost. there was.
또한 상기에서 스퍼터링법은 성막시(成膜時) 기판을 가열하여야 하지만 그 가열온도가 기판의 내열온도로 제한되므로 고품질의 ITO 성막을 제조하기 어렵게 되는 바, 예를 들어 비내열성 폴리에틸렌테레프탈레이트(PET; Polyethylene Terephtalate)필름 기판의 스퍼터링 처리온도가 120℃ 전후로 제한되기 때문에 200Ω/cm2이하의 저저항치 ITO 성막을 제조하는 것이 곤란하게 된다.In addition, the sputtering method is required to heat the substrate during film formation, but since the heating temperature is limited to the heat resistance temperature of the substrate, it is difficult to produce high quality ITO film, for example, non-heat-resistant polyethylene terephthalate (PET Polyethylene Terephtalate) Since the sputtering treatment temperature of the film substrate is limited to around 120 ° C, it is difficult to produce a low resistance value ITO film of 200 Ω / cm 2 or less.
한편 도포소성법(塗布燒成法)은 투명도전막 형성할 때에 기판면에 ITO 전구체나 Sn 용액을 스프레이나 코팅으로 도포한 후 도포막을 400~550℃로 고온건조소성시키기 때문에 비내열성의 플라스틱필름기판의 투명도전막 성형에 사용할 수가 없게 된다.On the other hand, the coating firing method is a non-heat-resistant plastic film substrate because it is applied to the substrate surface by spraying or coating an ITO precursor or Sn solution when forming a transparent conductive film and then drying the coating film at 400 to 550 ° C. at high temperature. Can not be used for forming the transparent conductive film.
그리고 기판의 반도체 및 컬러필터 등의 적층위에 투명전극회로층을 구성하는 데에는 도포 소성법으로 형성하는 것이 곤란하며, 스퍼터링법으로는 적층막표면에 플라즈마에 의한 손상이 있게 되고, 에칭액이나 에칭공정에 의한 적층막에 손상을 주게 되는 문제가 있게 된다.In addition, it is difficult to form a transparent electrode circuit layer on a stack of a semiconductor, color filter, etc. of a substrate by a coating baking method, and the sputtering method causes damage on the surface of the laminated film by plasma, There is a problem that damages the laminated film.
투명도전막을 형성하는 인듐-주석 산화물(ITO; Indium Tin Oxide)이나 인듐-아연 산화물(IZO; Indium Zinc Oxide)은 고순도 유기금속화합물을 사용하는 무색투명한 것으로, 스크린 인쇄방법에 의해 박막의 저저항성과 고투명성을 저온도에서 형성하는 제조프로세스가 필요하다.Indium tin oxide (ITO) or indium zinc oxide (IZO) forming a transparent conductive film is colorless and transparent using high purity organometallic compounds. There is a need for a manufacturing process for forming high transparency at low temperatures.
비내열플라스틱필름 기판 등에 ITO나 IZO 투명전도막을 형성할 때는 기판 특성 때문에 막 형성 온도가 100℃이하의 저온처리가 가능하여야 하며, 기판에 밀착성이 좋은 투명도전막층을 형성하는 방법이 요구된다.When forming an ITO or IZO transparent conductive film on a non-heat-resistant plastic film substrate, a low temperature treatment with a film formation temperature of 100 ° C. or lower should be possible due to substrate characteristics, and a method of forming a transparent conductive film layer having good adhesion to a substrate is required.
본 발명은 유기금속화합물을 조성하는 ITO나 IZO 전구체를 포함하는 조성물과 그를 통한 스크린 인쇄법으로, 그 목적이 투명전극회로와 투명박막도전막을 형성하고, 진공자외선조사, 단파장 자외선 조사법에 의한 광여기반응으로 저온에서 특성과 기능이 뛰어난 ITO나 IZO 투명도전막을 적은 비용으로 얻을 수 있도록 하는 표시소자 기판의 투명전도막 회로 조성물 및 투명전도막 회로 형성방법을 제공하는 데에 있는 것이다.The present invention is a composition comprising an ITO or IZO precursor for organizing an organometallic compound and a screen printing method through the same, the purpose of which is to form a transparent electrode circuit and a transparent thin film conductive film, the optical excitation by vacuum ultraviolet irradiation, short wavelength ultraviolet irradiation It is an object of the present invention to provide a transparent conductive film circuit composition and a transparent conductive film circuit forming method of a display device substrate which can obtain an ITO or IZO transparent conductive film having excellent properties and functions at low temperatures by low reaction.
