KR20030000992A - OLED with a additive bonding layer between anode and organic layer - Google Patents
OLED with a additive bonding layer between anode and organic layer Download PDFInfo
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- KR20030000992A KR20030000992A KR1020010037275A KR20010037275A KR20030000992A KR 20030000992 A KR20030000992 A KR 20030000992A KR 1020010037275 A KR1020010037275 A KR 1020010037275A KR 20010037275 A KR20010037275 A KR 20010037275A KR 20030000992 A KR20030000992 A KR 20030000992A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76855—After-treatment introducing at least one additional element into the layer
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/351—Thickness
Abstract
Description
본 발명은 유기 전계발광 표시소자에 관한 것으로서, 더욱 상세하게는 ITO 전극 표면의 수산기(-OH)를 화학적인 표면개질을 통해 제거함으로써 ITO 전극과 상부 유기층과의 밀착성을 향상시키고 상부 유기층으로의 산소의 확산을 방지하여 안정적이고 높은 효율을 나타내도록 애노드/유기 결합층을 가지는 유기 전계발광 표시소자에 관한 것이다.The present invention relates to an organic electroluminescent display device, and more particularly, by removing the hydroxyl group (-OH) on the surface of the ITO electrode through chemical surface modification to improve the adhesion between the ITO electrode and the upper organic layer and oxygen to the upper organic layer. The present invention relates to an organic electroluminescent display device having an anode / organic bonding layer so as to prevent diffusion of ions and exhibit stable and high efficiency.
일반적으로 유기 전계발광 표시소자는 도 1에 도시된 바와 같이, 투명 기판위에 ITO(Indium Tin Oxide) 등의 애노드(anode) 전극(1)과, 정공수송층(hole transport layer)(2), 발광층(3), 전자수송층(electron transport layer)(4) 및 캐소드(cathod) 전극이 순차적으로 형성되어 구성된다.In general, as shown in FIG. 1, an organic electroluminescent display device includes an anode electrode 1 such as indium tin oxide (ITO), a hole transport layer 2, and a light emitting layer on a transparent substrate. 3), an electron transport layer 4 and a cathode are formed sequentially.
이 때, 상기 발광층에서의 전자와 정공의 재결합 효율을 향상시키기 위하여 애노드 전극(1)과 정공수송층(2) 사이에는 정공주입층(hole injection layer)이, 상기 전자수송층(4)과 캐소드(5) 사이에는 전자주입층이 각각 개재되어 구성될 수 있다.At this time, in order to improve the recombination efficiency of electrons and holes in the light emitting layer, a hole injection layer is provided between the anode electrode 1 and the hole transport layer 2, and the electron transport layer 4 and the cathode 5 The electron injection layer may be interposed therebetween.
그러나, 상기와 같은 유기 전계발광 표시소자의 애노드로 사용되는 ITO 전극(1)은 그 표면에 수산기(-OH)를 포함하고 있기 때문에 정공수송층(2), 발광층(3), 전자수송층(4) 등의 상부 유기층과의 밀착성이 떨어진다. 이는 무기물질인 ITO(1)와 유기층(2)(3)(4)의 계면상에서 상반된 계면물성으로 인하여 밀착성이 떨어지게 되는 일반적인 현상으로 이로 인해 발광이 개시되는 문턱전압(Threshold Voltage; Vth)등이 패널(panel) 전체에 걸쳐 균일하지 못하게 되고 정공의 수송효율이 떨어지는 문제점이 있었다.However, since the ITO electrode 1 used as an anode of the organic electroluminescent display device as described above contains a hydroxyl group (-OH) on its surface, the hole transport layer 2, the light emitting layer 3, and the electron transport layer 4 are used. Adhesion with upper organic layers, such as these, is inferior. This is a general phenomenon that the adhesion is inferior due to the interfacial physical properties on the interface of the inorganic material ITO (1) and the organic layer (2) (3) (4), which causes a threshold voltage (V th ), etc. There was a problem that the uniformity over the entire panel (panel) and the hole transport efficiency is lowered.
