JP2002117973A - Organic electroluminescent element and its manufacturing device - Google Patents
Organic electroluminescent element and its manufacturing deviceInfo
- Publication number
- JP2002117973A JP2002117973A JP2001146910A JP2001146910A JP2002117973A JP 2002117973 A JP2002117973 A JP 2002117973A JP 2001146910 A JP2001146910 A JP 2001146910A JP 2001146910 A JP2001146910 A JP 2001146910A JP 2002117973 A JP2002117973 A JP 2002117973A
- Authority
- JP
- Japan
- Prior art keywords
- film
- protective film
- organic
- electroluminescent device
- organic electroluminescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 230000001681 protective effect Effects 0.000 claims abstract description 244
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 72
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 41
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 34
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229930192474 thiophene Natural products 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 229920006254 polymer film Polymers 0.000 claims description 49
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 150000003577 thiophenes Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 404
- 238000001816 cooling Methods 0.000 abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 16
- 239000010409 thin film Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 77
- 239000000758 substrate Substances 0.000 description 55
- 238000000034 method Methods 0.000 description 28
- 238000002347 injection Methods 0.000 description 27
- 239000007924 injection Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000006866 deterioration Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 10
- 239000006059 cover glass Substances 0.000 description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 9
- 230000005525 hole transport Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 thiophene Chemical class 0.000 description 6
- 230000035882 stress Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000008646 thermal stress Effects 0.000 description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000427 thin-film deposition Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 102100033040 Carbonic anhydrase 12 Human genes 0.000 description 1
- 101000867855 Homo sapiens Carbonic anhydrase 12 Proteins 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、有機電界発光素
子（以下有機ＥＬ素子という）、特にこの素子を保護す
るための保護膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device (hereinafter, referred to as an organic EL device), and more particularly to a protective film for protecting the device.
【０００２】[0002]
【従来の技術】有機ＥＬ素子は、基板上に、電極及び電
極間に形成された有機発光層を備え、両側の電極から有
機発光層に電子と正孔を注入し、有機発光層で発光を起
こさせる素子であり、高輝度発光が可能である。また有
機化合物の発光を利用しているため発光色の選択範囲が
広いなどの特徴を有し、光源やディスプレイなどとして
期待されており現在実用化が始まりつつある。2. Description of the Related Art An organic EL device comprises an electrode and an organic light emitting layer formed between the electrodes on a substrate. Electrons and holes are injected into the organic light emitting layer from the electrodes on both sides to emit light with the organic light emitting layer. It is an element that causes light emission and can emit light with high luminance. In addition, since it uses light emission of an organic compound, it has a feature such as a wide selection range of emission colors, and is expected to be used as a light source or a display.
【０００３】[0003]
【発明が解決しようとする課題】有機ＥＬ素子は、長時
間駆動すると輝度が減少するという劣化現象、即ち経時
劣化が発生することが知られている。このような有機Ｅ
Ｌ素子の経時劣化の原因の一つとして、素子駆動中に発
生するジュール熱により素子温度が上昇し、これにより
有機化合物に変質等が発生することが考えられている。
そこで、経時劣化を抑えるためには、素子を冷却し、駆
動中に発生するジュール熱による素子温度の上昇を抑制
する必要がある。It is known that the organic EL element suffers from a deterioration phenomenon that the luminance decreases when driven for a long time, that is, a deterioration with time. Such organic E
As one of the causes of the time-dependent deterioration of the L element, it is considered that the element temperature rises due to Joule heat generated during the operation of the element, thereby causing the organic compound to deteriorate or the like.
Therefore, in order to suppress the deterioration over time, it is necessary to cool the element and suppress an increase in the element temperature due to Joule heat generated during driving.
【０００４】素子を効率よく冷却するには、発生した熱
を効率よく放熱させることが必要で、そのためには、ペ
ルチェ素子やファンなどを設け、有機ＥＬ素子を直接冷
却するかまたは熱伝導度の高い物質を介して冷却する手
法が考えられる。In order to cool the element efficiently, it is necessary to efficiently radiate the generated heat. For this purpose, a Peltier element or a fan is provided to directly cool the organic EL element or to reduce the thermal conductivity. A method of cooling through a high material is conceivable.
