KR101411830B1 - 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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- KR101411830B1 KR101411830B1 KR1020110017361A KR20110017361A KR101411830B1 KR 101411830 B1 KR101411830 B1 KR 101411830B1 KR 1020110017361 A KR1020110017361 A KR 1020110017361A KR 20110017361 A KR20110017361 A KR 20110017361A KR 101411830 B1 KR101411830 B1 KR 101411830B1
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- C—CHEMISTRY; METALLURGY
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
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- 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
본 발명은 차세대 플렉시블디스플레이의 구동 스위칭 소자로 응용이 가능한 유기박막트랜지스터(OTFT)의 핵심 구성 성분인 유기절연체의 신규 합성 및 이를 이용한 유기박막 트랜지스터의 제조에 관한 것이다. 보다 상세히 기술하면 최종으로 유기용매에 용해 가능한 폴리이미드 고분자에 화학적 반응을 통하여 광경화가 가능한 기능기를 도입하여 제조된 새로운 구조의 광경화성 및 가용성의 폴리이미드계 고분자, 이의 제조방법 및 이를 이용한 유기박막 트랜지스터의 제조에 관한 것이다.
본 발명에 따른 폴리이미드계 고분자는 유기용매에 용해가능하여 용액공정으로 용이하게 유기절연막을 형성할 수 있고 광경화를 통하여 절연체의 누설전류를 최소화시킬 수 있어 유기절연막의 절연특성을 향상시키고 박막제조 시 공정온도를 낮추는 효과가 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel synthesis of an organic insulator, which is a key component of an organic thin film transistor (OTFT) applicable to a drive switching element of a next generation flexible display, and to the production of an organic thin film transistor using the same. More specifically, the present invention relates to a photo-curable and soluble polyimide-based polymer having a novel structure prepared by introducing a photo-curable functional group into a polyimide polymer soluble in an organic solvent through chemical reaction, a process for producing the same, and an organic thin film transistor ≪ / RTI >
The polyimide-based polymer according to the present invention can be dissolved in an organic solvent to easily form an organic insulating film in a solution process and minimize leakage current of the insulator through photocuring, thereby improving the insulating property of the organic insulating film, There is an effect of lowering the process temperature at the time of the heat treatment.
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 relates to a process for preparing a novel organic insulator which can be photo-cured by a low-temperature process and a photopolymerization process which can be used for an organic thin film transistor (OTFT) applicable as a driving switching element in a next generation flexible display and the like, 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.Researches on organic thin film transistors (OTFTs) using organic materials as active layers have been actively conducted worldwide since the 1980's. The organic thin film transistor is structurally similar to the conventional silicon-transistor (Si-TFT), but differs in that organic materials are used instead of silicon in the semiconductor region. The organic thin film transistor can be used in a conventional spin coating or printing process instead of a physical / chemical deposition method using an inorganic thin film of a silicon transistor, which can simplify the manufacturing process and enable a 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, silicon dioxide (SiO 2 ), which is an inorganic material, is used as an insulator of an organic thin film transistor, and organic materials such as polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polymethyl methacrylate (PMMA) and polyimide PI) have been used. Since the insulator forms an interface with the organic semiconductor, the crystallinity and the shape of the organic semiconductor depend on the interface characteristics of the insulator, which is a key 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 excellent characteristics of an organic thin film transistor, it is necessary to develop an organic insulator having excellent insulating characteristics. In order to realize an organic thin film transistor on a flexible substrate, a process temperature for forming an organic insulator thin film must also be low. The organic insulator also needs to be patterned to fabricate real array devices using organic thin film transistors.
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 condensation polymerization of an aromatic tetracarboxylic acid or a derivative thereof with an aromatic diamine or an aromatic diisocyanate, and may have various molecular structures depending on the type of the 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 a polyimide resin is an insoluble and non-refferable ultra high heat resistant resin, and has characteristics such as excellent heat resistance and oxidation, high usable temperature, excellent electrochemical and mechanical properties, radiation resistance, excellent low temperature processability and excellent chemical resistance Has a high surface tension due to a high polar group density and has a low dielectric constant for application as an insulator for a thin film transistor and has a disadvantage that a process temperature for imidization reaction is high and formation of a pattern due to light curing is not easy.