또한, 상기 유기 전계발광 표시소자의 유기층(2)(3)(4)과 저 일함수를 갖는 캐소드 금속(cathode metal)(5)은 수분 및 산소에 취약하기 때문에 애노드 전극(1)과 유기층 계면상의 산소가 소자의 동작이 진행됨에 따라 유기층으로 확산되면 발광 효율이 저하되고 소자의 열화가 촉진되어 소자의 수명이 단축되는 문제점이 있었다.In addition, since the organic layers 2, 3, and 4 of the organic electroluminescent display device and the cathode metal 5 having a low work function are vulnerable to moisture and oxygen, the interface between the anode electrode 1 and the organic layer As the oxygen of the phase diffuses into the organic layer as the operation of the device proceeds, the luminous efficiency is lowered, the degradation of the device is accelerated, and the life of the device is shortened.
이와 같은 문제점들을 개선하기 위하여 정공수송층과 ITO 전극 사이에 다공성 물질층을 더 포함하여 구성되는 유기 전계발광 표시소자가 국내 특허출원 제1999-16190호에 개시되어 있으나, 상기 다공성 물질층은 ITO 전극 상부에 견고히 적층시키기가 용이하지 않을 뿐 아니라 그 두께가 1,500Å 이하인 것을 특징으로 하므로 얇은 두께와 표면의 균일함을 요하는 유기 전계발광 표시소자에 있어서 실질적인 정공의 수송 효율 증대 효과는 그리 만족스럽지 못하였다.In order to improve such problems, an organic electroluminescent display device comprising a porous material layer between the hole transport layer and the ITO electrode is disclosed in Korean Patent Application No. 1999-16190, but the porous material layer is formed on the upper part of the ITO electrode. In addition, it is not easy to stack it firmly, and its thickness is not more than 1,500Å, so that the effect of increasing hole transport efficiency is not satisfactory in the organic electroluminescent display device requiring thin thickness and uniformity of surface. .
본 발명은 종래의 상기와 같은 문제점들을 해결하기 위해 안출된 것으로서, 무기물질인 애노드 전극과 유기층의 계면접합 특성을 향상시킨, 애노드/유기 결합층을 가지는 유기 전계발광 표시소자를 제공하는 것을 목적으로 한다.Disclosure of Invention The present invention has been made to solve the above problems, and an object of the present invention is to provide an organic electroluminescent display device having an anode / organic bonding layer, which improves the interface bonding property of an anode electrode and an organic layer, which is an inorganic material. do.
본 발명의 다른 목적은 애노드 전극 표면에 존재하는 산소의 유기층으로의 확산을 방지하여 발광 효율을 향상시키고 소자의 수명을 연장시킨, 애노드/유기 결합층을 가지는 유기 전계발광 표시소자를 제공하는 것이다.Another object of the present invention is to provide an organic electroluminescent display device having an anode / organic bonding layer, which prevents diffusion of oxygen present on the anode electrode surface into an organic layer, thereby improving luminous efficiency and extending the life of the device.
본 발명의 상기와 같은 목적들은 애노드 전극 표면을 유기 상태로 개질시키기 위하여 상부 유기층과의 접촉면에 실란 결합제(silane coupling agent)를 도포 건조시켜 애노드/유기 결합층을 형성시킨 유기 전계발광 표시소자를 제공함으로써 달성되는데, 상기 애노드/유기 결합층은 애노드 전극 표면의 수산기(-OH)를 제거하여 소수성으로 변화시키므로 애노드 전극 표면과 유기층과의 계면접합 특성을 향상시키고 애노드 전극 표면과 견고한 Si-O 공유결합을 형성하여 산소의 유기층으로의확산을 방지할 수 있다.The above objects of the present invention provide an organic electroluminescent display device in which an silane coupling agent is applied and dried on a contact surface with an upper organic layer to form an anode / organic coupling layer in order to modify an anode electrode surface to an organic state. The anode / organic bonding layer is hydrophobic by removing the hydroxyl group (-OH) on the surface of the anode electrode, thereby improving the interfacial bonding property between the anode electrode surface and the organic layer, and the solid Si-O covalent bond with the anode electrode surface. Can be formed to prevent diffusion of oxygen into the organic layer.