본 발명은 상기의 목적을 달성하기 위하여 인듐과 주석을 함유하는 유기금속화합물을 안정용제에 용해시켜 무색투명하고 점성이 있는 액체상태로 만든 ITO 전구체에 유기 고분자 도전성 폴리머, 또는 유기 고분자 유전성 폴리머를 혼합하여 표시소자 기판의 투명전도막 회로 조성물을 만드는 것과, 이 조성물로 스크린 인쇄법으로 인쇄하여 기판에 투명전도막을 형성하는 것 등을 특징으로 하며, 이하 그구체적인 기술내용을 첨부도면에 의거하여 더욱 자세히 설명하면 다음과 같다.In order to achieve the above object, an organic polymer conductive polymer or an organic polymer dielectric polymer is mixed with an ITO precursor prepared by dissolving an organometallic compound containing indium and tin in a stable solvent to form a colorless, transparent and viscous liquid. To form a transparent conductive film circuit composition of the display device substrate, and to form a transparent conductive film on the substrate by screen printing using the composition, and the specific technical details are further described based on the accompanying drawings. The explanation is as follows.
즉, 본 발명의 투명전도막 회로 조성물은 ITO 전구체에 유기 고분자 전도성 폴리머, 또는 유기 고분자 유전성 폴리머를 혼합하여서 되는 것인 바,That is, the transparent conductive film circuit composition of the present invention is obtained by mixing an organic polymer conductive polymer or an organic polymer dielectric polymer with an ITO precursor.
ITO 전구체는ITO precursors
In(CH3)3, In(C2H5)3, Sn(CH3)4, Sn(C2H5)4등의 유기금속알킬화합물과Organometallic alkyl compounds such as In (CH 3 ) 3 , In (C 2 H 5 ) 3 , Sn (CH 3 ) 4 and Sn (C 2 H 5 ) 4;
In(OC2H5)3, In(C3H7)3, In(OC4H9)3, Sn(OC2H5)4, Sn(OC3H7)4, Sn(OC4H9)4등의 유기금속알콕시드화합물,In (OC 2 H 5 ) 3 , In (C 3 H 7 ) 3 , In (OC 4 H 9 ) 3 , Sn (OC 2 H 5 ) 4 , Sn (OC 3 H 7 ) 4 , Sn (OC 4 H 9 ) organometallic alkoxide compounds such as 4 ,
In(C5H7O2)2, In(C5H7O2)3, In(C5H7O2)3, In(C6H5)3, Sn(C5H7O2)2, Sn(C5H9)4등의 유기금속아세틸아세톤화합물을In (C 5 H 7 O 2 ) 2 , In (C 5 H 7 O 2 ) 3 , In (C 5 H 7 O 2 ) 3 , In (C 6 H 5 ) 3 , Sn (C 5 H 7 O 2 Organometallic acetylacetone compounds such as) 2 , Sn (C 5 H 9 ) 4
안정용제인 1,2-디메톡시에탄(dimethoxyetane)이나 디그라임 등에 용해시켜 In에 대한 Sn의 함유비를 100:2.5에서 100:10까지의 범위로 조합하여 무색투명하고 점성이 있는 액체상태로 만든 것이며,It is dissolved in the 1,2-dimethoxyetane or diglyme, which is a stable solvent, and the content of Sn to In is combined in the range of 100: 2.5 to 100: 10 to make a colorless, transparent and viscous liquid. ,
유기 고분자 전도성 폴리머, 또는 유기 고분자 유전성 폴리머는Organic polymer conductive polymer, or organic polymer dielectric polymer
폴리이소치아나프텐(PITN; Polyisothionaphtene),Polyisothionaphtene (PITN),
폴리에틸렌다이옥시사이오펜(PEDT; Polyethylenedioxythiophene),Polyethylenedioxythiophene (PEDT),
폴리스타일렌설포네이트(PSS; Polystyrenesulfonate),Polystyrenesulfonate (PSS),
폴리알킬플루오렌(PAF; Polyalkylfluorene),Polyalkylfluorenes (PAF),
폴리페닐비닐렌(PPV; Polyphenylvinylene),Polyphenylvinylene (PPV),
폴리사이오펜(PAT; Polythiophene),Polythiophene (PAT),
폴리비닐카바졸(PVC; Polyvinylcarbasol)Polyvinylcarbasol (PVC)
중의 어느 하나, 또는 하나 이상을 일정 비율로 혼합한 것이다.Any one or more than one is mixed by a fixed ratio.
