KR20110026460A - Low temperature processable and photo-crosslinkable organic gate insulator, and organic thin film transistor device using the same - Google Patents
Low temperature processable and photo-crosslinkable organic gate insulator, and organic thin film transistor device using the same Download PDFInfo
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- KR20110026460A KR20110026460A KR1020110017361A KR20110017361A KR20110026460A KR 20110026460 A KR20110026460 A KR 20110026460A KR 1020110017361 A KR1020110017361 A KR 1020110017361A KR 20110017361 A KR20110017361 A KR 20110017361A KR 20110026460 A KR20110026460 A KR 20110026460A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
- H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
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Abstract
Description
본 발명은 차세대 플렉시블디스플레이등에서 구동스위칭 소자로서 응용이 가능한 유기박막트랜지스터(OTFT)에 이용 가능한 저온 공정 및 광중합법에 의해 광경화가 가능한 신규 유기절연체의 제조 방법 및 이로부터 제조된 유기절연체를 포함하는 유기박막트랜지스터에 관한 것이다. The present invention provides a method for preparing a new organic insulator that can be photocured by a low temperature process and a photopolymerization method that can be used as an organic thin film transistor (OTFT) that can be applied as a driving switching device in a next-generation flexible display, and an organic insulator prepared therefrom. It relates to a thin film transistor.
1980년대 이후 유기물을 활성층(active layer)으로 사용하는 유기박막트랜지스터(Organic Thin Film Transistor;OTFT)에 관한 연구가 전세계적으로 활발히 진행되고 있다. 유기박막트랜지스터는 기존의 실리콘-트랜지스터(Si-TFT)와 구조적으로 거의 유사하나 반도체 영역에서 실리콘 대신 유기물을 사용하는 점에서 차이가 있다. 유기박막트랜지스터는 기존의 실리콘 트랜지스터의 무기박막을 이용한 물리적/화학적 증착 방법 대신 상압의 스핀코팅 또는 프린팅 공정법의 종용이 가능해 제조공정을 단순화 시킬 수 있으며 저온 공정이 가능한 장점이 있다.Since the 1980s, research on organic thin film transistors (OTFTs) using organic materials as active layers has been actively conducted worldwide. The organic thin film transistor is almost similar in structure to a conventional silicon transistor (Si-TFT), but there is a difference in using an organic material instead of silicon in the semiconductor region. The organic thin film transistor can simplify the manufacturing process by using spin coating or printing method of atmospheric pressure instead of the physical / chemical deposition method using the inorganic thin film of the conventional silicon transistor, and has the advantage of low temperature process.
일반적으로 유기박막트랜지스터의 절연체로는 무기물인 실리콘 디옥사이드 (SiO2)등이 사용되며 유기물로는 폴리비닐알코올(PVA), 폴리비닐페놀(PVP), 폴리메틸메타아크릴레이트(PMMA) 및 폴리이미드(PI) 등의 물질이 이용되고 있다. 절연체는 유기반도체와 계면을 형성하게 되므로 절연체의 계면특성에 따라 유기반도체의 결정성, 형태 등이 좌우되기 때문에 최종 박막트랜지스터의 소자특성에 핵심적인 부분이다. In general, as an insulator of an organic thin film transistor, inorganic silicon dioxide (SiO 2 ) is used, and as organic materials, polyvinyl alcohol (PVA), polyvinylphenol (PVP), polymethylmethacrylate (PMMA), and polyimide ( Substances such as PI) are used. Since the insulator forms an interface with the organic semiconductor, the crystallinity and shape of the organic semiconductor depend on the interface characteristics of the insulator, which is an essential part of the device characteristics of the final thin film transistor.
유기박막트랜지스터의 우수한 특성을 얻기 위해서는 절연특성이 우수한 유기절연체의 개발이 필수적이며 유연한 기판에 유기박막트랜지스터를 구현하기 유기절연체 박막의 형성공정 온도 또한 저온 공정이 가능하여야 한다. 또한 유기절연체는 유기박막트랜지스터를 이용한 실제 어레이 소자제작을 위해서 패터닝 되어야 될 필요가 있다. In order to obtain the excellent characteristics of the organic thin film transistor, it is necessary to develop an organic insulator having excellent insulating properties. In order to implement the organic thin film transistor on a flexible substrate, the process temperature of forming the organic insulator thin film must be low temperature process. In addition, the organic insulator needs to be patterned in order to manufacture an actual array device using an organic thin film transistor.
폴리이미드 수지는 방향족 테트라카르복시산 또는 그 유도체와 방향족 디아민 또는 방향족 디이소시아네이트를 축중합 후 이미드화하여 제조되는 고내열 수지로서, 사용된 단량체의 종류에 따라 여러 가지의 분자구조를 가질 수 있다.The polyimide resin is a high heat resistant resin prepared by imidating an aromatic tetracarboxylic acid or a derivative thereof and an aromatic diamine or an aromatic diisocyanate, and may have various molecular structures depending on the type of monomer used.
이와 같은 폴리이미드 수지는 불용·불융의 초고내열성 수지로서 뛰어난 내열산화성, 높은 사용 가능 온도, 뛰어난 전기화학적·기계적 특성, 내방사선성 및 우수한 저온 공정 특성, 우수한 내약품성 등의 특성을 가지고 있으나, 반면에 높은 극성기 밀도로 인해 표면장력이 높으며, 박막트랜지스터용 절연체로 적용하기에는 낮은 유전 상수 등을 가지며, 이미드화 반응을 위한 공정온도가 높고 광경화에 의한 패턴의 형성이 용이하지 않은 단점을 가지고 있다. Such polyimide resins are insoluble and insoluble ultra-high heat resistant resins, and have excellent thermal oxidation resistance, high usable temperature, excellent electrochemical and mechanical properties, radiation resistance and low temperature process characteristics, and excellent chemical resistance. Due to the high polar group density, the surface tension is high, it has a low dielectric constant, etc. to be applied as an insulator for thin film transistors, has a high process temperature for imidization reaction, and it is not easy to form a pattern by photocuring.
폴리이미드 고분자의 경우 최종 고분자가 일반적인 유기용매에 녹는 경우와 고분자 전구체 상태에서 절연막을 형성한 후 고온의 열처리과정을 통해 최종 유기절연막을 형성하는 경우로 나눌 수 있다. 전자의 경우 최종 고분자를 유기용매에 녹여서 바로 박막공정을 진행하여 저온의 용매 건조 과정을 통해 최종 절연막을 형성할 수 있으나 용해도를 위해 도입한 고분자의 곁사슬 등은 유기절연막의 절연 특성 및 내화학성을 낮추는 단점이 있어왔다. 이러한 문제점에도 불구하고 최종으로 용해 가능한 유기절연체의 개발은 차세대 저가 디스플레이 및 유기소자의 구현에 필수적이이다.In the case of polyimide polymer, the final polymer may be divided into a case in which a final polymer is dissolved in a general organic solvent and a final organic insulating film is formed through a high temperature heat treatment after forming an insulating film in a polymer precursor state. In the former case, the final polymer may be melted in an organic solvent to proceed to a thin film process to form a final insulating film through a low temperature solvent drying process, but the side chains of the polymer introduced for solubility may lower the insulating properties and chemical resistance of the organic insulating film. There have been disadvantages. Despite these problems, the development of finally soluble organic insulators is essential for the implementation of next-generation low-cost displays and organic devices.
따라서, 최종 폴리이미드 고분자가 용액공정이 가능할 정도로 우수한 가공성을 가지면서, 고분자 곁사슬에 광경화 가능한 경화기를 도입하여 저온에서 절연막 형성 공정을 진행하고 광경화를 통하여 절연 특성 및 내화학성이 향상된 유기절연막을 형성할 수 있는 유기고분자 개발이 필요하다.
Therefore, while the final polyimide polymer has excellent processability enough to enable a solution process, a photocurable hardener is introduced into the polymer side chain to proceed with an insulating film formation process at a low temperature, and an organic insulating film having improved insulating properties and chemical resistance through photocuring is obtained. There is a need for developing organic polymers that can be formed.
본 발명에서는 차세대 플렉시블디스플레이 등에서 구동스위칭 소자로서 응용이 가능한 유기박막트랜지스터(OTFT)의 핵심 구성 성분인 유기절연체를 제조하기 위한 새로운 폴리이미드계 유기고분자를 제공하고자 하는 것으로서, 구체적으로는 열안정성 및 우수한 내화학성을 보이는 폴리이미드 유기절연체를 광 경화가 가능한 기능기와 반응시켜 궁극적으로 유기절연체의 경화 온도의 감소 및 절연 특성의 향상을 도모하고자 하는 것이다.
In the present invention, to provide a new polyimide-based organic polymer for manufacturing an organic insulator, which is a key component of the organic thin film transistor (OTFT) that can be applied as a driving switching device in the next-generation flexible display, specifically, thermal stability and excellent The polyimide organic insulator exhibiting chemical resistance is reacted with a functional group capable of photocuring to ultimately reduce the curing temperature of the organic insulator and improve the insulation characteristics.