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.The polyimide polymer can be divided into two types: the case where the final polymer is dissolved in a common organic solvent; and the case where an insulating film is formed in a polymer precursor state and a final organic insulating film is formed through a heat treatment process at a high temperature. In the former case, the final polymer may be dissolved in an organic solvent and then the thin film may be directly processed to form a final insulating film through a low-temperature solvent drying process. However, the side chain of the polymer introduced for solubility lowers the insulating property 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, the final polyimide polymer has an excellent processability to allow solution process, introducing a photo-curable curing agent to the side chain of polymer, proceeding the process of forming the insulation film at low temperature and improving the insulating property and chemical resistance through photo- It is necessary to develop 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.
The present invention provides a novel polyimide-based organic polymer for producing an organic insulator which is a key component of an organic thin film transistor (OTFT) applicable as a driving switching element in a next-generation flexible display and the like. Specifically, A polyimide organic insulator exhibiting chemical resistance is reacted with a photo-curable functional group 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, a novel organic polymer is prepared by reacting a polyimide-based polymer containing a hydroxy group with various acryloyl groups such as a cinnamoyl group in order to enable a curing reaction by a photoisomerization reaction, The application of organic thin film transistor device as an organic insulating film solves the problem of leakage current and hysteresis in the device. It is not a high temperature thermal curing reaction but also lowers the process temperature of organic insulator thin film manufacturing process by ultraviolet ray irradiation, The effect of improving the insulation characteristics of the mid-system 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 new polyimide-based organic polymer having various structures of acryloyl groups introduced as a photo-curable functional group on a polyimide-based polymer containing a hydroxy group, and a process for producing the same. The polyimide- An organic thin film transistor including an organic insulating film formed through application and curing of a polymer.
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-based organic polymer represented by the following general formula (1) or (2), and is suitable for the production of an organic insulating film of an organic thin film transistor.
[화학식 1][Chemical Formula 1]
[화학식 2](2)
[상기 화학식 1 내지 화학식 2에서 
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 integers of 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 1 to 16 natural numbers.]
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. The polyimide-based organic polymer of Formula 1 or Formula 2 preferably 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 And when the molecular weight exceeds 1,000,000, it is disadvantageous in that the workability due to a high molecular weight is remarkably deteriorated in the organic insulating film forming step. The polyimide-based organic polymer according to the present invention has an intrinsic viscosity of 0.1 to 1.5 dL / g and a glass transition temperature of 150 to 300 ° C.
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 can be produced by reacting a photopolymerizable polyimide resin having an aprotic polarity such as dimethylacetamide (DMAc), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) And easily dissolves at room temperature for an organic solvent such as meta-cresol including a solvent. Particularly, it is preferable to use tetrahydrofuran (THF), cyclohexane And low-boiling solvents such as chloroform and low-absorptive solvents such as gamma-butyrolactone exhibit high solubilities of 10 wt% or more at room temperature. And exhibits a high solubility in a mixed solvent thereof.
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-based organic polymer represented by Chemical Formulas 1 and 2 according to the present invention has a surface tension of 20 to 50 dyne / cm and a dielectric constant of 2 to 6. In addition, by irradiating ultraviolet light having a wavelength of 300 to 400 nm, it is possible to form a fine pattern of 10 to 50 μm. Due to its excellent solubility, polycarbonate, polysulfone polyether sulfone sulfone) on a plastic substrate.
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 relates to a process for producing a polyimide-based organic polymer represented by the above formula (1) or (2), which comprises reacting an acryloyl halide of the following formula (4) or (5) with a polyimide having a hydroxy group of the following formula A method for producing a soluble polyimide-based organic polymer is provided.