한편 본 발명의 표시소자 기판의 투명전도막 회로 형성방법은 스크린 인쇄법을 등의 도포법을 이용하여 기판에 상기 투명전도막 회로 조성물로 투명전극막패턴을 인쇄하고, 진공 챔버나 질소 등의 불활성 가스 챔버에서 일정영역의 진공자외선을 조사(예를 들면 중수소램프 115nm~125nm를 조사)하거나 일정영역의 단파장자외선을 조사(예를 들면 엑시머램프 147nm전후를 조사)하여 광여기(光勵起)에 의한 유기금속화합물의 분자 해리 또는 결합에 의해 금속박막을 형성한 후 생성된 금속박막에 대해 공기 중에서 다시 자외선을 조사하여 O2나 O3에 의해 산화시킴으로써 In2O3와 SnO2가 함유된 ITO 투명전도막을 형성하는 것을 특징으로 하는 것이다.On the other hand, in the method of forming a transparent conductive film circuit of the display device substrate of the present invention, the transparent electrode film pattern is printed on the substrate using the screen printing method or the like coating method, and the inert vacuum chamber or nitrogen is inert. In the gas chamber, vacuum ultraviolet rays of a predetermined region (e.g., deuterium lamps 115nm to 125nm) are irradiated or short wavelength ultraviolet rays of a certain region (e.g., around 147nm of excimer lamps) are irradiated to the optical excitation. After forming a metal thin film by molecular dissociation or bonding of the organometallic compound, the resultant metal thin film was irradiated with ultraviolet rays in the air again and oxidized by O 2 or O 3 to thereby contain ITO containing In 2 O 3 and SnO 2. It is characterized by forming a transparent conductive film.
그리고 본 발명에 있어서는 투명전도막 회로 조성물을 기판 전면에 도포한 후 그 도포막면에 진공자외선영역의 엑시머레이저를 조사하여 조사한 개소에만 투명전도막을 형성할 수도 있다.In addition, in this invention, after apply | coating a transparent conductive film circuit composition to the whole board | substrate, a transparent conductive film can also be formed only in the place irradiated by irradiating the excimer laser of a vacuum ultraviolet region to the coating film surface.
한편 본 발명의 조성물에서 In과 Sn을 포함하는 ITO 전구체 대신에 In과 Zn을 포함하는 IZO 전구체를 사용하면 In2O3와 ZnO2가 함유된 IZO 투명전도막을 형성할 수 있게 되며, 이 IZO 투명전도막은 전술한 ITO 투명전도막과 동등한 투명전도성를 갖는다.On the other hand, using the IZO precursor containing In and Zn in place of the ITO precursor containing In and Sn in the composition of the present invention, it is possible to form an IZO transparent conductive film containing In 2 O 3 and ZnO 2 , the IZO transparent The conductive film has a transparent conductivity equivalent to the above-described ITO transparent conductive film.