【０００５】しかし、有機ＥＬ素子は、一般に基板とし
て熱伝導度の低いガラス基板が用いられており、ガラス
基板による冷却効果はそれほど期待できない。従って、
このような基板の上に形成された素子部側からの放熱が
必要となる。However, a glass substrate having low thermal conductivity is generally used as the organic EL element, and the cooling effect of the glass substrate cannot be expected so much. Therefore,
It is necessary to dissipate heat from the element portion formed on such a substrate.
【０００６】また、有機ＥＬ素子、特にその有機化合物
層は空気中の水分や酸素による浸食を受けやすく、これ
ら水分や酸素存在下では、ダークスポットと呼ばれる発
光不能な領域が発生する等の劣化が起きやすい。そこ
で、有機ＥＬ素子では、乾燥窒素やアルゴンガスなどの
雰囲気中で、カバーガラスや缶パッケージなどの封止部
材などを用い、基板上に形成された素子部側を封止した
り、素子部側を保護膜で覆うなどの対策が施されること
が知られている。このため、素子部側から有機ＥＬ素子
を直接冷却することは不可能であり、封止部材、保護膜
などを介して強制冷却が行われることとなる。Further, the organic EL device, particularly its organic compound layer, is susceptible to erosion by moisture or oxygen in the air, and in the presence of such moisture or oxygen, deterioration such as generation of a dark spot called a non-light emitting area occurs. Easy to get up. Therefore, in the organic EL element, the element portion side formed on the substrate is sealed or sealed in a dry nitrogen or argon gas atmosphere using a sealing member such as a cover glass or a can package. It is known that countermeasures such as covering with a protective film are taken. Therefore, it is impossible to directly cool the organic EL element from the element part side, and forced cooling is performed via a sealing member, a protective film, and the like.
【０００７】しかし、このカバーガラスや缶パッケージ
による封止の場合、素子とこれら封止部材との間には、
熱伝導度の低い乾燥窒素層やアルゴンガス層が存在す
る。これらの層は、有機ＥＬ素子部を構成する薄膜に比
べて非常に厚く、冷却効果が極めて低い。従って、冷却
による素子寿命の向上の効果が低い。However, in the case of sealing with this cover glass or can package, there is a gap between the element and these sealing members.
There is a dry nitrogen layer or argon gas layer with low thermal conductivity. These layers are much thicker than the thin films constituting the organic EL element portion, and have a very low cooling effect. Therefore, the effect of improving the element life by cooling is low.
【０００８】保護膜としては、シリコン窒化膜やシリコ
ン酸化膜やＤＬＣ（Diamond Like Carbon、特開平５−
１０１８８５号公報）の他、有機材料としてポリパラキ
シレン（特開平５−１０１８８６号公報）、ポリ尿素
（特開平８−２２２３６８号公報）等を用いることが提
案されている。As a protective film, a silicon nitride film, a silicon oxide film, DLC (Diamond Like Carbon,
In addition to this, it has been proposed to use polyparaxylene (Japanese Patent Laid-Open No. 5-101886), polyurea (Japanese Patent Laid-Open No. 8-222368), or the like as an organic material.
【０００９】これらの保護膜の内、シリコン窒化膜やシ
リコン酸化膜は、空気中の水分や酸素に対する遮蔽性、
熱伝導率は高いが、これらの膜を製造するためのコスト
は高い。特に、ストライプ状に形成された第１及び第２
電極が、有機発光層を挟んで互いに交差するように配置
された単純マトリクス型有機ＥＬ素子では、低製造コス
トであることの要求が強い。また、この単純マトリクス
型では素子部自体を製造するにあたっては、シリコン窒
化膜などのみを保護膜に使用すると、厚いシリコン窒化
膜が必要なために製造コストの上昇につながってしま
う。また、上述のような有機ポリマーやＤＬＣ等を保護
膜として用いた場合、空気中の水分や酸素の遮蔽性が十
分高いとは言えず、素子の劣化を防止する機能が低くな
ってしまう。Among these protective films, a silicon nitride film and a silicon oxide film have a shielding property against moisture and oxygen in air,
Although the thermal conductivity is high, the cost to manufacture these films is high. In particular, the first and second stripe-shaped first and second
In a simple matrix type organic EL device in which electrodes are arranged so as to cross each other with an organic light emitting layer interposed therebetween, there is a strong demand for low manufacturing cost. Also, in the simple matrix type, when only the silicon nitride film or the like is used for the protective film in manufacturing the element portion itself, a thick silicon nitride film is required, which leads to an increase in manufacturing cost. Further, when the above organic polymer, DLC, or the like is used as a protective film, it cannot be said that the property of shielding moisture and oxygen in the air is sufficiently high, and the function of preventing the element from deteriorating is reduced.