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 5][Chemical Formula 5]
[상기 화학식 3에서 
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 acid anhydride 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.The tetracarboxylic acid dianhydride monomer is an aliphatic tetracarboxylic acid dianhydride corresponding to the structure represented by the above (a) to (f) as an anhydride monomer. A mid organo-insulator polymer can be produced. Accordingly, in the present invention, the aliphatic tetracarboxylic acid corresponding to the structures (a) to (f) is 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, examples of the tetracarboxylic acid dianhydride monomer include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride [CBDA; (a)], 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride [CPDA; (c), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic acid dianhydride (b) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dihydrate [DOCDA; (d)], 4- (2,5-dioxotetrahydrofuryl-3-yl) -tetralin-1,2-dicarboxylic acid dianhydride [DOTDA; (e)], and bicyclooctene-2,3,5,6-tetracarboxylic acid dianhydride [BODA; (f)] as an essential component.
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 a polyimide organic insulator of one kind selected from the group consisting of pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, biphthalic dianhydride and hexafluoroisopropylidene diphthalic acid dianhydride Or two or more aromatic tetracarboxylic acid 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.Examples of the diamine monomers include para-phenylenediamine (p-PDA), meta-phenylenediamine (m-PDA), 4,4-oxydianiline (ODA), 4,4- -Bisaminophenylhexafluoropropane (HFDA), meta bisaminophenoxydiphenyl sulfone (m-BAPS), parabisaminophenoxydiphenyl sulfone (p-BAPS), 1,4-bisaminophenoxybenzene (TPE -Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP) and 2,2-bisaminophenoxyphenylhexafluoropropane (HFBAPP) And at least one aromatic diamine compound having at least 1 to 16 hydroxy groups capable of reacting with a photocurable functional group can be used.
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.The introduction of the photo-curing agent is carried out by preparing a soluble polyimide of the above formula (3) and then reacting it with the acryloyl halide of the formula (4) or (5) to react the hydroxy group of the soluble polyimide with the photo- 2 < / RTI > of a soluble polyimide polymer.
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-based organic polymer of Formula 1 is prepared through the reaction between the compound of Formula 3 and the compound of Formula 4, and the polyimide-based organic polymer 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 acid dianhydride [DOCDA (c)] and diamine monomers include hydroxy (3,3-dihydroxybenidine (HAB), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (3-amino-4-hydroxyphenyl) hexafluoropropane (6FHAB) were synthesized, and cinnamoyl chloride, which can be photo-cured finally, was synthesized with hydroxy Group and introduced into the side chain of the polymer. Examples of the compound having a functional group capable of photo-curing include cinnamoyl chloride as well as 3-naphthalen-1-yl-acryloyl substituted with an acryloyl group capable of reacting with a hydroxy group of a side chain of a polymer 3-naphthalen-1-yl-acyloyl chloride and 3-biphenyl-4-yl-acyloyl chloride are also usable.
또한 본 발명은 상기 화학식 1 또는 화학식 2의 폴리이미드계 유기고분자를 사용하여 용액공정을 통해 유기절연막을 제조하는 방법 및 상기 유기절연막을 포함하는 유기 박막트랜지스터를 제공한다.The present invention also provides a method for producing an organic insulating film through a solution process using the polyimide-based organic polymer of Formula 1 or 2 and an organic thin film transistor including the organic insulating film.