본 발명에 있어서 유기금속화합물을 유기금속 안정용매로 폴리머상으로 조합한 ITO 전구체를 유기 고분자 도전성 폴리머 또는 유기 고분자 유전성 폴리머와 혼합한 조성물은 상온에서 안정된 점성과 유동성을 갖으며, 스크린인쇄법으로 도포패턴의 형성정도(形成精度)와 형성막수정도(形成膜厚精度), 형성막계면정도(形成膜界面精度)를 얻을 수 있다.In the present invention, a composition in which an ITO precursor obtained by combining an organometallic compound in a polymer phase with an organometallic stable solvent is mixed with an organic polymer conductive polymer or an organic polymer dielectric polymer has stable viscosity and fluidity at room temperature, and is applied by screen printing. The degree of formation of the pattern, the number of formed films, and the degree of forming film interface can be obtained.
그리고 본 발명에 있어서 이러한 막형성은 진공자외선조사 및 단파장자외선조사 등의 광조사법에 의한 광여기반응으로 유기화합물과 유기용매의 유기물을 해리분해 및 결합시킴으로써 이루어지는 것이므로 저온에서도 이루어질 수 있다.In the present invention, such a film is formed by dissociating and combining organic compounds and organic solvents of organic solvents by photo-excited reactions by light irradiation methods such as vacuum ultraviolet irradiation and short wavelength ultraviolet irradiation.
본 발명에 있어서는 유기금속 ITO 전구체나 IZO 전구체를 포함하는 조성물을 기판상에 스크린인쇄법으로 형성한 도포막에 대해 일정범위(115nm~174nm)의 자외선을 조사하는 바, 자외선의 조사는 진공상태 또는 불활성가스속에서 이루어지며, 자외선조사의 여기반응으로 화학반응이 생겨 유기금속화합물과 그 전구체 및 유기용매의 분자구조의 해리, 결합, 중합 등이 상온상태에서 반응 작용하여 유기금속화합물의 유기화합물구조는 해리되고, IT0 금속생성막 또는 IZO 금속생성막이 형성된다.In the present invention, the coating film formed by screen printing a composition containing an organometallic ITO precursor or an IZO precursor is irradiated with ultraviolet rays in a predetermined range (115 nm to 174 nm). It is formed in an inert gas, and chemical reaction occurs due to excitation reaction of UV irradiation, so that the dissociation, bonding, and polymerization of the molecular structure of organic metal compound and its precursor and organic solvent reacts at room temperature. Is dissociated and an IT0 metal film or an IZO metal film is formed.
상기에서 금속생성막이 형성된 기판을 조사실에서 배출하여 활성가스 주입 또는 대기중에서 ITO 생성막이나 IZO 생성막에 단파장자외선을 조사하면 자외선조사에 의해 O2와 O3가 발생하고, 이들은 ITO 생성막 또는 IZO 생성막에 결합하여 산화구조를 형성하게 되므로 In2O3와 SnO2또는 In2O3와 ZnO2의 투명저저항도전성 아몰퍼스(amorphous;비정질) 막을 형성한다.When the substrate on which the metal production film is formed is discharged from the irradiation chamber and irradiated with short wavelength ultraviolet rays to the ITO film or the IZO film in the active gas injection or air, O 2 and O 3 are generated by ultraviolet irradiation, and these are the ITO film or IZO. Since the oxide layer is formed by bonding to the resulting film, a transparent low resistance conductive amorphous film of In 2 O 3 and SnO 2 or In 2 O 3 and ZnO 2 is formed.
한편 240℃ 이상의 내열성을 갖는 유리, 세라믹, 폴리아미드 등의 기판에서는 형성된 아몰퍼스막을 240℃ 이상의 열처리하여 다결정막질(多結晶膜質)로 개질(改質) 형성한다.On the other hand, in a substrate such as glass, ceramic, polyamide or the like having heat resistance of 240 ° C or higher, the formed amorphous film is heat-treated at 240 ° C or higher to form a polycrystalline film.
[실시예]EXAMPLE
ITO 또는 IZO는 유기금속화합물인 알킬금속화합물, 알콕시드금속화합물 등의 고순도 유기금속화합물류를 사용한다.ITO or IZO uses high purity organometallic compounds such as alkyl metal compounds and alkoxide metal compounds which are organometallic compounds.