【００１０】また、上記シリコン窒化膜や、シリコン酸
化膜は、半導体プロセスの通常のプロセスによって成膜
すると成膜時に下層にある有機化合物膜にダメージを与
える可能性があるため、ダメージを与えないよう、ＥＣ
ＲプラズマＣＶＤ（特開平１０−２６１４８７号公報）
を用いて成膜することが提案されている。しかしＥＣＲ
プラズマＣＶＤ法によって成膜されたシリコン窒化膜や
シリコン酸化膜は水分及び酸素の遮蔽性は不十分であっ
た。Further, the silicon nitride film and the silicon oxide film may be damaged by a normal process of a semiconductor process since the underlying organic compound film may be damaged at the time of film formation. , EC
R plasma CVD (Japanese Patent Laid-Open No. 10-261487)
It has been proposed to form a film by using. But ECR
The silicon nitride film and the silicon oxide film formed by the plasma CVD method have insufficient moisture and oxygen shielding properties.
【００１１】そこで、上記課題を解決するために、この
発明では、有機ＥＬ素子の冷却効果が高く、かつ、空気
中の水分や酸素の遮蔽性の高い優れた保護膜を備える有
機ＥＬ素子を低コストで提供することを目的とする。Therefore, in order to solve the above-mentioned problems, according to the present invention, an organic EL element having a high cooling effect of the organic EL element and having an excellent protective film having a high shielding property against moisture and oxygen in the air is required. The purpose is to provide at a cost.
【００１２】[0012]
【課題を解決するための手段】上記目的を達成するため
にこの発明は、有機電界発光素子において、電極間に少
なくとも一層の有機化合物層を備えた素子領域と、該素
子領域を覆って形成された保護膜と、を備え、前記保護
膜がヘテロ環式化合物の重合体を含む有機保護膜を有す
ることを特徴とする。According to the present invention, there is provided an organic electroluminescent device comprising: a device region having at least one organic compound layer between electrodes; and an organic electroluminescent device formed to cover the device region. And a protective film, wherein the protective film has an organic protective film containing a polymer of a heterocyclic compound.
【００１３】また本発明の他の態様は、上記ヘテロ環式
化合物は、五員環化合物であることである。Another aspect of the present invention is that the heterocyclic compound is a five-membered ring compound.
【００１４】本発明の他の態様は、前記ヘテロ環式化合
物の重合体膜は、フラン、ピロール、チオフェンのいず
れかの重合体又は２つ以上からなる共重合体を含むこと
である。Another aspect of the present invention is that the polymer film of the heterocyclic compound contains a polymer of any one of furan, pyrrole, and thiophene or a copolymer of two or more.
【００１５】このようなヘテロ環式化合物の重合体を含
む有機保護膜を有する保護膜は、水や酸素等に対し十分
な遮蔽性を発揮する。また、熱伝導度が比較的高いた
め、素子領域を覆って構成した場合に、素子領域で発生
した熱を放熱させることができ、熱による劣化が起きや
すい有機ＥＬ素子の寿命を向上させることが可能とな
る。また、素子領域をこのヘテロ環式化合物の重合膜を
有する保護膜が直接覆うことにより、保護膜をさらに強
制冷却手段等で冷却することが可能で、より容易かつ効
率的に有機ＥＬ素子を冷却することが可能となる。さら
にこの重合膜は低コストで製造することができる。A protective film having an organic protective film containing a polymer of such a heterocyclic compound exhibits sufficient shielding properties against water, oxygen and the like. In addition, since the thermal conductivity is relatively high, when the device is configured to cover the element region, heat generated in the element region can be radiated, and the life of the organic EL element, which is likely to be deteriorated by heat, can be improved. It becomes possible. Further, by directly covering the element region with the protective film having the polymerized film of the heterocyclic compound, the protective film can be further cooled by forced cooling means or the like, so that the organic EL element can be cooled more easily and efficiently. It is possible to do. Further, the polymer film can be manufactured at low cost.