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 coating a coating liquid containing a polyimide-based organic polymer into which a photoreactive unit having the formula (1) or (2) has been introduced on a substrate having a gate electrode formed thereon and photo-
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 shows the structure of a bottom-gate organic thin film transistor according to an 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 a polyimide-based organic polymer. Suitable solvents include chloroform, tetrahydrofuran (THF), and cyclohexane . The application may 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.FIG. 1 shows a curing mechanism by photopolymerization of a polyimide-based organic polymer according to the present invention, which is cured by reaction between acryloyl groups as photocurable functional groups of the polyimide-based 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.In the present invention, photo-curing is carried out by heat treatment at 100 ° C to 200 ° C after UV irradiation. In the absence of a photo-curing process, the process can be performed at a significantly lower temperature than that required for heat treatment in excess of 200 ° C. It is more preferable that the UV irradiation energy is performed in the range of 500 mJ to 2000 mJ in terms of maintaining the curability 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 layer can be controlled within the range of 30 nm to 1000 nm, and adjustment within the above range is more advantageous in terms of insulation of the organic insulating layer 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 may include at least one of pentacene, metal phthalocyanine, polythiophene or phenylenevinylene, C 60 , phenylenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, , Fluorophthalocyanine, 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 an electric field mobility in the range of 0.01 to 10 cm 2 / Vs, and the range is a range of electric field mobility values of a conventional organic thin film transistor, which means that the organic thin film transistor has a suitable performance as an 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.
The present invention also provides a display device using the organic thin film transistor according to the present invention, wherein the display device is an organic light emitting display, an electronic paper, a liquid crystal display, or the like.
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 photo-curable and soluble polyimide-based polymers according to the present invention have good solubility in general organic solvents, so that a thin film can be formed at a low temperature and a photo-curing agent is introduced into the polymer produced through polymerization, . In addition, the photo - curing of the organic insulator thin film improved the chemical resistance of the thin film and gave important patterning characteristics in the actual array device fabrication process.
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. Further, in the case of the novel polyimide organic insulator into which the photo-curing device developed in the present invention is introduced, low-temperature processes of about 150 to 160 ° C can be carried out when the organic insulator is used as an organic insulating thin film, .
고분자에 광경화기의 도입 반응이 가능한 하이드록시 그룹이 있는 경우 폴리이미드 뿐만 아니라 다른 모든 고분자에 본 발명의 광경화기 도입 방법이 응용이 될 수 있다.In the case where there is a hydroxy group capable of introducing a photo-curing agent into the polymer, the method of introducing the photo-curing agent of the present invention can be applied not only to polyimide but also to 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 novel photo-curable organic insulator of the present invention can be used in an organic thin film transistor which can be applied as a drive switch to a next-generation flexible display and sensor, and the like. In comparison with the conventional organic insulator, the process temperature, chemical resistance, . ≪ / RTI >
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-based organic polymer according to the present invention,
FIG. 2 is a cross-sectional view illustrating the structure of a top-contact organic thin film transistor according to an embodiment of the present invention,
3 shows the leakage current density before and after photo-curing of the novel organic insulator (KPSPI-1) of the present invention,
4 shows the leakage current density before and after photo-curing 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 photo-curing 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 photo-curing 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.
Hereinafter, the present invention will be described in more detail by way of 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] Production of polyimide-based high molecular material ( KPSPI- 1)
KSPIKSPI -1 제조-1 manufacture
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-dihydroxybenzyl 1.0812 g (5 mmol) of 3,3-dihydroxybenidine (HAB) is prepared in a 50 mL round bottom flask and 21.6212 g of m-cresol is added as a polymerization solvent to completely dissolve the two monomers. The solids content in the reaction solvent of the monomers was adjusted to 10 wt%. The reaction was heated slowly to 70 DEG C over 2 hours and the temperature was raised from 70 DEG C to 160 over 1 hour. The reaction was terminated at 160 < 0 > C for 30 minutes. The viscosity of the final reaction solution was measured at 18,000 cps. The final reaction mixture was precipitated in an excess amount of methanol to obtain a final polymer as a white powder. After that, the solvent was removed by vacuum filtration and the residual solvent was completely removed from the oven to obtain the final hydroxy group-substituted KSPI-1 .