유기금속화합물류의 조성은 안정 유기 용매인 1,2-디메톡시에탄 (dimethoxyetane)이나 디그라임에 용해시켜 In 100%에 대해 Sn 2.5~10%를 함유하도록 배합 조성한 무색투명하고 점성이 있는 액체상태의 ITO 전구체를 만든다.Organometallic compounds are composed of colorless, transparent and viscous liquid which is dissolved in a stable organic solvent, 1,2-dimethoxyetane or diglyme to contain 2.5 to 10% Sn to 100% In. Make an ITO precursor.
또한 IZO에는 In 30~70%에 대해 Zn 30~70%를 함유하도록 배합 조성한 무색투명하고 점성이 있는 액체상태의 IZO 전구체를 만든다In addition, IZO produces a colorless, transparent and viscous liquid IZO precursor that is formulated to contain 30 to 70% of Zn to 30 to 70% of In.
플라스틱필름기판에 인쇄할 때에는 전구체화합물의 밀착성을 향상시키기 위해 전술한 전구체 화합물에 유기 고분자 도전성 폴리머인 폴리이소치아나프텐(PITN) 30% 용해액을 10~20% 첨가하여 만든 투명전도막 회로 조성물을 사용한다.When printing on a plastic film substrate, in order to improve the adhesion of the precursor compound, a transparent conductive film circuit composition made by adding 10 to 20% of a 30% solution of polyisothiaphnaphthene (PITN), an organic polymer conductive polymer, to the precursor compound described above. Use
ITO 전구체에 폴리이소치아나프텐(PITN)을 첨가한 투명전도막 회로 조성물의 용액은 PITN구조에 유기금속화합물 In, Sn, Zn 등이 금속착체(金屬錯體)로서 도핑되어 약간 담황녹의 투명용액색이 되는 경우가 있으며, PITN 자체의 도전성은 향상된다.In the solution of the transparent conductive film circuit composition in which polyisothianaphthene (PITN) is added to the ITO precursor, the organic solution of In, Sn, Zn, etc. is doped as a metal complex in the PITN structure, so that the solution is slightly pale yellow rust. It may become a color, and the electroconductivity of PITN itself improves.
또한 투명전도막 회로 조성물에 아크릴시클로펜타디아닐파라디움 (Acrylcyclopentadianylparadiume)을 0.3~0.8% 첨가하면 필름기판에 대한 밀착성이좋아지게 된다.In addition, when 0.3 to 0.8% of acrylcyclopentadianylparadium is added to the transparent conductive film circuit composition, adhesion to the film substrate is improved.
[실시예1]Example 1
투명전도막 회로 조성물의 배합예Formulation Example of Transparent Conductive Film Circuit Composition
유기금속화합물 순도 99.99(In-27.85%)100Organometallic Compound Purity 99.99 (In-27.85%) 100
유기금속화합물 순도 99.99(Sn-27.52%)4.9Organometallic Compound Purity 99.99 (Sn-27.52%) 4.9
유기용매 디그라임 70~Organic Solvent Degradation 70 ~
유기용매 1,2-디메톡시에탄30~Organic solvent 1,2-dimethoxyethane 30 ~
유기용제50~Organic Solvent 50 ~
폴리이소치아나프텐(PITN)60~Polyisothianaphthene (PITN) 60 ...
[실시예2]Example 2
스크린인쇄법을 사용하여 전극패턴 형성의 330~480 메슈 폴리에스테르나 α-메슈 V-PAR 스크린 메슈 등의 쇄판(刷版)으로 인쇄 도포하고, 상온이나 40℃ 전후의 저온도상태로부터 진공자외선조사실에 도입하여 질소불활성가스속에서 122nm의 광조사를 20~240초간 행하여 광여기화학반응으로 유기금속 전구체화합물을 해리하여 기판위에 투명한 산화전의 ITO막을 생성한다.Using screen printing, printing is applied with a printing plate such as 330 to 480 mesh polyester of electrode pattern formation or α-mesh V-PAR screen mesh, and vacuum-ultraviolet irradiation room at low temperature around 40 ° C It is introduced into a nitrogen-inert gas and subjected to 122 nm light irradiation for 20 to 240 seconds to dissociate the organometallic precursor compound by a photoexcited chemical reaction to form a transparent ITO film on the substrate.