【００１６】また、本発明の他の態様において、上記有
機保護膜は、前記ヘテロ環式化合物をプラズマ重合して
得た重合膜である。In another embodiment of the present invention, the organic protective film is a polymer film obtained by plasma-polymerizing the heterocyclic compound.
【００１７】プラズマ重合法を用いれば、有機ＥＬ素子
の素子領域上に薄膜として保護膜を形成することが容易
であり、また、素子領域を水分や酸素等に晒すことなく
この素子領域を保護膜で覆うことが可能となる。If the plasma polymerization method is used, it is easy to form a protective film as a thin film on the device region of the organic EL device, and the device region is protected by exposing the device region to moisture or oxygen. It becomes possible to cover with.
【００１８】また、本発明の他の態様では、上記保護膜
は、上記有機保護膜と、さらに無機保護膜を備えた積層
構造を有する。In another aspect of the present invention, the protective film has a laminated structure including the organic protective film and an inorganic protective film.
【００１９】さらに、この無機保護膜としては、窒化膜
又は酸化膜又は炭素膜又はシリコン膜のいずれかを有す
る。無機保護膜は、より具体的には、窒化珪素膜、窒化
硼素膜、窒化アルミニウム膜、酸化珪素膜、酸化アルミ
ニウム膜、酸化チタン膜、アモルファスシリコン膜膜又
はダイアモンド状カーボン（ＤＬＣ）等が採用可能であ
る。Further, the inorganic protective film has any one of a nitride film, an oxide film, a carbon film, and a silicon film. More specifically, the inorganic protective film can be a silicon nitride film, a boron nitride film, an aluminum nitride film, a silicon oxide film, an aluminum oxide film, a titanium oxide film, an amorphous silicon film film, a diamond-like carbon (DLC), or the like. It is.
【００２０】このような、ヘテロ環式化合物の重合体等
からなる有機保護膜と、窒化膜、酸化膜、シリコン膜、
ＤＬＣ膜等を用いた無機保護膜とを有する保護膜は、水
や酸素に対し十分な遮蔽性を発揮すると同時に、熱サイ
クルに対しても耐久性を有する有機ＥＬ素子を提供する
ことができる。つまり、積層構造体の熱伝導率は比較的
高く、素子領域で発生した熱を放熱することができ、熱
による劣化がおきやすい有機ＥＬ素子の寿命を向上させ
ることが可能となる。また、保護膜を強制冷却手段で冷
却することが可能で、より容易かつ効率的に有機ＥＬ素
子を冷却することが可能となる。さらに、本発明の積層
構造を有する保護膜は、通常実施されているカバーガラ
スや缶パッケージなど封止に比べ、低コストで製造する
ことができる。An organic protective film made of such a heterocyclic compound polymer, a nitride film, an oxide film, a silicon film,
A protective film having an inorganic protective film using a DLC film or the like can provide an organic EL device that exhibits sufficient shielding properties against water and oxygen and has durability against a heat cycle. That is, the heat conductivity of the laminated structure is relatively high, and the heat generated in the element region can be radiated, so that the life of the organic EL element, which is easily deteriorated by heat, can be improved. In addition, the protective film can be cooled by the forced cooling means, and the organic EL element can be cooled more easily and efficiently. Further, the protective film having the laminated structure of the present invention can be manufactured at a lower cost as compared with conventional sealing such as a cover glass and a can package.