KPSPIKPSPI -1의 제조-1 production
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 added to a 25 mL round bottom pulsar and cinnamoyl chloride was added to 3.98 g (24 mmol) of the reaction vessel as a photopolymerizer. NMP was used as a reaction solvent. 2.45 g (24 mmol) of triethylamine as a base for the reaction promotion was added and the reaction was carried out at room temperature for 12 hours. After the reaction was completed, a small amount of the reaction solution was added to an excess amount of methanol to finally obtain KPSPI-1 having a photo-curing unit introduced therein as a solid. In order to remove the impurities contained in the final polymer, the polymer was repeatedly dissolved in the solvent and the precipitation was repeated. The final polymer was subjected to vacuum distillation, followed by removal of the solvent. Finally, the remaining solvent was removed from the vacuum oven, A soluble polyimide (KPSPI-1) into which a photo-curing agent 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 (?, 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). ( M n ): FT-IR (cm -1, KBR pellet) 1717 (C = O ketone), 1631 (C = C stretching), 1499 21,000 g / mol, a weight average molecular weight ( M w ) of 36,000 g / mol.
[실시예 2] 폴리이미드계 고분자 물질( KPSPI -1)의 제조 [Example 2] Production of polyimide-based high molecular material ( KPSPI- 1)
KSPIKSPI -2의 제조-2 production
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- 1.8313 g (5 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FHAB) was prepared in a 50 mL round bottom flask, - 11.1769 g of m-cresol is added to completely dissolve the two monomers. The solids content in the reaction solvent of the monomers was adjusted to 21 wt%. The reaction was gradually heated to 70 DEG C over 2 hours, and the temperature was raised from 70 DEG C to 160 DEG C over 1 hour. The reaction was terminated by further reaction at 160 DEG C for 1 hour. The viscosity of the final reaction solution was measured at 6500 cps. The resulting reaction mixture was precipitated in an excess amount of methanol to obtain a final polymer as a white powder. After that, the resultant was subjected to pressure filtration to remove the solvent, and the residual solvent was completely removed from the oven to obtain the final hydroxy group-substituted KSPI-2 .
KPSPIKPSPI
-2의 제조-2 production
*
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 added to a 25 mL round bottom pulsar and cinnamoyl chloride was added to 1.99 g (12 mmol) of the reaction vessel as a photopolymerizer. NMP was used as a reaction solvent, and 1.23 g (12 mmol) of triethylamine as a base for the reaction promotion was added and the reaction was carried out at room temperature for 12 hours. After the reaction was completed, a small amount of the reaction solution was added to an excess amount of methanol to finally obtain KPSPI-2 having a photo-curing unit introduced therein as a solid. In order to remove the impurities contained in the final polymer, the polymer was repeatedly dissolved in the solvent and the precipitation was repeated. The final polymer was subjected to vacuum distillation, followed by removal of the solvent. Finally, the remaining solvent was removed from the vacuum oven, Soluble polyimide (KPSPI-2) into which a photo-curing agent 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 광경화[Example 3] Preparation and photo-curing 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 rate of 3000 rpm using a solution of 9 wt% of KPSPI-1 substituted with a neomoyl group in a γ-butylolactone solvent. The thickness of the fabricated thin film was adjusted to 300 nm. The fabricated thin film was subjected to soft baking (90 ° C, 10 minutes) to remove excess solvent. UV irradiation of 1000 mJ ~ 1500 mJ (average 1250 mJ) was performed for photocuring of the thin film. After UV irradiation, finally baking at 90 ° C for 10 minutes and 160 ° C for 30 minutes, as shown in the above reaction formula, The developed organic insulator thin films were prepared.
[실시예 4] 신나모일기가 치환된 KPSPI-2 박막의 제조 및 광경화[Example 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.
The procedure of Example 3 was repeated except that a solution prepared by dissolving KPSPI-2 substituted with cinnamoyl group in a cyclohexanone solvent at a concentration of 7 wt% was used, and as shown in the above reaction formula, An insulator thin film was prepared.
[비교예 1] 광경화되지 않은 KPSPI-1 박막의 제조[Comparative Example 1] Production of a photo-curable 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.