도 1은 일반적인 유기 전계발광 표시소자의 단면도,1 is a cross-sectional view of a general organic electroluminescent display device;
도 2a, 2b는 본 발명의 일 실시예에 따른, TMCS를 이용한 ITO 전극의 표면개질 전·후의 유기 전계발광 표시소자의 단면도이다.2A and 2B are cross-sectional views of organic electroluminescent display devices before and after surface modification of an ITO electrode using TMCS according to an embodiment of the present invention.
* 도면의 주요 부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings
11 : 애노드 전극 12 : 정공수송층11 anode electrode 12 hole transport layer
13 : 발광층 14 : 전자수송층13 light emitting layer 14 electron transport layer
15 : 캐소드 전극 20 : 애노드/유기 결합층15 cathode electrode 20 anode / organic bonding layer
본 발명은 유리 기판위에 형성된 ITO 전극과 캐소드 전극 사이에 복수의 유기층을 포함하여 구성되는 유기 전계발광 표시소자에 있어서, 상기 ITO 전극이 상부 유기층과의 접촉면에 실란 결합제(silane coupling agent)를 도포 건조시켜 애노드/유기 결합층을 형성시킨 것을 특징으로 하는, 유기 전계발광 표시소자에 관한 것이다.The present invention provides an organic electroluminescent display device comprising a plurality of organic layers between an ITO electrode and a cathode electrode formed on a glass substrate, wherein the ITO electrode is coated and dried with a silane coupling agent on the contact surface with the upper organic layer. To form an anode / organic coupling layer.
유기 전계발광 디스플레이에 있어서 중요한 것 중의 하나는 애노드 전극인 ITO 전극의 표면상태이다. 이는 전류구동을 하는 유기 전계발광 표시소자에 있어서 상부 유기층으로의 정공 주입 및 소자 수명 등에 큰 영향을 끼친다. 따라서, 본 발명에서는 유기 전계발광 표시소자의 애노드 전극 표면을 화학적으로 개질하여 소자전체의 밀착성을 증대시키기 위하여 애노드 전극 표면의 수산기를 실란 결합제를 이용하여 제거하고 애노드 전극 표면을 유기 상태로 변화시켰다.One of the important things in organic electroluminescent displays is the surface state of the ITO electrode, which is the anode electrode. This greatly affects the hole injection, device lifetime, and the like in the organic electroluminescent display device which drives current. Therefore, in the present invention, in order to chemically modify the anode electrode surface of the organic electroluminescent display device to increase the adhesion of the entire device, the hydroxyl group on the anode electrode surface was removed using a silane binder, and the anode electrode surface was changed to an organic state.
실란 결합제는 유기물과 규소로 구성된 화합물로서 분자중에 무기질 재료와 화학적 결합을 하는 반응기와 고분자재료와 화학적 결합을 하는 반응기를 모두 가지고 있기 때문에 이러한 반응기들이 고분자재료와 무기물 재료를 결합시키는 중개역할을 한다．Silane binder is a compound composed of organic material and silicon, and since it has both a reactor that chemically bonds inorganic material and a polymer material in the molecule, and a reactor that chemically bonds with a polymer material, these reactors act as an intermediary to bond the polymer material and the inorganic material.