본 발명에서는 하이드록시기를 포함하는 폴리이미드계 고분자를 광이성화 반응으로 인해 경화반응이 가능하게 하기 위하여 신나모일(cinnamoyl) 그룹 등 다양한 아크릴로일(acryloyl) 그룹과 반응시켜 신규 유기고분자를 제조하여 이를 유기박막트랜지스터 소자의 유기절연막으로 응용함으로써 소자에서 누설전류나 히스테리시스를 가져올 수 있는 문제를 해결하였으며 고온의 열적 경화 반응이 아니고 자외선 조사에 의한 광경화 방법을 통해서 유기절연체 박막제조의 공정온도도 낮추고 폴리이미드계 유기절연체의 절연특성을 향상시키는 효과를 얻을 수 있었다. In the present invention, in order to enable the curing reaction of the polyimide-based polymer containing a hydroxyl group by the photoisomerization reaction, it is reacted with various acryloyl groups such as cinnamoyl group to prepare a new organic polymer and Solving the problem of leakage current or hysteresis in the device by applying it as the organic insulating film of the organic thin film transistor device, and lowering the process temperature of the organic insulator thin film manufacturing by the photocuring method by ultraviolet irradiation, not the high temperature thermal curing reaction The effect of improving the insulation characteristics of the mid type organic insulator was obtained.
본 발명은 하이드록시기를 포함하는 폴리이미드계 고분자에 광경화 가능한 기능기로서 다양한 구조의 아크릴로일 (acryloyl)기가 도입된 새로운 폴리이미드계 유기고분자, 이의 제조방법을 제공하며, 상기 폴리이미드계 유기고분자의 도포 및 경화를 통해 형성되는 유기절연막을 포함하는 유기박막트랜지스터를 제공한다. The present invention provides a novel polyimide-based organic polymer in which acryloyl group of various structures is introduced as a photocurable functional group in a polyimide-based polymer including a hydroxy group, and a method of preparing the same. An organic thin film transistor comprising an organic insulating film formed through coating and curing of a polymer is provided.
이하에서 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 하기 화학식 1 또는 화학식 2로 표시되는 광경화 및 가용성 폴리이미드계 유기고분자에 관한 것으로 유기박막트랜지스터의 유기절연막 제조에 적합하다.The present invention relates to a photocurable and soluble polyimide organic polymer represented by the following formula (1) or (2), and is suitable for the manufacture of an organic insulating film of an organic thin film transistor.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[상기 화학식 1 내지 화학식 2에서 은 하기 구조 중에서 선택된 1종 또는 2종 이상의 4가기로서, 반드시 구조식 (a), (b), (c), (d), (e) 및 (f) 중에서 선택된 1종 또는 2종 이상의 지방족 고리계 4가기를 포함하며[In
; ;
은 하기 구조 중에서 선택된 1종 이상의 2가기이고 Is at least one divalent selected from the structures
; ;
n 및 m은 독립적으로 10 내지 2000의 자연수이며;n and m are independently a natural number from 10 to 2000;
a 및 b는 독립적으로 0 내지 10의 정수이고;a and b are independently an integer from 0 to 10;
X11 내지 X19 및 X21 내지 X27은 독립적으로 수소(H), (C1~C10)알킬, 시아노 또는 할로겐으로부터 선택되며;X 11 to X 19 and X 21 to X 27 are independently selected from hydrogen (H), (C 1 -C 10) alkyl, cyano or halogen;
y 및 z는 독립적으로 1 내지 16의 자연수이다.]y and z are independently a natural number of 1 to 16.]
상기 화학식 1 또는 화학식 2의 폴리이미드계 유기고분자는 중량평균 분자량 5,000 내지 1,000,000 g/mol인 것이 바람직한데, 이는 상기 분자량이 5,000 미만인 경우에는 유기절연막 자체의 저분자량에 의한 누설전류 등의 문제점이 발생할 수 있고, 상기 분자량이 1,000,000을 초과하는 경우에는 유기절연막 형성 공정에서 높은 분자량에 의한 가공성이 현저히 떨어지는 점에서 불리할 수 있기 때문이다. 또한 본 발명에 따른 폴리이미드계 유기고분자는 고유점도 0.1 내지 1.5 dL/g, 유리전이 온도 범위 150 내지 300 ℃의 특성을 가진다. Preferably, the polyimide organic polymer of Formula 1 or Formula 2 has a weight average molecular weight of 5,000 to 1,000,000 g / mol. If the molecular weight is less than 5,000, problems such as leakage current due to low molecular weight of the organic insulating film itself may occur. This is because, when the molecular weight exceeds 1,000,000, it may be disadvantageous in that the workability due to the high molecular weight is remarkably inferior in the organic insulating film forming step. In addition, the polyimide organic polymer according to the present invention has an intrinsic viscosity of 0.1 to 1.5 dL / g, the glass transition temperature range of 150 to 300 ℃.
또한, 본 발명에 따른 광경화 가용성 폴리이미드 수지는 디메틸아세트아미드(DMAc), 디메틸포름아미드(DMF), N-메틸-2-피롤리돈(NMP), 아세톤, 에틸아세테이트와 같은 비양성자성 극성용매를 비롯하여 메타-크레졸과 같은 유기용매에 대해 상온에서 쉽게 용해되는 특성을 가진다. 특히, 테트라히드로푸란(THF), 씨클로헥산 및 클로로포름과 같은 저비점 용매 및 감마-부티로락톤과 같은 저흡수성 용매에 대해서도 상온에서 10 중량% 이상의 높은 용해도를 나타낸다. 또한 이들의 혼합용매에 대해서도 높은 용해도를 나타낸다.In addition, the photocurable soluble polyimide resin according to the present invention has an aprotic polarity such as dimethylacetamide (DMAc), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), acetone, ethyl acetate Easily dissolved at room temperature with respect to organic solvents such as meta-cresol, including the solvent. In particular, tetrahydrofuran (THF), cyclohexane And low solubility solvents such as gamma-butyrolactone and low boiling point solvents such as chloroform. Moreover, high solubility is shown also about these mixed solvents.
본 발명에 따른 상기 화학식 1 및 2 로 표시되는 폴리이미드계 유기고분자는, 표면장력이 20 ~ 50 dyne/cm의 범위에 있으며, 유전상수가 2 ~ 6 범위에 있다. 또한, 300~400 nm의 파장을 가지는 자외광을 조사함에 의해 10 ~ 50 ㎛의 미세패턴이 형성이 가능하였으며 우수한 용해도로 인하여 폴리카르보네이트(polycarbonate), 폴리설폰(polysulfone) 폴리에테르설폰(polyether sulfone) 등의 플라스틱 기판위에서 저온 공정이 가능하다.The polyimide organic polymer represented by Chemical Formulas 1 and 2 according to the present invention has a surface tension in the range of 20 to 50 dyne / cm, and a dielectric constant in the range of 2 to 6. In addition, by irradiating with ultraviolet light having a wavelength of 300 ~ 400 nm, a fine pattern of 10 ~ 50 ㎛ was possible, and due to its excellent solubility, polycarbonate, polysulfone polyether sulfone (polyether) Low temperature processes are possible on plastic substrates such as sulfone).
본 발명은 상기 화학식 1 또는 화학식 2로 표시되는 폴리이미드계 유기고분자의 제조방법으로서, 하기 화학식 3의 히드록시기를 갖는 폴리이미드로부터 하기 화학식 4 또는 화학식 5의 아크릴로일계 할라이드를 반응시켜 광경화기를 갖는 가용성 폴리이미드계 유기고분자를 제조하는 방법을 제공한다.The present invention is a method for producing a polyimide-based organic polymer represented by the formula (1) or (2), by reacting the acryloyl halide of the formula (4) or formula (5) from a polyimide having a hydroxyl group of the formula (3) having a photocurable group Provided is a method for producing a soluble polyimide organic polymer.
[화학식 3](3)
[화학식 4][Formula 4]
[화학식 5][Chemical Formula 5]
[상기 화학식 3에서 , , a, b, X11 내지 X19 및 X21 내지 X27은 청구항 제1항에서 정의한 바와 같고, p는 10 내지 2000의 자연수이며, q는 0 내지 10의 정수이고, L은 할로겐원소를 나타낸다.][In Chemical Formula 3] , , a, b, X 11 to X 19 and X 21 to X 27 are as defined in
상기 화학식 3의 폴리이미드계 고분자는 카르복실산이무수물 및 히드록시기를 갖는 디아민 단량체의 중합에 의하여 제조된다.The polyimide-based polymer of Formula 3 is prepared by polymerization of a diamine monomer having a carboxylic dianhydride and a hydroxyl group.
테트라카르복실산이무수물 단량체로서 상기 (a)~(f)로 표시되는 구조에 해당하는 지방족 테트라카르복실산이무수물을 적절한 비율로 혼압 사용하여 기계적 특성과 내열성의 저하를 최소로 하면서도 용해성이 개선된 폴리이미드 유기절연체 고분자를 제조할 수 있다. 이에, 본 발명에서는 상기 (a)~(f)로 표시되는 구조에 해당하는 지방족 테트라카르복실산을 전체 산이무수물 사용량에 대하여 1내지 99 몰% 범위로 사용한다.As the tetracarboxylic dianhydride monomer, an aliphatic tetracarboxylic dianhydride corresponding to the structure represented by the above (a) to (f) is mixed and mixed at an appropriate ratio to minimize the degradation of mechanical properties and heat resistance while The mid organic insulator polymer can be manufactured. Thus, in the present invention, aliphatic tetracarboxylic acids corresponding to the structures represented by the above (a) to (f) are used in the range of 1 to 99 mol% based on the total amount of the acid dianhydride.