An organic insulator thin film was prepared by spin coating at a rate of about 3000 rpm using a solution of KPSPI-1 dissolved in a γ-butylolactone solvent at a concentration of 9 wt%. The fabricated thin film was adjusted to a thickness of 300 nm. The resulting thin film was subjected to soft baking (90 ° C, 10 minutes) to remove excess solvent, followed by hard baking at 160 ° C for 30 minutes. Finally, the non-photocurable KPSPI- 1 organic insulator thin films were prepared.
[비교예 2] 광경화되지 않은 KPSPI-2 박막의 제조[Comparative Example 2] Production of a photo-curable 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 rate of about 3000 rpm using a solution of KPSPI-2 dissolved in a cyclohexanone solvent at a concentration of 7 wt%. The fabricated thin film was adjusted to a thickness of 300 nm. The resulting thin film was subjected to soft baking (90 ° C, 10 minutes) to remove excess solvent, followed by hard baking at 160 ° C for 30 minutes. Finally, the non-photocurable KPSPI- 2 organic insulator thin films were prepared.
제조된 유기절연체 박막의 특성 평가Characterization of Organic Insulator Thin Films Prepared
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. The chemical resistance of organic thin films, which are important in the fabrication of organic thin film transistors through solution process, was evaluated by measuring the surface roughness of thin films after dipping thin films into cyclohexanone, chloroform and N, N-dimethylformamide (NMP). In the case of Cyclohexanone, chloroform and NMP solvents, in the case of KPSPI-1 and KPSPI-2 (Examples 1 and 2) in which cinnamoyl groups were introduced before curing, the thin film completely dissolved again in the solvent (Examples 3 and 4) after UV curing, no surface damage was observed on the organic solvent. Atomic force microscopy (AFM) analysis showed that the surface roughness, RMS value, was 0.5 nm or less even after organic solvent treatment.
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 good solubility in general organic solvents and organic insulator thin films were formed 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, which is the most important characteristic of KPSPI-1 and KPSPI-2 as an organic insulator thin film, was compared before and after photocuring. And the metal-insulator-metal (MIM) structure was fabricated. The manufacturing conditions of the dielectric were the same as the manufacturing conditions of the thin films of Comparative Examples 1 and 2 and the photocuring conditions of Examples 3 and 4 To prepare a thin film. Gold (Au) was deposited using a patterned indium-tin-oxide (ITO) electrode as a lower electrode and a shadow mask as an upper electrode. The thickness of the organic insulating film was 300 nm Respectively.
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.FIG. 3 shows the leakage current density of KPSPI-1 before and after photo-curing. In the case of KPSPI-1, the leakage current density was 1.20 × 10 -10 A / cm 2 based on 2 MV / cm before light curing, but improved to 7.84 × 10 -11 after photocuring (irradiation of 1500 mJ energy) Voltage (breakdown voltage). In the case of KPSPI-1, which was not photo-cured, device breakdown occurred at 2.5MV or more. The dielectric breakdown voltage of the photo-cured KPSPI-1 is higher than that of organic polymers such as polyvinyl alcohol (PVA) and polyvinyl phenol (PVP) And it can be interpreted that the packing density of the polymer film is increased to the photo-curing between the chains of the polymer.
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.
FIG. 4 shows the leakage current density of KPSPI-2 before and after photo-curing. In the case of KPSPI-2, the leakage current density of 1.68 × 10 -5 A / cm 2 based on 2MV / cm before the photo-curing showed a good characteristic of leakage current of the organic insulator, but after photo- curing (irradiation of 1000 ~ 1500 mJ energy) 1.84X10 -10 . In particular, the breakdown voltage of the MIM device is not degraded even at a voltage of 3MV / cm or more. It can be seen that the packing density of the polymer film is increased by the curing reaction of the cinnamoyl group of the side chain of the polymer by the photo-curing.