막을 생성한 기판을 배출하여 대기나 산소중에서 단파장 자외선 174~254nm를 조사하면 산소 라디칼화에 의한 O2와 O3의 발생으로 생성막은 산화되어 ITO막을 형성한다.When the substrate on which the film is formed is discharged and irradiated with short wavelength ultraviolet rays from 174 to 254 nm in the air or oxygen, the resulting film is oxidized by the generation of O 2 and O 3 by oxygen radicalization to form an ITO film.
[실시예3-1]Example 3-1
투명전도막 회로 조성물의 스크린 인쇄처방Screen Printing Prescription of Transparent Conductive Film Circuit Composition
제판스크린메슈α400Engraving Screen Mesh α400
바이어스27"Bias27 "
장강도(長强度)텐션13.5kg/cmLong Tension 13.5kg / cm
감광유제도포막8㎛Photosensitive emulsion coating film 8㎛
기판유리(글라스)1.1mm광투과율92.0%Substrate glass (glass) 1.1mm light transmittance 92.0%
인쇄클리어런스2mmPrint clearance 2mm
스퀴즈각도75°Squeeze Angle 75 °
평행사쇄(平行斜刷)170°Parallel grinding 170 °
실인압(實印壓)1.2kg총압4.8kgActual pressure 1.2kg Gross pressure 4.8kg
인쇄속도0.15㎧Print Speed 0.15㎧
판간격10mm10mm between plates
도포두께2.2㎛/wet비접촉 레이저 포커스 측정Coating Thickness 2.2㎛ / wet Non-Contact Laser Focus Measurement
조사진공자외선광122nm~중수소자외선램프Irradiation Vacuum Ultraviolet Light 122nm ~ Heavy Duty Ultraviolet Lamp
창재(窓材)고순도 열선흡수 석영글라스Changjae high purity heat absorption quartz glass
환경온도48℃Environment temperature 48 ℃
대기공기 가급(加給)Atmospheric air possible
조사시간40~180secIrradiation time 40 ~ 180sec
제판 스크린 인쇄 조사처리 및 산화처리는 상기 각 조건에서 제조하였다.Engraving screen printing irradiation treatment and oxidation treatment were prepared under each of the above conditions.
[실시예3-2]Example 3-2
특성성막두께0.3㎛Characteristic film thickness 0.3㎛
광투과율89.5%1.1mm글라스 포함Light transmittance 89.5% 1.1mm with glass
표면저항치6.45Ω/㎠4단자측정Surface resistance 6.45Ω / ㎠ 4 terminal measurement
막경도6HFilm hardness 6H
상기 측정한 투명전도막을 형성하였다.The measured transparent conductive film was formed.
[실시예4-1]Example 4-1
실시예3-1의 처방에 따라 피리딜아조레조르신(PAR) 필름위에 스크린인쇄법으로 자발광소자(自發光素子)용 도트패턴전극의 ITO막을 형성한다.According to the prescription of Example 3-1, an ITO film of a dot pattern electrode for a self-light emitting element was formed by screen printing on a pyridyl azoresorcin (PAR) film.
기판PAR-125㎛필름광투과율92.5%Substrate PAR-125㎛ film light transmittance 92.5%
도트1.6 ×1.6mm(1.9 ×1.6mm/p)19200 도트Dot 1.6 × 1.6 mm (1.9 × 1.6 mm / p) 19200 dots
막두께ITO0.4㎛ 비접촉 레이저포커스 변위법ITO 0.4㎛ non-contact laser focus displacement method
막경도ITO6HMembrane hardness ITO6H
밀착도 PAR/ITO100:1001mm cross cut peelAdhesion level PAR / ITO100: 1001mm cross cut peel
투명도 ITO투명무색Transparency ITO Transparent Colorless
광투과율 PAR/ITO92.0%Light transmittance PAR / ITO92.0%
표면저항 ITO47Ω/㎠4단자측정Surface resistance ITO47Ω / ㎠ 4 terminal measurement
[실시예4-2]Example 4-2
실시예4-1의 전극도트패턴 ITO막위에 자발광소자를 스크린인쇄법을 사용 적층 구조로 만든다.On the electrode dot pattern ITO film of Example 4-1, a self-light emitting device was formed into a laminated structure using a screen printing method.