즉, 테트라카르복실산이무수물 단량체로서는 1,2,3,4-시클로부탄 테트라카르복실산이무수물[CBDA; (a)], 1,2,3,4-시클로펜탄 테트라카르복실산이무수물[CPDA; (b)], 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물(c), 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸-3-시클로헥센-1,2-디카르복실산이수물 [DOCDA; (d)], 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물[DOTDA; (e)], 및 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물[BODA; (f)] 중에서 선택된 1종 또는 2종 이상의 지방족산이무수물이 필수성분으로 포함된다. That is, as the tetracarboxylic dianhydride monomer, 1,2,3,4-cyclobutane tetracarboxylic dianhydride [CBDA; (a)], 1,2,3,4-cyclopentane tetracarboxylic dianhydride [CPDA; (b)], 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride (c), 5- (2,5-dioxotetrahydrofuryl ) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dihydrate [DOCDA; (d)], 4- (2,5-dioxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride [DOTDA; (e)] and bicyclooctene-2,3,5,6-tetracarboxylic dianhydride [BODA; One or two or more aliphatic dianhydrides selected from (f)] are included as essential ingredients.
동시에 본 발명의 가용성 폴리이미드 유기절연체는 피로멜리트산이무수물, 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물 및 헥사플루오로이소프로필리덴디프탈산이무수물 등 중에서 선택된 1종 또는 2종 이상의 방향족 테트라카르복실산이무수물이 포함될 수 있다.At the same time, the soluble polyimide organic insulator of the present invention is selected from pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, nonphthalic dianhydride and hexafluoroisopropylidene diphthalic dianhydride. Or two or more aromatic tetracarboxylic dianhydrides.
디아민 단량체로서는 파라-페닐렌디아민(p-PDA), 메타-페닐렌디아민(m-PDA), 4,4-옥시디아닐린(ODA), 4,4-메틸렌디아닐린(MDA), 2,2-비스아미노페닐헥사풀루오로프로판(HFDA), 메타비스아미노페녹시디페닐설폰(m-BAPS), 파라비스아미노페녹시디페닐설폰(p-BAPS), 1,4-비스아미노페녹시벤젠(TPE-Q), 1,3-비스아미노페녹시벤젠(TPE-R), 2,2-비스아미노페녹시페닐프로판(BAPP) 및 2,2-비스아미노페녹시페닐헥사풀루오로프로판(HFBAPP) 등 중에서 선택된 1종 또는 2종 이상의 방향족 디아민계 화합물에 광경화 가능한 기능기와 반응이 가능한 하이드록시 그룹을 각각 최소 1개 내지 16개 까지 보유한 단량체를 사용할 수 있다.As the diamine monomer, para-phenylenediamine (p-PDA), meta-phenylenediamine (m-PDA), 4,4-oxydianiline (ODA), 4,4-methylenedianiline (MDA), 2,2 Bisaminophenylhexafluoropropane (HFDA), metabisaminophenoxydiphenylsulfone (m-BAPS), parabisaminophenoxydiphenylsulfone (p-BAPS), 1,4-bisaminophenoxybenzene (TPE) -Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP) and 2,2-bisaminophenoxyphenylhexafuluropropane (HFBAPP) A monomer having at least one to sixteen hydroxyl groups each capable of reacting with a photocurable functional group may be used in one or two or more aromatic diamine compounds selected from the above.
광경화기의 도입은 상기 화학식 3의 가용성 폴리이미드를 만든 후에 상기 화학식 4 또는 화학식 5의 아크릴로일계 할라이드와 반응시켜 가용성 폴리이미드의 하이드록시 그룹과 광경화가 가능한 기능기의 반응에 의해 화학식 1 또는 화학식 2의 광경화가 가능한 가용성 폴리이미드 고분자를 완성한다.Introduction of the photocuring group may be performed by preparing a soluble polyimide of Chemical Formula 3 and then reacting with acryloyl halide of Chemical Formula 4 or Chemical Formula 5 to react the hydroxyl group of the soluble polyimide with a functional group capable of photocuring. A soluble polyimide polymer capable of photocuring 2 is completed.
상기 화학식 3의 화합물과 화학식 4의 화합물과의 반응을 통하여 화학식 1의 폴리이미드계 유기고분자가 제조되고, 상기 화학식 3의 화합물과 화학식 5의 화합물과의 반응을 통하여 상기 화학식 2의 폴리이미드계 유기고분자가 제조된다.The polyimide organic polymer of Formula 1 is prepared by reacting the compound of
본 발명의 일 실시예에서는 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물[DOCDA;(c)] 과 디아민 단량체로는 하이드록시 그룹이 치환된, 3,3-디하이드록시베니딘(3,3-dihydroxybenidine ;HAB)와 2,2-비스(3-아미노-4-하이드록시페닐)헥사플루오로프로판(2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane;6FHAB)를 각각 이용하여 하이드록시 그룹이 치환된 가용성 폴리이미드를 합성하고 합성된 고분자를 이용하여 최종적으로 광경화가 가능한 신나모일 클로라이드(cinnamoyl chloride)를 하이드록시 그룹과 반응시켜서 고분자 곁사슬에 도입하였다. 광경화가 가능한 기능기를 가지는 화합물로는 신나모일 클로라이드 (cinnamoyl chloride) 뿐만 아니라 고분자 곁사슬의 하이드록시 그룹과 반응이 가능한 아크릴로일(acrylol) 그룹이 치환되어 있는 3-나프탈렌-1-일-아크릴로일 클로라이드(3-naphthalen-1-yl-acyloyl chloride), 3-바이페닐-4-일-아크릴로일 클로라이드(3-biphenyl-4-yl-acyloyl chloride)등 또한 이용이 가능하다.In one embodiment of the present invention, 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride [DOCDA; (c)] and a diamine monomer are hydroxy. 3,3-dihydroxybenidine (HAB) and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (2,2-Bis) with group substituted (3-amino-4-hydroxyphenyl) hexafluoropropane; 6FHAB) was used to synthesize soluble polyimides substituted with hydroxy groups, and finally synthesized cinnamoyl chloride, which can be photocured, using the synthesized polymer. Reaction with the group was introduced into the polymer side chain. As a compound having a photocurable functional group, 3-naphthalen-1-yl-acryloyl in which not only cinnamoyl chloride is substituted, but also acryloyl group capable of reacting with a hydroxyl group of the polymer side chain is used. 3-naphthalen-1-yl-acyloyl chloride and 3-biphenyl-4-yl-acyloyl chloride may also be used.
또한 본 발명은 상기 화학식 1 또는 화학식 2의 폴리이미드계 유기고분자를 사용하여 용액공정을 통해 유기절연막을 제조하는 방법 및 상기 유기절연막을 포함하는 유기 박막트랜지스터를 제공한다.In another aspect, the present invention provides a method for producing an organic insulating film through a solution process using the polyimide organic polymer of
본 발명에 따른 유기박막트랜지스터는 상기 화학식 1 또는 화학식 2의 광반응기가 도입된 폴리이미드계 유기고분자를 함유하는 코팅액을 게이트 전극이 형성된 기판 상에 도포한 후 광경화하여 형성된 유기절연막을 포함한다.The organic thin film transistor according to the present invention includes an organic insulating film formed by applying a coating liquid containing a polyimide-based organic polymer into which the photoreactor of
도 2에서는 본 발명의 하나의 구현 예에 따른 하 게이트(bottom gate) 상 접촉(top-contact) 유기박막트랜지스터의 구조를 나타낸다. 도 3을 참조하면, 유리 또는 플라스틱 등의 기판(1) 위에 게이트 전극(2), 유기절연막(3), 유기반도체층(4), 소스 전극(5), 드레인 전극(6)이 형성되어 있으며, 도시되지는 않았으나 소스 전극 및 드레인 전극상에 보호층을 더 형성할 수 있다. FIG. 2 illustrates a structure of a bottom gate top-contact organic thin film transistor according to an exemplary embodiment of the present invention. Referring to FIG. 3, a
유기절연막을 형성하기 위한 코팅액은 점도 조절을 용이하게 하고 폴리이미드계 유기고분자에 대한 용해성이 우수한 용매를 포함할 수 있으며, 적절한 용매로는 클로로포름, 테트라히드로푸란(THF), 씨클로헥산 등을 예로 들 수 있다. 상기 도포는 스핀코팅, 잉크젯 프린팅, 롤코팅, 스크린 프린팅, 및 딥핑으로부터 선택되는 하나 이상의 방법으로 수행될 수 있다.The coating liquid for forming the organic insulating film may include a solvent that facilitates viscosity control and has excellent solubility in polyimide organic polymers. Examples of suitable solvents include chloroform, tetrahydrofuran (THF), cyclohexane, and the like. Can be. The application can be performed by one or more methods selected from spin coating, ink jet printing, roll coating, screen printing, and dipping.