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. The organic thin film transistor was fabricated using the polyimide organic insulator thin film which can be cured at low temperatures and photosensitized. As organic semiconductors, Pentacene, which is most widely used in organic thin film transistors and has 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 were used. The device structure of the organic thin film transistor is top-contact type, and the method of manufacturing the device is as follows. Since the cleanliness of the substrate is one of the most important factors in manufacturing electronic devices, if the substrate is glass, ultrasonic cleaning is performed using a detergent, distilled water, acetone, and isopropyl alcohol, and the substrate is sufficiently dried in an oven. Only the protective film was desorbed without using a separate washing process and used as it was.
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. A 2 mm wide gate electrode was formed to a thickness of 40 nm on the well-cleaned substrate by thermal vacuum deposition at 1 x 10 -6 torr using gold shadow mask. The low temperature process of the present invention and the photo-curable polyimide organic insulator (KPSPI-1 and KPSPI-2) were spin-coated to a thickness of 300 nm and dried at 90 DEG C for 10 minutes, 1500 mL of UV irradiation. Finally, KPSPI-1 was dried at 160 ° C for 30 minutes and KPSPI-2 at 150 ° C for 30 minutes to obtain a photocurable polyimide organic 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.In order to confirm the effect of introducing a photo-curing agent as a comparative example, an organic insulator thin film was prepared by omitting 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.On the organic insulator thin films thus prepared, pentacene, an organic semiconductor, was deposited to a thickness of 50 nm by thermal vacuum deposition at a vacuum of 1 × 10 -6 torr. At this time, the temperature of the substrate, which greatly influences the crystallization of pentacene, was kept constant at 90 ° C. Finally, gold was deposited to a thickness of 50 nm in the same manner as gate deposition to form source and drain electrodes. The bottom-contact device was fabricated by changing the order of forming pentacene, source and drain electrodes. The characteristics of the device fabricated as above were measured by using E5272 equipment of Agilent Technologies Co., Ltd., and measuring the gate voltage-drain current curves according to the drain voltage-drain current and the drain voltage according to the gate voltage, Current, and voltage.
상기 식에서 V T 는 문턱전압, Vgs 는 인가된 게이트 전압, μ는 전계효과 전하이동도, W와 L은 채널의 너비와 길이, C는 절연막의 커패시턴스이다. 문턱전압은 
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.FIG. 5 shows the current-voltage characteristics of the organic thin film transistor including the photo-cured KPSPI-1 and the photo-curable KPSPI-1 prepared in Example 3 and Comparative Example 1 as the organic insulator thin film. Photo-current of the light before and after KPSPI-1 (on current) value is shown to be similar as 1.54X10 2.06X10 -5 -5 A and A. However, the off current was improved from 1.98 × 10 -9 A to 1.04 × 10 -10 A, which can be interpreted that the packing density of the KPSPI-1 thin film due to the photo-curing is increased and the insulation is improved. The Ion / Ioff ratio, which is important for transistor performance, is also improved from 7.78X10 3 to 1.98X10 5 . In addition, the subthreshold slope (SS) value increased by two times from 5.08 (V / dec) to 2.76 (V / dec) before photocuring. The mobility of the transistor also improved the characteristics of the transistor with KPSPI-1 photo-curing at 0.12 cm 2 / Vs and 0.16 cm 2 / Vs. Table 1 summarizes the important characteristics of organic thin film transistors using KPSPI-1 before and after photo-curing as an organic insulator thin film.
[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.FIG. 6 shows the current-voltage characteristics of the organic thin film transistor including the photo-cured KPSPI-2 and the photo-curable 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 photo-curing showed similar values as 1.77 × 10 -5 A and 2.10 × 10 -5 A, respectively. However, the off current was greatly improved from 3.95 × 10 -9 A to 5.88 × 10 -12 A, which is similar to that of KPSPI-1. This is because the packing density of KPSPI-2 thin film due to photo- Can be interpreted as improved. The ratio of Ion / Ioff, which is important for transistor performance, is also improved from 4.48 × 10 3 to 3.57 × 10 6 . In addition, the subthreshold slope (SS) value was improved by about 3 times from 5.42 (V / dec) to 1.87 (V / dec) before photocuring. The mobility of the transistor was 0.14 cm 2 / Vs before and after photocuring. Table 2 summarizes the important characteristics of organic thin film transistors using KPSPI-2 before and after photo-curing as an organic insulator thin film.