본 발명에 있어서 실란 결합제로는 트리-메틸-클로로-실란(tri-methyl- chloro-silane; TMCS), 비닐-트리-클로로-실란(vinyl-tri- chloro-silane), 비닐-트리-에톡시-실란(vinyl-tri-ethoxy-silane), 비닐-트리-메톡시-실란(vinyl-tri-methoxy-silane), 트리-메톡시-실란(tri-methoxy-silane), 메틸-디-에톡시-실란 (methyl-di-ethoxy-silane), 트리-메톡시-실란(tri-methoxy-silane), 메틸-디-메톡시-실란(methyl-di-methoxy-silane), 트리-메톡시-실란(tri-methoxy- silane) 등이 사용될 수 있으며, 그 중에서도 트리-메틸-클로로-실란(tri-methyl-chloro-silane; TMCS)이 사용되는 것이 가장 바람직하다.In the present invention, the silane binder may include tri-methyl-chloro-silane (TMCS), vinyl-tri-chloro-silane, and vinyl-tri-ethoxy. Vinyl-tri-ethoxy-silane, vinyl-tri-methoxy-silane, tri-methoxy-silane, methyl-di-ethoxy Silane (methyl-di-ethoxy-silane), tri-methoxy-silane, methyl-di-methoxy-silane, tri-methoxy-silane (tri-methoxy-silane) and the like can be used, and among them, tri-methyl-chloro-silane (TMCS) is most preferably used.
또한, 상기 애노드/유기 결합층은 두께가 10Å보다 커질 경우 ITO 전극 표면의 수산기 제거 효과가 크게 증대되지 않으므로 10Å 이하의 두께를 갖는 것이 바람직하다.In addition, the anode / organic bonding layer preferably has a thickness of 10 kPa or less since the effect of removing hydroxyl groups on the surface of the ITO electrode is not greatly increased when the thickness is greater than 10 kPa.
이하 본 발명을 실시예를 들어 상세히 설명하고자 하나, 본 발명이 기술된 실시예에 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the described embodiments.
도 2a 및 2b는 본 발명의 일 실시예에 따른 트리-메틸-클로로-실란(tri-methyl-chloro-silane; TMCS)을 이용한 표면개질 전·후의 ITO 전극을 나타낸 것이다.2A and 2B illustrate ITO electrodes before and after surface modification using tri-methyl-chloro-silane (TMCS) according to an embodiment of the present invention.
ITO 전극(11)의 표면에는 도 2a에 도시된 바와 같이 수많은 수산기가 존재하고 있는데 상기 수산기는 ITO 전극과 상부 유기층과의 결합시 밀착성을 저하시킬 뿐 아니라 향후 유기층으로 확산되는 산소의 공급원이 되어 소자의 수명을 단축시키게 된다.A large number of hydroxyl groups exist on the surface of the ITO electrode 11 as shown in FIG. 2A. The hydroxyl groups not only reduce adhesion when the ITO electrode is combined with the upper organic layer, but also become a source of oxygen diffused into the organic layer in the future. Will shorten the life of the product.
본 발명에서는 이러한 수산기를 제거하고 ITO 전극 표면을 유기 상태로 개질시키기 위하여 트리-메틸-클로로-실란(tri-methyl-chloro-silane; TMCS)(A)과 같은 실란 결합제를 ITO 전극 표면에 도포 건조시켜 애노드/유기 결합층(20)을 형성시켰다.In the present invention, a silane binder such as tri-methyl-chloro-silane (TMCS) (A) is applied to the surface of the ITO electrode in order to remove such hydroxyl groups and to modify the surface of the ITO electrode into an organic state. To form the anode / organic bonding layer 20.
이 때의 반응식은 다음과 같다.The reaction formula at this time is as follows.
본 발명에 있어서, 애노드/유기 결합층(20)이 상부에 형성된 ITO 전극(11)은 표면이 유기상태를 나타내므로 정공수송층(12), 발광층(13), 전자수송층(14) 등의 상부 유기층과의 밀착성이 증대된다.In the present invention, since the surface of the ITO electrode 11 having the anode / organic coupling layer 20 formed thereon is in an organic state, the upper organic layer such as the hole transport layer 12, the light emitting layer 13, and the electron transport layer 14 is formed. Adhesion with is increased.