도 1은 본 발명에 따른 폴리이미드계 유기고분자의 광중합에 의한 경화 메카니즘을 도시한 것으로 화학식 1 또는 화학식 2로 표시되는 폴리이미드계 유기고분자의 광경화 작용기인 아크릴로일기 사이의 반응에 의해 경화되는 것을 나타낸다.1 illustrates a curing mechanism by photopolymerization of a polyimide organic polymer according to the present invention and is cured by a reaction between acryloyl groups, which are photocuring functional groups of a polyimide organic polymer represented by
본 발명에서 광경화는 UV 조사 후 100℃ 내지 200℃의 열처리를 통하여 이루어진다. 광경화 과정이 없는 경우에는 200℃를 초과하는 열처리가 요구되는 것에 비하여 현저히 낮은 온도에서 공정이 가능하다. 상기 UV조사 에너지는 500mJ 내지 2000mJ 범위에서 수행되는 것이 경화성 및 물성 유지 측면에서 더욱 바람직하다.Photocuring in the present invention is carried out through a heat treatment of 100 ℃ to 200 ℃ after UV irradiation. In the absence of a photocuring process, the process is possible at significantly lower temperatures than heat treatment in excess of 200 ° C. is required. The UV irradiation energy is more preferably performed in the range of 500mJ to 2000mJ in terms of curing properties and physical properties.
본 발명에서 유기절연막은 두께가 30 nm 내지 1000 nm 범위로 조절할 수 있으며, 상기 범위 내에서 조절하는 것이 유기절연막의 절연성과 최종 유기박막트랜지스터의 저전압 구동 측면에서 더욱 유리하다.In the present invention, the thickness of the organic insulating film can be adjusted in the range of 30 nm to 1000 nm, it is more advantageous to control within the above range in terms of insulation of the organic insulating film and low voltage driving of the final organic thin film transistor.
본 발명에서 유기 반도체층은 펜타센, 금속 프탈로시아닌, 폴리티오펜 또는 페닐렌비닐렌, C60, 페닐렌테트라카르복실산2무수물(phenylenetetracarboxylic dianydride), 나프탈렌테투라카르복실산2무수물(naphthalenetetracarboxylic dianydride), 플루오르화 프탈로시아닌 (fluorophthalocyanine) 및 이들의 유도체로 부터 선택되는 1종 이상으로 이루어진다.In the present invention, the organic semiconductor layer is pentacene, metal phthalocyanine, polythiophene or phenylenevinylene, C 60 , phenylenetetracarboxylic dianydride, naphthalenetetracarboxylic dianydride, and naphthalenetetracarboxylic dianydride. , At least one selected from fluorinated phthalocyanine and derivatives thereof.
본 발명에 따른 유기박막 트랜지스터는 전계이동도가 0.01 ~ 10cm2/Vs의 범위에 있으며, 상기 범위는 통상적인 유기박막 트랜지스터의 전계이동도 값의 범위로서 유기박막 트랜지스터로서 적합한 성능을 가지는 것을 의미한다.The organic thin film transistor according to the present invention has a field mobility of 0.01 to 10 cm 2 / Vs, which means that the organic thin film transistor has suitable performance as an organic thin film transistor as a range of field mobility values of a conventional organic thin film transistor. .
또한 본 발명은 본 발명에 따른 유기박막 트랜지스터를 이용한 표시소자를 제공하며, 상기 표시소자는 유기발광디스플레이, 전자종이 또는 액정디스플레이 등을 들 수 있다.
In addition, the present invention provides a display device using the organic thin film transistor according to the present invention, the display device may be an organic light emitting display, an electronic paper or a liquid crystal display.
본 발명에 따른 광경화성 및 가용성 폴리이미드계 고분자는 일반적인 유기용매에 좋은 용해도를 가지므로 저온에서 박막형성이 가능하고 중합을 통해 생성된 고분자에 광경화기를 도입함으로써 최종 유기절연체 박막의 패킹 밀도 및 절연성이 향상된다. 또한 유기절연체 박막의 광경화를 통하여 박막의 내화학성을 향상시켰으며 실제 어레이 소자 제작과정에서 중요한 패터닝 특성을 부여하였다. The photocurable and soluble polyimide-based polymers according to the present invention have good solubility in general organic solvents, so that thin films can be formed at low temperatures, and the packing density and insulation property of the final organic insulator thin film are introduced by introducing a photocuring group into the polymer produced through polymerization. This is improved. In addition, through the photocuring of the organic insulator thin film, the chemical resistance of the thin film was improved and important patterning characteristics were given in the process of fabricating the array device.
또한, 본 발명에서 개발된 광경화기가 도입된 신규 폴리이미드 유기절연체의 경우 유기절연 박막으로의 이용 시 150~160 ℃ 정도의 저온공정이 가능하기 때문에 유연한 플라스틱기판에 소자구현에 있어서 전혀 문제가 없다. In addition, in the case of the novel polyimide organic insulator in which the photocuring group developed in the present invention is introduced, a low temperature process of about 150 to 160 ° C. is possible when using the organic insulating thin film, so there is no problem in implementing a device on a flexible plastic substrate. .
고분자에 광경화기의 도입 반응이 가능한 하이드록시 그룹이 있는 경우 폴리이미드 뿐만 아니라 다른 모든 고분자에 본 발명의 광경화기 도입 방법이 응용이 될 수 있다.When the polymer has a hydroxy group capable of introducing a photocurable group, the method of introducing the photocurable group of the present invention may be applied to not only polyimide but all other polymers.
따라서 본 발명의 신규 광경화가 가능한 유기절연체의 경우 실제 차세대 플렉시블 디스플레이 및 센서 등등에 구동스위치로 응용이 가능한 유기박막트랜지스터에 사용이 가능하며 기존의 유기절연체와 비교하여 공정온도, 내화학성, 전기적 특성 등의 향상을 가져올 수 있다.
Therefore, the new photocurable organic insulator of the present invention can be used in an organic thin film transistor that can be applied as a driving switch to a next-generation flexible display and a sensor, and can be used as a process temperature, chemical resistance, electrical characteristics, etc. Can bring improvement.
도 1은 본 발명에 따른 폴리이미드계 유기고분자의 광중합에 의한 경화 메카니즘을 나타낸 것이고,
도 2는 본 발명의 하나의 구현 예에 따른 하 게이트 (bottom gate) 상 접촉 (top-contact) 유기박막트랜지스터의 구조를 나타낸 단면도이고,
도 3은 본 발명의 신규 유기절연체(KPSPI-1)의 광경화 전후의 누설전류 밀도를 나타낸 것이고,
도 4는 본 발명의 신규 유기절연체(KPSPI-2)의 광경화 전후의 누설전류 밀도를 나타낸 것이고,
도 5는 본 발명의 신규 유기절연체(KPSPI-1)의 광경화 전후의 유기박막트랜지스터 소자의 전류-전압 (I-V) 곡선이며,
도 6은 본 발명의 신규 유기절연체(KPSPI-2)의 광경화 전후의 유기박막트랜지스터 소자의 전류-전압 (I-V) 곡선이다.1 shows a curing mechanism by photopolymerization of a polyimide organic polymer according to the present invention,
2 is a cross-sectional view illustrating a structure of a bottom gate top-contact organic thin film transistor according to one embodiment of the present invention;
Figure 3 shows the leakage current density before and after photocuring of the novel organic insulator (KPSPI-1) of the present invention,
Figure 4 shows the leakage current density before and after photocuring of the novel organic insulator (KPSPI-2) of the present invention,
5 is a current-voltage (IV) curve of an organic thin film transistor element before and after photocuring of the novel organic insulator (KPSPI-1) of the present invention.
6 is a current-voltage (IV) curve of an organic thin film transistor element before and after photocuring of the novel organic insulator (KPSPI-2) of the present invention.
아래에 실시예를 통하여 본 발명을 더 구체적으로 설명한다. 단, 하기 실시예는 본 발명의 예시에 불과한 것으로서 본 발명의 특허 청구 범위가 이에 따라 한정되는 것은 아니다.
The present invention will be described in more detail with reference to the following Examples. However, the following examples are merely examples of the present invention, and the claims of the present invention are not limited thereto.
[실시예 1] 폴리이미드계 고분자 물질( KPSPI -1)의 제조 Example 1 Preparation of Polyimide Polymer Material ( KPSPI- 1)
KSPIKSPI -1 제조-1 manufacturing
5-(2,5-디옥소테트라히드로퓨릴)-3-메틸-3-시클로헥센-1,2-디카르복실산이수물[DOCDA] 1.3212 g (5 mmol) 과 3,3-디하이드록시베니딘(3,3-dihydroxybenidine ;HAB) 1.0812g (5 mmol)을 50 mL 둥근바닥 플라스크에 준비하고 중합용매로서 m-크레졸(m-cresol)을 21.6212 g 첨가하여 두 단량체를 완전히 녹인다. 단량체의 반응용매에 고형분 비율은 10wt% 로 맞추었다. 반응은 70 ℃까지 서서히 2시간에 걸쳐서 반응용기를 가열하고 70℃에서 160 까지 1시간에 걸쳐서 온도를 상승시켰다. 160℃에서 30분 반응을 보내고 반응을 종결시켰다. 최종 반응 용액의 점도는 18,000 cps로 측정되었다. 종결된 반응 혼합물은 과량의 메탄올(methanol)에 침전시켜서 최종 고분자를 백색의 파우더로 얻었으며 이후 감압 필터 하여 용제를 없애고 오븐에서 잔류 용제를 완전히 제거하여 최종 하이드록시 그룹이 치환된 KSPI-1을 얻었다.1.3212 g (5 mmol) of 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dihydrate [DOCDA] and 3,3-dihydroxybeni 1.0812 g (5 mmol) of dine (3,3-dihydroxybenidine (HAB)) was prepared in a 50 mL round bottom flask, and 21.6212 g of m-cresol was added as a polymerization solvent to completely dissolve both monomers. Solid content ratio was set to 10 wt% in the reaction solvent of the monomer. The reaction was slowly heated to 70 ° C. over 2 hours and the temperature was raised from 70 ° C. to 160 over 1 hour. The reaction was sent at 160 ° C. for 30 minutes and the reaction was terminated. The viscosity of the final reaction solution was measured at 18,000 cps. The terminated reaction mixture was precipitated in excess methanol to obtain the final polymer as a white powder, which was then filtered under reduced pressure to remove the solvent and completely free of residual solvent in the oven to give the final hydroxy group substituted KSPI-1. .