[표 2][Table 2]
<도면의 주요부분에 대한 부호의 설명>
1: 기판 2: 게이트 전극 3: 유기절연막
4: 유기반도체층 5: 소스 전극 6: 드레인 전극Description of the Related Art
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
n은 10 내지 2000의 자연수이며;
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 polyimide- And then heat-treated at 150 to 160 ° C to form a photo-cured organic thin film transistor.
[Chemical Formula 1]
[Formula 1]
n is a natural number from 10 to 2000;
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 from 1 to 10.]
상기 UV 조사는 500mJ 내지 2000mJ 범위에서 수행되는 유기박막트랜지스터.The method according to claim 1,
Wherein the UV irradiation is performed in a range of 500 mJ to 2000 mJ.
상기 도포는 스핀코팅, 잉크젯 프린팅, 롤코팅, 스크린 프린팅, 및 딥핑으로부터 선택되는 하나 이상의 방법으로 수행되는 유기박막트랜지스터.The method according to claim 1,
Wherein the application is performed by at least one method selected from spin coating, inkjet printing, roll coating, screen printing, and dipping.
상기 유기절연막은 두께가 30 nm 내지 1000 nm 범위인 유기박막트랜지스터.The method according to claim 1,
The organic insulating film has a thickness of 30 nm to 1000 nm Organic thin film transistor.
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 according to claim 1,
Wherein the organic semiconductor layer is selected from the group consisting of pentacene, metal phthalocyanine, polythiophene or phenylenevinylene, C 60 , phenylenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, An organic thin film transistor comprising at least one selected from the group consisting of fluorophthalocyanine and derivatives thereof.
유기박막 트랜지스터는 전계이동도가 0.01 ~ 10cm2/Vs의 범위에 있는 것을 특징으로 하는 유기박막 트랜지스터.The method according to claim 6,
Wherein the organic thin film transistor has an electric field mobility of 0.01 to 10 cm 2 / Vs.
상기 표시소자는 유기발광디스플레이, 전자종이 또는 액정디스플레이로부터 선택되는 표시소자.9. The method of claim 8,
Wherein the display element is selected from an organic light emitting display, an electronic paper, or a liquid crystal display.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR0166886B1 (en) * | 1994-06-28 | 1999-01-15 | 이헌조 | Photopolymer using polyimide fluoro cinnamate and liquid crystal aligning film using same |
| US6307002B1 (en) | 1998-11-09 | 2001-10-23 | Kaneka Corporation | Polyimide composition and process for producing the same |
| KR20050081824A (en) * | 2004-02-12 | 2005-08-19 | 한국화학연구원 | Photosensitive polyamic acid derivatives and polyimides for insulator of organic thin film transistor |
| KR100720454B1 (en) * | 2005-06-14 | 2007-05-22 | 엘지.필립스 엘시디 주식회사 | Liquid Crystal Display Device, and method of fabricating the same |
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| KR0166886B1 (en) * | 1994-06-28 | 1999-01-15 | 이헌조 | Photopolymer using polyimide fluoro cinnamate and liquid crystal aligning film using same |
| US6307002B1 (en) | 1998-11-09 | 2001-10-23 | Kaneka Corporation | Polyimide composition and process for producing the same |
| KR20050081824A (en) * | 2004-02-12 | 2005-08-19 | 한국화학연구원 | Photosensitive polyamic acid derivatives and polyimides for insulator of organic thin film transistor |
| KR100720454B1 (en) * | 2005-06-14 | 2007-05-22 | 엘지.필립스 엘시디 주식회사 | Liquid Crystal Display Device, and method of fabricating the same |
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