ITO 전도도 및 자발광소자 등의 전기전도특성은 스퍼터 ITO막과 동일한 특성치를 측정했다.The electrical conductivity of the ITO conductivity and the self-luminous element was measured at the same characteristics as those of the sputter ITO film.
PAR-125㎛필름 기판에 스크린인쇄법으로 Ag 전하구동전극회로(電荷驅動電極回路)를 만들고, Ag 전극회로에 접촉하는 위치에 발광소자용 투명전극 ITO막을 만든다.An Ag charge driving electrode circuit is made by screen printing on a PAR-125 탆 film substrate, and a transparent electrode ITO film for a light emitting element is made at a position in contact with the Ag electrode circuit.
ITO막위에 폴리에틸렌다이옥시사이오펜(PEDT; Polyethylendioxythiophene) 유기도전성고분자폴리머를 버퍼층으로 0.3㎛막을 만들고 도트피치부분에 절연층을 만든다.On the ITO membrane, a 0.3 μm film is made of a polyethylene polyoxyendioxy (PEDT) organic conductive polymer polymer as a buffer layer and an insulating layer is formed on the dot pitch portion.
버퍼층위에는 폴리에틸렌다이옥시사이오펜/ 폴리스타일렌설포네이트 (PEDT/PSS) 또는 폴리알킬플루오렌(PAF) 유기도전성 고분자 폴리머에 유기형광색소 및 발광유도체를 도핑하여 발광색으로 하는 발광층을 0.3㎛ 적층하고, 그 위에 폴리비닐카바졸(PVC)이나 폴리에틸렌다이옥시사이오펜(PEDT)에 하이드로퀴노린알루미나(Alq3; Hidro Quinoline Alumina) 금속착제를 도핑한 전자수송층을 적층 형성한다.On the buffer layer, an organic fluorescent dye and a light emitting conductor are doped with polyethylene dioxythiophene / polystyrene sulfonate (PEDT / PSS) or polyalkyl fluorene (PAF) organic conductive polymer to stack a light emitting layer having a light emitting color of 0.3 μm, and On the polyvinylcarbazole (PVC) or polyethylene dioxythiophene (PEDT), an electron transport layer doped with a hydroquinoline alumina (Alq 3 ; Hidro Quinoline Alumina) metal complex is formed.
도트주변에 절연막을 만들고 평형한 막면으로 만든다.An insulating film is made around the dot and made into a flat film surface.
이 막면위에 Al/Ag의 음극전극회로를 적층 형성하고 실리콘레진으로 단자부분 이외는 봉지(封止) 도포하여 발광소자구조로 한다.An Al / Ag cathode electrode circuit is formed on this film surface, and a silicon resin is used to seal a portion other than the terminal portion to form a light emitting device structure.
[실시예4-3]Example 4-3
유기고분자발광소자의 공정Process of Organic Polymer Light Emitting Diode
Ag전하구동전극회로막Ag charge driving electrode circuit film
ITO발광소자전극ITO light emitting device electrode
절연막Insulating film
PAF발광막PAF light emitting film
PEDT전자수송막PEDT electron transport membrane
절연막Insulating film
Al/Ag음극회로막Al / Ag cathode circuit film
봉지막(封止膜)Sealing film
9공정 적층 프로세스9 process lamination process
ITO의 전기특성 저항치는 47Ω/㎠부터 PEDT 막면상에서는 330~460Ω/㎠로 저항치가 증가하지만 PEDT는 도전성과 전하수송기능의 작용을 갖는 발광소자구조이며, DC/3.3.V에서 발광하고, DC/9V의 발광휘도는 6,800cd/㎡에 달한다.ITO resistivity increases from 47 특성 / ㎠ to 330 ~ 460Ω / ㎠ on PEDT membrane, but PEDT is a light emitting device structure that has the function of conductivity and charge transport function, and emits light at DC / 3.3.V. The luminous intensity of / 9V reaches 6,800 cd / m 2.