KPSPIKPSPI -1의 제조Manufacture of -1
제조된 KSPI-1을 질량으로 4.44g (10 mmol) 준비하여 25 mL 둥근바닥 풀라스크에 첨가하고 광경화기로서 신나모일 클로라이드(cinnamoyl chloride)를 3.98 g (24 mmol) 반응용기에 첨가하였다. 반응용매로는 NMP을 이용하였으며 반응 촉진을 위한 염기로서 트리에틸아민(triethyl amine)을 2.45 g (24 mmol) 첨가하여 상온에서 12시간 반응을 진행하였다. 반응이 완결된 후 과량의 메탄올(methanol)에 반응 용액을 소량씩 첨가하여 최종으로 광경화기가 도입된 KPSPI-1을 고체 상태로 얻었다. 최종 고분자에 포함되어 있는 불순물을 제거하기 위하여 여러 번 고분자를 용매에 녹이고 침전을 잡는 과정을 반복하였으며 최종으로 얻은 고분자는 감압증류 후 용매를 제거하고 마지막으로 진공오븐에서 잔량의 용매를 제거 한 후 최종 광경화기가 도입된 가용성 폴리이미드(KPSPI-1)를 얻었다. 4.44 g (10 mmol) of the prepared KSPI-1 was prepared and added to a 25 mL round bottom pool flask, and cinnamoyl chloride (cinnamoyl chloride) was added to a 3.98 g (24 mmol) reaction vessel as a photocuring machine. NMP was used as the reaction solvent, and the reaction was carried out at room temperature for 12 hours by adding 2.45 g (24 mmol) of triethylamine as a base for promoting the reaction. After the reaction was completed, a small amount of the reaction solution was added to the excess methanol (methanol) to finally obtain KPSPI-1 into which the photocuring machine was introduced as a solid state. In order to remove impurities contained in the final polymer, the process of dissolving the polymer in a solvent and sedimentation was repeated several times. Finally, the obtained polymer was distilled under reduced pressure, and then the solvent was removed. The soluble polyimide (KPSPI-1) into which the photocuring group was introduced was obtained.
1H-NMR (δ, DMSO-d 6 ) 6.89-7.49 (broad m, Aromatic H, 16H), 6.46-6.85 (broad m, vinyl H, 4H, 3.45-1.25 (broad m, Aliphatic H, 12H). FT-IR (cm-1, KBR pellet) 1717 (C=O ketone), 1631 (C=C stretching), 1499 (C=C aromatic), C-N (1374). 분자량: 수평균분자량 (M n): 21,000 g/mol, 질량평균분자량 (M w) 36,000 g/mol.
1 H-NMR (δ, DMSO- d 6 ) 6.89-7.49 (broad m, Aromatic H, 16H), 6.46-6.85 (broad m, vinyl H, 4H, 3.45-1.25 (broad m, Aliphatic H, 12H). FT-IR (cm-1, KBR pellet) 1717 (C = O ketone), 1631 (C = C stretching), 1499 (C = C aromatic), CN (1374) .Molecular weight: Number average molecular weight ( M n ): 21,000 g / mol, mass average molecular weight ( M w ) 36,000 g / mol.
[실시예 2] 폴리이미드계 고분자 물질( KPSPI -1)의 제조 Example 2 Preparation of Polyimide Polymer Material ( KPSPI- 1)
KSPIKSPI -2의 제조Manufacture of -2
5-(2,5-디옥소테트라히드로퓨릴)-3-메틸-3-시클로헥센-1,2-디카르복실산이수물[DOCDA] 1.3212 g (5 mmol) 과 2,2-비스(3-아미노-4-하이드록시페닐)헥사플루오로프로판(2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane;6FHAB) 1.8313g (5 mmol)을 50 mL 둥근바닥 플라스크에 준비하고 중합용매로서 m-크레졸(m-cresol)을 11.1769g 첨가하여 두 단량체를 완전히 녹인다. 단량체의 반응용매에 고형분 비율은 21wt% 로 맞추었다. 반응은 70 ℃까지 서서히 2시간에 걸쳐서 반응용기를 가열하고 70 ℃에서 160 ℃까지 1시간에 걸쳐서 온도를 상승시켰다. 160 ℃에서 1시간 더 반응을 보내고 반응을 종결시켰다. 최종 반응 용액의 점도는 6500 cps로 측정되었다. 종결된 반응 혼합물은 과량의 메탄올(methanol)에 침전시켜서 최종 고분자를 백색의 파우더로 얻었으며 이후 감압 필터 하여 용제를 없애고 오븐에서 잔류 용제를 완전히 제거하여 최종 하이드록시 그룹이 치환된 KSPI-2을 얻었다.1.3212 g (5 mmol) of 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dihydrate [DOCDA] and 2,2-bis (3- 1.8313 g (5 mmol) of amino-4-hydroxyphenyl) hexafluoropropane (2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane; 6FHAB) was prepared in a 50 mL round bottom flask and m as a polymerization solvent. Add 11.1769 g of m-cresol to completely dissolve both monomers. Solid content ratio was set to 21 wt% in the reaction solvent of the monomer. The reaction was slowly heated to 70 ° C. over 2 hours and the temperature was raised over 1 hour from 70 ° C. to 160 ° C. The reaction was further sent for 1 hour at 160 ° C. and the reaction was terminated. The viscosity of the final reaction solution was measured at 6500 cps. The terminated reaction mixture was precipitated in excess methanol to give the final polymer as a white powder, which was then filtered under reduced pressure to remove the solvent and completely free of residual solvent in the oven to give the final hydroxy group substituted KSPI-2. .
KPSPIKPSPI
-2의 제조Manufacture of -2
* *
제조된 KSPI-2을 질량으로 2.37g (4 mmol) 준비하여 25 mL 둥근바닥 풀라스크에 첨가하고 광경화기로서 신나모일 클로라이드(cinnamoyl chloride)를 1.99 g (12 mmol) 반응용기에 첨가하였다. 반응용매로는 NMP을 이용하였으며 반응 촉진을 위한 염기로서 트리에틸아민(triethyl amine)을 1.23 g (12 mmol) 첨가하여 상온에서 12시간 반응을 진행하였다. 반응이 완결된 후 과량의 메탄올(methanol)에 반응 용액을 소량씩 첨가하여 최종으로 광경화기가 도입된 KPSPI-2을 고체 상태로 얻었다. 최종 고분자에 포함되어 있는 불순물을 제거하기 위하여 여러 번 고분자를 용매에 녹이고 침전을 잡는 과정을 반복하였으며 최종으로 얻은 고분자는 감압증류 후 용매를 제거하고 마지막으로 진공오븐에서 잔량의 용매를 제거 한 후 최종 광경화기가 도입된 가용성 폴리이미드(KPSPI-2)를 얻었다. 2.37 g (4 mmol) of the prepared KSPI-2 was prepared and added to a 25 mL round bottom pool flask, and cinnamoyl chloride (cinnamoyl chloride) was added to a 1.99 g (12 mmol) reactor as a photocuring machine. NMP was used as the reaction solvent and 1.23 g (12 mmol) of triethylamine was added as a base for promoting the reaction, and the reaction was performed at room temperature for 12 hours. After the reaction was completed, a small amount of the reaction solution was added to the excess methanol (methanol) to finally obtain KPSPI-2 into which the photocuring machine was introduced as a solid state. In order to remove impurities contained in the final polymer, the process of dissolving the polymer in a solvent and sedimentation was repeated several times. Finally, the obtained polymer was distilled under reduced pressure, and then the solvent was removed. The soluble polyimide (KPSPI-2) into which the photocuring group was introduced was obtained.
1H-NMR (δ, DMSO-d 6 ) 6.95-7.59 (broad m, Aromatic H, 16H), 6.56-6.90 (broad m, vinyl H, 4H), 3.55-1.35 (broad m, Aliphatic H, 12H). FT-IR (cm-1, KBR pellet) 1720 (C=O ketone), 1631 (C=C stretching), 1510 (C=C aromatic), C-N (1372). 분자량: 수평균분자량 (M n): 54,000 g/mol, 질량평균분자량 (M w) 101,000 g/mol.