또한, 본 발명은 애노드/유기 결합층(20)과 ITO 전극(11)의 계면에 형성된 견고한 Si-O 공유결합으로 인하여 산소가 유기층(12)(13)(14) 및 캐소드 금속(15)으로 유입되지 못하므로 소자의 열화로 인한 수명단축을 방지할 수 있게 된다.In addition, the present invention provides oxygen to the organic layers 12, 13, 14 and the cathode metal 15 due to the strong Si—O covalent bonds formed at the interface between the anode / organic bonding layer 20 and the ITO electrode 11. Since it does not flow, it is possible to prevent the shortening of the life due to deterioration of the device.
한편, 상기 실시예에서는 ITO 전극(11)과 애노드/유기 결합층(20) 상부에 정공수송층(12), 발광층(13), 전자수송층(14) 등의 유기층이 형성되었으나, 본 발명은 이에 한정되는 것이 아니며, 고효율의 발광을 얻기 위하여 ITO 전극과 정공수송층사이에 정공주입층을 개재시키거나 전자수송층과 캐소드 사이에 전자주입층을 개재시키는 등 다양한 변형이 이루어질 수 있다.In the above embodiment, an organic layer such as a hole transport layer 12, a light emitting layer 13, and an electron transport layer 14 is formed on the ITO electrode 11 and the anode / organic coupling layer 20, but the present invention is limited thereto. Various modifications may be made such that a hole injection layer is interposed between the ITO electrode and the hole transport layer or an electron injection layer is interposed between the electron transport layer and the cathode in order to obtain high efficiency light emission.
상기한 바와 같이 본 발명에 의한 유기 전계발광 표시소자는 ITO 전극 표면의 수산기를 화학적인 표면개질을 통해 제거함으로서 소자전체의 밀착성이 증대되어 소자 전체에 걸쳐서 균일한 문턱전압을 나타낸다.As described above, the organic electroluminescent display device according to the present invention removes hydroxyl groups on the surface of the ITO electrode through chemical surface modification, thereby increasing the adhesion of the entire device, thereby exhibiting a uniform threshold voltage throughout the device.
또한, 본 발명은 ITO 전극 표면과 애노드/유기 결합층의 견고한 Si-O 공유결합으로 인하여 산소의 유기층으로의 확산을 방지할 수 있어 소자의 동작 특성이 향상되며 더 안정적이고 우수한 발광 효율을 나타낸다.In addition, the present invention can prevent the diffusion of oxygen into the organic layer due to the solid Si-O covalent bonding of the surface of the ITO electrode and the anode / organic bonding layer improves the operating characteristics of the device and shows a more stable and excellent luminous efficiency.
Claims (3)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930015141A (en) * | 1991-12-20 | 1993-07-23 | 이헌조 | Manufacturing method of photodiode |
| JPH065365A (en) * | 1991-12-24 | 1994-01-14 | Mitsui Toatsu Chem Inc | Organic thin film el element |
| JPH08185973A (en) * | 1994-12-27 | 1996-07-16 | Fuji Xerox Co Ltd | Organic electroluminescent element and its manufacture |
| KR19980071238A (en) * | 1997-02-10 | 1998-10-26 | 르네 뮬러 | Process for obtaining a transparent substrate and a transparent substrate provided with one or more thin layers based on silicon nitride or oxynitride |
| KR20000073117A (en) * | 1999-05-06 | 2000-12-05 | 김영환 | Organic electroluminescent display device |
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2001
- 2001-06-28 KR KR1020010037275A patent/KR20030000992A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930015141A (en) * | 1991-12-20 | 1993-07-23 | 이헌조 | Manufacturing method of photodiode |
| JPH065365A (en) * | 1991-12-24 | 1994-01-14 | Mitsui Toatsu Chem Inc | Organic thin film el element |
| JPH08185973A (en) * | 1994-12-27 | 1996-07-16 | Fuji Xerox Co Ltd | Organic electroluminescent element and its manufacture |
| KR19980071238A (en) * | 1997-02-10 | 1998-10-26 | 르네 뮬러 | Process for obtaining a transparent substrate and a transparent substrate provided with one or more thin layers based on silicon nitride or oxynitride |
| KR20000073117A (en) * | 1999-05-06 | 2000-12-05 | 김영환 | Organic electroluminescent display device |
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