종래기술인 스퍼터 ITO필름의 200Ω/㎠면에 형성한 PEDT막면에서는 2100~2800Ω/㎠와 비교해 유기금속화합물에 의한 ITO막은 성능면에서 더욱 우수하다.On the surface of the PEDT film formed on the surface of 200 kV / cm 2 of the prior art sputtered ITO film, the ITO film made of an organometallic compound is more excellent in performance than the 2100-2800 kW / cm 2.
이상에서 설명한 바와 같이 본 발명은 ITO 전도체에 유기 고분자 도전성 폴리머 또는 유기 고분자 유전성 폴리머를 혼합하여 투명전도막 회로 조성물을 만들고, 이 조성물로 스크린인쇄법 등을 사용하여 기판에 투명전도막 회로를 형성하는 것으로, 본 발명에 의하면 저항치의 도전특성과 고투명성, 광투과율, 밀착성 등의 기능을 갖는 투명전도막 회로를 저온도에서 쉽게 형성할 수 있게 된다.As described above, the present invention provides a transparent conductive film circuit composition by mixing an organic polymer conductive polymer or an organic polymer dielectric polymer with an ITO conductor, and using the composition to form a transparent conductive film circuit on a substrate using a screen printing method. According to the present invention, it is possible to easily form a transparent conductive film circuit having a function of resistance, high transparency, light transmittance, adhesion, and the like at low temperature.
또한 본 발명에 의하면 기재의 내열성과 무관하게 스크린인쇄도포법과 저온형성법으로 박막형의 플렉시블한 필름액정 디스플레이와 필름 유기EL디스플레이 등의 표시소자를 고정도(高精度), 경량박형화, 대형화, 자유로운 사이즈 형상으로 저렴하게 제작할 수 있게 되며, 이러한 ITO 투명전도막은 에칭공정 등을 삭감할 수 있게 되므로 그 비용을 대폭 줄일 수 있게 되는 등의 효과를 얻을 수 있게 된다.According to the present invention, display devices such as thin film-type flexible film liquid crystal displays and film organic EL displays can be formed with high precision, light weight, large size, and free size shapes regardless of the heat resistance of the substrate by the screen printing coating method and the low temperature forming method. It is possible to manufacture inexpensively, and the ITO transparent conductive film can reduce the etching process and the like, so that the cost can be greatly reduced.
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| US8137794B2 (en) * | 2007-03-20 | 2012-03-20 | Evonik Degussa Gmbh | Transparent electrically conductive layer, a process for producing the layer and its use |
| KR20170053555A (en) * | 2015-11-05 | 2017-05-16 | 한국전자통신연구원 | Fabrication method for transparent conductive oxide thin film |
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| JPH10226535A (en) * | 1997-02-12 | 1998-08-25 | Showa Denko Kk | Production of transparent electroconductive film having high electric conductivity |
| KR100231790B1 (en) * | 1997-11-22 | 1999-12-01 | 성재갑 | Transparent conductive coating composition and its applications |
| KR100322063B1 (en) * | 1999-01-13 | 2002-03-12 | 김순택 | Composition for forming conductive layer, method for manufacturing the same and cathode ray tube employing conductive layer formed by using the same |
| KR100340410B1 (en) * | 1999-12-18 | 2002-06-12 | 이형도 | Organic light emitting device having double barrier quantum well structure |
| JP4872142B2 (en) * | 2000-04-28 | 2012-02-08 | Ｊｓｒ株式会社 | Antistatic curable composition, cured film and antistatic antireflection laminate |
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| US8137794B2 (en) * | 2007-03-20 | 2012-03-20 | Evonik Degussa Gmbh | Transparent electrically conductive layer, a process for producing the layer and its use |
| KR20170053555A (en) * | 2015-11-05 | 2017-05-16 | 한국전자통신연구원 | Fabrication method for transparent conductive oxide thin film |
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