1 H-NMR (δ, DMSO- d 6 ) 6.95-7.59 (broad m, Aromatic H, 16H), 6.56-6.90 (broad m, vinyl H, 4H), 3.55-1.35 (broad m, Aliphatic H, 12H) . FT-IR (cm-1, KBR pellet) 1720 (C = O ketone), 1631 (C = C stretching), 1510 (C = C aromatic), CN (1372). Molecular weight: Number average molecular weight ( M n ): 54,000 g / mol, Mass average molecular weight ( M w ) 101,000 g / mol.
[실시예 3] 신나모일기가 치환된 KPSPI-1 박막의 제조 및 광경화Example 3 Preparation and Photocuring of KPSPI-1 Thin Film Substituted with Cinnamoyl Group
신나모일기가 치환된 KPSPI-1를 γ-부틸로락톤 용매에 9wt% 농도로 용해시킨 용액을 이용하여 3000rpm 정도의 속도로 스핀코팅 방법을 통하여 유기절연체 박막을 제조하였다. 제조 박막은 두께를 300 nm로 조절하였으며 제조된 박막은 여분의 용매를 제거하기 위해 소프트 베이킹(90 ℃, 10 분)을 실시하였다. 박막의 광경화를 위하여 1000 mJ ~ 1500mJ(평균 1250mJ)의 UV를 조사하였으며 UV조사 후 최종적으로 90 ℃에서 10분, 160 ℃ 30분 동안 하드 베이킹을 통해서 상기 반응식에 도시한 바와 같이 최종적으로 광경화가 진행된 유기절연체 박막을 제조하였다.
An organic insulator thin film was prepared by spin coating at a speed of about 3000 rpm using a solution in which KPSPI-1 substituted with cinnamoyl group was dissolved at a concentration of 9 wt% in a γ-butyrolactone solvent. The prepared thin film was adjusted to 300 nm in thickness and the prepared thin film was subjected to soft baking (90 ° C., 10 minutes) to remove excess solvent. UV light of 1000 mJ ~ 1500mJ (average 1250mJ) was irradiated for the photocuring of the thin film. Finally, the photocuring was finally performed as shown in the reaction scheme through hard baking for 10 minutes at 90 ° C and 160 ° C for 30 minutes after UV irradiation. An advanced organic insulator thin film was prepared.
[실시예 4] 신나모일기가 치환된 KPSPI-2 박막의 제조 및 광경화Example 4 Preparation and Photocuring of KPSPI-2 Thin Film Substituted with Cinnamoyl Group
신나모일기가 치환된 KPSPI-2를 사이클로헥사논(cyclohexanone) 용매에 7wt% 농도로 용해시킨 용액을 이용하는 것을 제외하고는 실시예 3과 동일한 방법으로 진행하여 상기 반응식에 나타낸 바와 같이 광경화된 유기절연체 박막을 제조하였다.
Photocured organic as shown in the reaction scheme was carried out in the same manner as in Example 3, except for using a solution in which KPSPI-2 substituted with cinnamoyl group was dissolved in a cyclohexanone solvent at a concentration of 7wt%. An insulator thin film was prepared.
[비교예 1] 광경화되지 않은 KPSPI-1 박막의 제조Comparative Example 1 Preparation of Uncured KPSPI-1 Thin Film
KPSPI-1를 γ-부틸로락톤 용매에 9wt% 농도로 용해시킨 용액을 이용하여 3000rpm 정도의 속도로 스핀코팅 방법을 통하여 유기절연체 박막을 제조하였다. 제조 박막은 두께를 300 nm로 조절하였으며 제조된 박막은 여분의 용매를 제거하기 위해 소프트 베이킹(90 ℃, 10 분)을 실시한 후 160 ℃ 30분 동안 하드 베이킹을 통해서 최종적으로 광경화 되지 않은 KPSPI-1 유기절연체 박막을 제조하였다.
The organic insulator thin film was prepared by spin coating at a speed of about 3000 rpm using a solution in which KPSPI-1 was dissolved at a concentration of 9 wt% in a γ-butyrolactone solvent. The prepared thin film was adjusted to a thickness of 300 nm, and the prepared thin film was subjected to soft baking (90 ° C., 10 minutes) to remove excess solvent, and then hard baked for 160 ° C. for 30 minutes. 1 An organic insulator thin film was prepared.
[비교예 2] 광경화되지 않은 KPSPI-2 박막의 제조Comparative Example 2 Preparation of Uncured KPSPI-2 Thin Film
KPSPI-2를 사이클로헥사논(cyclohexanone) 용매에 7wt% 농도로 용해시킨 용액을 이용하여 3000rpm 정도의 속도로 스핀코팅 방법을 통하여 유기절연체 박막을 제조하였다. 제조 박막은 두께를 300 nm로 조절하였으며 제조된 박막은 여분의 용매를 제거하기 위해 소프트 베이킹(90 ℃, 10 분)을 실시한 후 160 ℃ 30분 동안 하드 베이킹을 통해서 최종적으로 광경화 되지 않은 KPSPI-2 유기절연체 박막을 제조하였다.
An organic insulator thin film was prepared by spin coating at a speed of about 3000 rpm using a solution in which KPSPI-2 was dissolved at 7 wt% in a cyclohexanone solvent. The prepared thin film was adjusted to a thickness of 300 nm, and the prepared thin film was subjected to soft baking (90 ° C., 10 minutes) to remove excess solvent, and then hard baked for 160 ° C. for 30 minutes. 2 organic insulator thin film was prepared.
제조된 유기절연체 박막의 특성 평가Characterization of Fabricated Organic Insulator Thin Films
용액공정을 통한 유기박막트랜지스터 제조에서 중요한 유기절연체 박막의 내화학성을 일반적인 유기용매 (cyclohexanone, chloroform 및 N,N-dimethylformamide: NMP)에 박막을 딥핑한 후 박막의 표면 거칠기를 측정하여 평가하였다. 사이클로헥사논(Cyclohexanone), 클로로포름(chloroform) 및 NMP 용매의 경우에는 경화 전의 신나모일(cinnamoyl)기가 도입된 KPSPI-1 및 KPSPI-2 (실시예 1 및 2)의 경우 완전히 박막이 용매에 다시 용해가 되었으며 UV 조사를 통하여 광경화 시킨 후 (실시예 3 및 4) 에는 유기용매에 전혀 표면의 손상을 입지 않았다. 원자현미경(Atomic force microscopy: AFM) 분석 결과 유기용매 처리 후에도 표면거칠기 특성인 RMS 값이 0.5 nm 이하의 우수한 특성을 보였다. Chemical resistance of the organic insulator thin film, which is important in the manufacture of organic thin film transistor through a solution process, was evaluated by dipping the thin film in general organic solvents (cyclohexanone, chloroform and N, N-dimethylformamide: NMP) and measuring the surface roughness of the thin film. In the case of cyclohexanone, chloroform and NMP solvent, KPSPI-1 and KPSPI-2 (Examples 1 and 2) in which cinnamoyl groups were introduced before curing were completely dissolved in the solvent. After photocuring through UV irradiation (Examples 3 and 4), the organic solvent was not damaged at all. Atomic force microscopy (AFM) analysis showed that the RMS value, which is the surface roughness, was excellent even after treatment with organic solvent.
KPSPI-1 및 KPSPI-2의 경우 모두 일반적인 유기용매에 우수한 용해도를 보였으며 150~160 ℃에서 유기절연체 박막 형성이 가능하였다.Both KPSPI-1 and KPSPI-2 showed excellent solubility in general organic solvents and were able to form organic insulator thin films at 150 ~ 160 ℃.
KPSPI-1 과 KPSPI-2의 유기절연체 박막으로서 가장 중요한 특성인 누설전류를 광경화 전후의 조건으로 비교 하였다. 전극-유전체-전극 (metal-insulator-metal: MIM) 구조의 소자를 각각 제조하였으며 유전체의 제조 조건은 광경화 없는 조건은 비교예 1 및 2의 박막 제조 조건으로 광경화 조건은 실시예 3 및 4의 조건으로 박막을 제조 하였다. 하부 전극으로는 패터닝된 인듐-틴-옥사이드(indium-tin-oxide;ITO) 전극을, 상부 전극으로는 세도우(shadow) 마스크를 이용하여 금(Au)을 증착하였으며 유기절연막의 두께는 300 nm를 맞추었다. The leakage current, the most important characteristic of KPSPI-1 and KPSPI-2 thin organic insulator films, was compared before and after photocuring. Devices of an electrode-dielectric-electrode (metal-insulator-metal (MIM)) structure were fabricated, respectively. The conditions for the preparation of the dielectric were the conditions for manufacturing the thin films of Comparative Examples 1 and 2, and the conditions for the photocuring were Examples 3 and 4, respectively. The thin film was prepared under the conditions of. Patterned indium-tin-oxide (ITO) electrode was used as a lower electrode, and gold (Au) was deposited using a shadow mask as an upper electrode, and the thickness of the organic insulating layer was 300 nm. Matched.
도 3에 광경화 전 후의 KPSPI-1 의 누설전류 밀도를 나타내었다. KPSPI-1의 경우 광 경화 전에 누설전류 밀도가 2MV/cm 기준 1.20X10-10 A/cm2 이었으나 광 경화 (1500 mJ 에너지 조사) 후에는 7.84X10-11로 향상되었으며 특히 3MV/cm 이상의 우수한 절연 파괴전압 (breakdown voltage)를 보였다. 광경화 되지 않은 KPSPI-1의 경우는 2.5MV 이상에서 소자의 파괴 (breakdown)이 발생하였다. 광경화된 KPSPI-1의 3MV/cm 이상의 절연파괴전압은 기존의 유기절연체로 많이 사용되어지고 있는 폴리비닐알코올 (PVA), 폴리비닐페놀 (PVP) 등의 유기고분자 (1~2 MV/cm)와 비교하여 상당히 향상된 값이며 이는 고분자 사슬간의 광경화에 고분자 막의 패킹 밀도가 높아진 것으로 해석할 수 있다.3 shows the leakage current density of KPSPI-1 before and after photocuring. In the case of KPSPI-1, the leakage current density was 1.20X10 -10 A / cm 2 at 2MV / cm before light curing, but improved to 7.84X10 -11 after light curing (1500 mJ energy irradiation), especially excellent dielectric breakdown of more than 3MV / cm The breakdown voltage was shown. In the case of uncured KPSPI-1, breakdown of the device occurred above 2.5 MV. The dielectric breakdown voltage of 3MV / cm or more of photocured KPSPI-1 is organic polymer (1 ~ 2 MV / cm) such as polyvinyl alcohol (PVA) and polyvinylphenol (PVP), which are widely used as conventional organic insulators. Compared with, the value is considerably improved, which can be interpreted as the increase in packing density of polymer membrane for photocuring between polymer chains.
도 4에 광경화 전 후의 KPSPI-2 의 누설전류 밀도를 나타내었다. KPSPI-2의 경우 광 경화 전에 누설전류 밀도가 2MV/cm 기준 1.68X10-5 A/cm2 유기절연체의 누설전류가 상당히 높은 안 좋은 특성을 보였으나 광 경화(1000~1500 mJ 에너지 조사) 후에는 1.84X10-10로 향상되었으며 특히 3MV/cm 이상의 전압에서도 MIM 소자가 파괴되지 않는 우수한 절연 파괴전압(breakdown voltage)를 보였다. 광경화에 의한 고분자 곁사슬의 신나모일 그룹의 경화 반응에 의하여 고분자 막의 패킹 밀도가 높아졌음을 알 수 있다.
4 shows the leakage current density of KPSPI-2 before and after photocuring. In the case of KPSPI-2, the leakage current density of 1.68X10 -5 A / cm 2 organic insulator based on 2MV / cm before the curing was very high, but after photo curing (1000 ~ 1500 mJ energy irradiation) It improved to 1.84X10 -10 and showed excellent breakdown voltage, especially that MIM device does not break even at voltages above 3MV / cm. It can be seen that the packing density of the polymer membrane was increased by the curing reaction of the cinnamoyl group in the polymer side chain by photocuring.
유기박막 트랜지스터의 제작 및 특성평가Fabrication and Characterization of Organic Thin Film Transistors
본 발명의 저온 공정 및 광경화가 가능한 폴리이미드 유기절연체 박막을 이용하여 유기 박막 트랜지스터를 제작하고 그 특성을 측정하였다. 유기반도체로는 유기 박막 트랜지스터에서 가장 널리 사용되고 상대적으로 좋은 성능을 가지는 펜타센을 사용하였다. 기판은 본 발명에서 개발된 유기절연체의 경우 공정온도가 150~160 ℃이므로 폴리에테르설폰과 같은 플라스틱 기판 및 유리를 사용하였다. 유기박막트랜지스터의 소자 구조는 상접촉(top-contact) 형식으로 소자 제작방법은 다음과 같다. 기판 청결도는 전자 소자를 제작할 때 가장 중요한 요소 중의 하나이므로 기판이 유리인 경우 세제, 증류수, 아세톤 그리고 아이소프로필알코올를 이용하여 초음파 세척을 한 후 오븐에서 충분히 건조시킨 것을 사용하였고, 플라스틱 기판은 시판되는 것을 별도의 세척공정 없이 보호막만 탈리시킨 후 그대로 사용하였다. An organic thin film transistor was fabricated using the low temperature process and the photocurable polyimide organic insulator thin film of the present invention, and its characteristics were measured. As an organic semiconductor, pentacene, which is widely used in organic thin film transistors and has a relatively good performance, was used. In the case of the organic insulator developed in the present invention, since the process temperature is 150 to 160 ° C., a plastic substrate such as polyethersulfone and glass are used. The device structure of the organic thin film transistor is a top-contact type (device) manufacturing method is as follows. Substrate cleanliness is one of the most important factors when manufacturing electronic devices, so if the substrate is glass, ultrasonic cleaning with detergent, distilled water, acetone, and isopropyl alcohol was used, followed by drying sufficiently in an oven. After detaching only the protective film without a separate washing process, it was used as it is.
잘 세척된 기판 위에 먼저 금을 새도우마스크를 이용하여 1x10-6 torr의 진공에서 열 진공 증착하여 2 mm 너비의 게이트 전극을 40 nm 두께로 형성하였다. 그 위에 본 발명의 저온 공정 및 광경화 가능한 폴리이미드 유기절연체(KPSPI-1 및 KPSPI-2)를 각각 300 nm 두께로 스핀코팅하고, 90 ℃에서 10분 간 건조한 후, 각각 1500 mL정도의 UV 조사를 통하여 광경화를 진행하고 마지막으로 KPSPI-1의 경우 160 ℃의 온도에서 30분 동안 그리고 KPSPI-2의 경우 150 ℃에서 30 분 동안 최종 건조를 하여 광경화된 폴리이미드 유기절연체 박막을 얻었다. On the well cleaned substrate, gold was first thermally vacuum-deposited in a vacuum of 1 × 10 −6 torr using a shadow mask to form a 2 mm wide gate electrode having a thickness of 40 nm. The low-temperature process and the photocurable polyimide organic insulators (KPSPI-1 and KPSPI-2) of the present invention were respectively spin-coated to a thickness of 300 nm and dried at 90 ° C. for 10 minutes, respectively. Photocuring was carried out through UV irradiation of about 1500 mL and finally dried for 30 minutes at 160 ℃ for KPSPI-1 and 30 minutes at 150 ℃ for KPSPI-2 An insulator thin film was obtained.
비교예로 광경화기 도입의 효과를 확인하기 위하여 KPSPI-1 및 KPSPI-2를 포함하는 유기박막트랜지스터 제조 과정에서 UV 조사만 생략한 유기절연체 박막을 제조하였다.As a comparative example, in order to confirm the effect of the introduction of the photocuring machine, an organic insulator thin film was fabricated by omitting only UV irradiation in the process of manufacturing an organic thin film transistor including KPSPI-1 and KPSPI-2.
상기와 같이 제조된 유기절연체 박막들 위에 유기반도체인 펜타센을 1X10-6 torr의 진공에서 열진공 증착을 이용하여 50 nm 두께로 증착하였다. 이때 펜타센의 결정화에 큰 영향을 미치는 기판의 온도는 90 ℃로 일정하게 유지하였다. 마지막으로 금을 게이트 증착과 같은 방법으로 50 nm의 두께로 증착하여 소오스와 드레인 전극을 형성하였다. 하접촉(bottom-contact) 소자는 펜타센과 소오스, 드레인 전극의 형성 순서를 서로 바꿈으로써 제작하였다. 위와 같이 제작된 소자의 특성은 에질런트 테크날리지사의 E5272장비를 이용하여 게이트 전압에 따른 드레인 전압-드레인 전류 및 드레인 전압에 따른 게이트 전압-드레인 전류 곡선들을 측정하여 포화영역(saturation) 영역에서 다음의 전류, 전압식을 이용하여 제반 특성들을 평가하였다.Pentacene, an organic semiconductor, was deposited to a thickness of 50 nm on the organic insulator thin films prepared as described above using thermal vacuum deposition in a vacuum of 1 × 10 −6 torr. At this time, the temperature of the substrate having a great influence on the crystallization of pentacene was kept constant at 90 ℃. Finally, gold was deposited to a thickness of 50 nm in the same manner as gate deposition to form a source and a drain electrode. Bottom-contact devices were fabricated by changing the order of formation of pentacene, source, and drain electrodes. The characteristics of the device fabricated as described above were measured in the saturation region by measuring the drain voltage-drain current according to the gate voltage and the gate voltage-drain current curve according to the drain voltage by using the E5272 device of Agilent Technology. Various characteristics were evaluated using the current and voltage equations.
상기 식에서 V T 는 문턱전압, Vgs 는 인가된 게이트 전압, μ는 전계효과 전하이동도, W와 L은 채널의 너비와 길이, C는 절연막의 커패시턴스이다. 문턱전압은 와 Vgs 의 그래프로부터 Ids 가 0인 게이트 전압으로 결정되고 전계효과 전하이동도는 와 Vgs의 그래프의 기울기로부터 산출하였다. Where V T Is the threshold voltage, V gs is the applied gate voltage, μ is the field effect charge mobility, W and L are the width and length of the channel, and C is the capacitance of the insulating film. Threshold voltage From the graphs of V gs and V gs , we determine the gate voltage with I ds 0 and the field effect charge mobility It was computed from the slope of the graph of and V gs .
도 5에서 실시예 3과 비교예 1에서 제조된 광경화된 KPSPI-1 및 광경화 처리하지 않는 KPSPI-1이 유기절연체 박막으로 포함된 유기박막트랜지스터의 전류-전압 특성치를 나타내었다. 광경화 전후 KPSPI-1의 점등전류(on current) 수치는 1.54X10-5A 와 2.06X10-5A 로서 유사한 값을 나타내었다. 하지만 점멸전류(off current)는 1.98X10-9A에서 1.04X10-10A으로 향상 되었으며 이는 광경화에 의한 KPSPI-1의 박막의 패킹 밀도가 높아져서 절연성이 향상된 것으로 해석할 수 있다. 트랜지스터의 성능에서 중요한 점등 전류와 점멸 전류의 비(Ion/Ioff) 역시 7.78X103에서 1.98X105으로 향상되었다. 또한 SS(subthreshold slope) 값은 광경화 전 5.08 (V/dec)에서 2.76 (V/dec)로 2배 정도 향상된 수치를 보였다. 트랜지스터의 이동도 특성 또한 0.12 cm2/Vs에서 0.16 cm2/Vs로 KPSPI-1 광경화 공정을 진행된 트랜지스의 특성이 더 향상되었다. 표 1에서 광경화 전후의 KPSPI-1을 유기절연체 박막으로 적용한 유기박막트랜지스터의 중요 특성을 정리하였다.5 shows the current-voltage characteristics of the organic thin film transistor including the photocured KPSPI-1 and the non-cured KPSPI-1 prepared in Example 3 and Comparative Example 1 as the organic insulator thin film. The on-current values of KPSPI-1 before and after photocuring showed similar values as 1.54X10 -5 A and 2.06X10 -5 A. However, the off current has been improved from 1.98X10 -9 A to 1.04X10 -10 A, which can be interpreted to improve insulation due to the increased packing density of KPSPI-1 thin film by photocuring. The ratio of the lighting current to the flashing current (Ion / Ioff), which is important for transistor performance, has also been improved from 7.78X10 3 to 1.98X10 5 . In addition, the value of the SS (subthreshold slope) increased by about 2 times from 5.08 (V / dec) to 2.76 (V / dec) before photocuring. The mobility characteristics of the transistors also improved the characteristics of the transistors undergoing the KPSPI-1 photocuring process from 0.12 cm 2 / Vs to 0.16 cm 2 / Vs. Table 1 summarizes the important characteristics of organic thin film transistors using KPSPI-1 as an organic insulator thin film before and after photocuring.
[표 1]TABLE 1
도 6에서 실시예 4와 비교예 2에서 제조된 광경화된 KPSPI-2 및 광경화 처리하지 않는 KPSPI-2이 유기절연체 박막으로 포함된 유기박막트랜지스터의 전류-전압 특성치를 나타내었다. 광경화 전후 KPSPI-2의 점등전류(on current) 수치는 1.77X10-5A 와 2.10X10-5A 로서 유사한 값을 나타내었다. 하지만 점멸전류(off current)는 KPSPI-1의 양상과 비슷하게 3.95X10-9A에서 5.88X10-12A으로 큰 폭으로 향상 되었으며 이는 역시 광경화에 의한 KPSPI-2의 박막의 패킹 밀도가 높아져서 절연성이 향상된 것으로 해석할 수 있다. 트랜지스터의 성능에서 중요한 점등 전류와 점멸 전류의 비 (Ion/Ioff) 역시 4.48X103에서 3.57X106으로 향상되었다. 또한 subthreshold slope (SS) 값은 광경화 전 5.42 (V/dec)에서 1.87 (V/dec)로 대략 3배 정도 향상된 수치를 보였다. 트랜지스터의 이동도 특성은 광경화 전 후에 0.14 cm2/Vs 로서 유사한 값을 보였다. 표 2에서 광경화 전후의 KPSPI-2를 유기절연체 박막으로 적용한 유기박막트랜지스터의 중요 특성을 정리하였다.6 shows the current-voltage characteristics of the organic thin film transistor including the photocured KPSPI-2 and the non-cured KPSPI-2 prepared in Example 4 and Comparative Example 2 as the organic insulator thin film. The on-current values of KPSPI-2 before and after photocuring showed similar values as 1.77X10 -5 A and 2.10X10 -5 A. However, similar to the KPSPI-1, the off current was greatly improved from 3.95X10 -9 A to 5.88X10 -12 A, which also increased the packing density of the thin film of KPSPI-2 by photocuring. It can be interpreted as an improvement. The ratio of lighting current to flashing current (Ion / Ioff), which is important for transistor performance, also improved from 4.48X10 3 to 3.57X10 6 . Also, the value of subthreshold slope (SS) was about three times improved from 5.42 (V / dec) to 1.87 (V / dec) before photocuring. The mobility characteristics of the transistors showed similar values as 0.14 cm 2 / Vs before and after photocuring. Table 2 summarizes the important characteristics of organic thin film transistors using KPSPI-2 as an organic insulator thin film before and after photocuring.
[표 2]TABLE 2
<도면의 주요부분에 대한 부호의 설명>
1: 기판 2: 게이트 전극 3: 유기절연막
4: 유기반도체층 5: 소스 전극 6: 드레인 전극<Description of the symbols for the main parts of the drawings>
1: substrate 2: gate electrode 3: organic insulating film
4: organic semiconductor layer 5: source electrode 6: drain electrode
Claims (9)
[화학식 1]
[상기 화학식 1에서 은 하기 구조 중에서 선택된 구조식 (a), (b), (c), (d), (e) 및 (f) 중에서 선택된 1종 또는 2종 이상의 지방족 고리계 4가기이고
;
은 하기 구조 중에서 선택된 1종 이상의 2가기이고
;
a는 0 내지 10의 정수이고;
X11 내지 X19은 독립적으로 수소(H), (C1~C10)알킬, 시아노 또는 할로겐으로부터 선택되며;
y는 1 내지 10의 자연수이다.]An organic thin film transistor comprising a gate electrode, an organic insulating film, an organic semiconductor layer, a source electrode, and a drain electrode on a glass and plastic substrate, wherein the organic insulating film comprises a coating liquid containing a polyimide-based organic polymer comprising a unit of Formula 1 below. An organic thin film transistor formed by coating on a substrate on which a gate electrode is formed and photocuring the same.
[Formula 1]
[In Formula 1 Is one or two or more aliphatic ring-based tetravalent groups selected from structural formulas (a), (b), (c), (d), (e) and (f) selected from the following structures:
;
Is at least one divalent selected from the structures
;
a is an integer from 0 to 10;
X 11 to X 19 are independently selected from hydrogen (H), (C 1 -C 10) alkyl, cyano or halogen;
y is a natural number between 1 and 10.]
상기 광경화는 UV 조사 후 100℃ 내지 200℃의 열처리를 통하여 이루어지는 유기박막트랜지스터.The method of claim 1,
The photocuring is an organic thin film transistor made through a heat treatment of 100 ℃ to 200 ℃ after UV irradiation.
상기 UV 조사는 500mJ 내지 2000mJ 범위에서 수행되는 유기박막트랜지스터.The method of claim 2,
The UV irradiation is an organic thin film transistor is performed in the range of 500mJ to 2000mJ.
상기 도포는 스핀코팅, 잉크젯 프린팅, 롤코팅, 스크린 프린팅, 및 딥핑으로부터 선택되는 하나 이상의 방법으로 수행되는 유기박막트랜지스터.The method of claim 1,
Wherein said coating is performed by one or more methods selected from spin coating, ink jet printing, roll coating, screen printing, and dipping.
상기 유기절연막은 두께가 30 nm 내지 1000 nm 범위인 유기박막트랜지스터.The method of claim 1,
The organic insulating film has a thickness of 30 nm to 1000 nm. Organic thin film transistor range.
상기 유기 반도체층은 펜타센, 금속 프탈로시아닌, 폴리티오펜 또는 페닐렌비닐렌, C60, 페닐렌테트라카르복실산2무수물(phenylenetetracarboxylic dianydride), 나프탈렌테투라카르복실산2무수물(naphthalenetetracarboxylic dianydride), 플루오르화 프탈로시아닌 (fluorophthalocyanine) 및 이들의 유도체로 부터 선택되는 1종 이상으로 이루어지는 유기박막트랜지스터.The method of claim 1,
The organic semiconductor layer is pentacene, metal phthalocyanine, polythiophene or phenylenevinylene, C 60 , phenylenetetracarboxylic dianydride, naphthalenetetracarboxylic dianydride, fluorine An organic thin film transistor comprising at least one member selected from fluorophthalocyanine and derivatives thereof.
유기박막 트랜지스터는 전계이동도가 0.01 ~ 10cm2/Vs의 범위에 있는 것을 특징으로 하는 유기박막 트랜지스터.The method according to claim 6,
The organic thin film transistor is an organic thin film transistor, characterized in that the field mobility is in the range of 0.01 ~ 10cm 2 / Vs.
상기 표시소자는 유기발광디스플레이, 전자종이 또는 액정디스플레이로부터 선택되는 표시소자.The method of claim 8,
The display device is selected from an organic light emitting display, an electronic paper or a liquid crystal display.
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