【００２１】また、本発明において、保護膜を形成する
前記ヘテロ環式化合物はプラズマ重合して得られた重合
膜を含んでおり、かつ前記窒化珪素膜、酸化珪素膜、Ｄ
ＬＣ膜等の無機保護膜はプラズマＣＶＤ法によって得ら
れたことを特徴とする。In the present invention, the heterocyclic compound forming the protective film includes a polymerized film obtained by plasma polymerization, and includes the silicon nitride film, silicon oxide film,
An inorganic protective film such as an LC film is obtained by a plasma CVD method.
【００２２】ヘテロ環式化合物をプラズマ重合法で形成
すれば、有機ＥＬ素子の素子領域上にダメージを与える
ことなく薄膜として薄膜を形成することが容易である。If a heterocyclic compound is formed by a plasma polymerization method, it is easy to form a thin film as a thin film without damaging the element region of the organic EL element.
【００２３】また、本発明の態様において、有機保護膜
と無機保護膜の積層構造は、素子側を上記有機保護膜と
する構造、或いは反対に素子側を無機保護膜とする構造
のいずれを採用することも可能である。In the embodiment of the present invention, the laminated structure of the organic protective film and the inorganic protective film employs either a structure in which the element side has the organic protective film or a structure in which the element side has an inorganic protective film. It is also possible.
【００２４】有機保護膜及び無機保護膜が素子領域側か
らこの順に形成された構成を採用すれば、有機保護膜は
無機保護膜と比べて熱応力が小さい為、素子駆動時に素
子が発熱した場合にも素子にかかる応力を低減できる。
また、有機保護膜が素子領域を覆った状態で無機保護膜
を形成することとなるため、無機保護膜の成膜にあた
り、強度の低い膜になりやすいＥＣＲプラズマでなく、
汎用のＲＦプラズマを用いることができ、最外層に位置
する無機保護膜の強度を向上でき、結果として有機ＥＬ
素子の保護機能を寄り向上させることが可能となる。If a structure in which an organic protective film and an inorganic protective film are formed in this order from the element region side is adopted, the organic protective film has a smaller thermal stress than the inorganic protective film. Also, the stress applied to the element can be reduced.
In addition, since the inorganic protective film is formed in a state where the organic protective film covers the element region, the inorganic protective film is not formed by ECR plasma which tends to be a low-strength film when forming the inorganic protective film.
General-purpose RF plasma can be used, and the strength of the inorganic protective film located on the outermost layer can be improved.
It becomes possible to further improve the protection function of the element.
【００２５】また、無機保護膜及び有機保護膜が素子領
域側からこの順に形成された構成を採用すれば、有機保
護膜中の重合体と素子中の有機化合物とが反応すること
を防止でき、素子の劣化防止が可能となる。またこの素
子側の無機保護膜を比較的薄い例えば５００ｎｍ程度の
厚さとすれば、この無機保護膜の熱応力による素子への
悪影響を低減することができる。Further, by adopting a constitution in which the inorganic protective film and the organic protective film are formed in this order from the element region side, it is possible to prevent the polymer in the organic protective film from reacting with the organic compound in the element, Element deterioration can be prevented. Further, if the inorganic protective film on the element side is relatively thin, for example, about 500 nm in thickness, the adverse effect on the element due to the thermal stress of the inorganic protective film can be reduced.
【００２６】さらに素子側から無機保護膜及び有機保護
膜がこの順に形成されている構成において、有機保護膜
を覆ってさらに無機保護膜を形成する保護膜の多層構造
も採用でき、最外層を無機保護膜として、有機保護膜を
外気と遮断していっそう保護膜としての耐性を高めるこ
とができる。Further, in a configuration in which an inorganic protective film and an organic protective film are formed in this order from the element side, a multilayer structure of a protective film which covers the organic protective film and further forms an inorganic protective film can be adopted. As the protective film, the organic protective film can be shielded from the outside air, and the resistance as the protective film can be further increased.
【００２７】本発明の他の態様は、電極間に少なくとも
一層の有機化合物層を備えた素子領域と、有機保護膜及
び無機保護膜の積層構造を備え該素子領域を覆って形成
された保護膜と、を備える有機電界発光素子の製造装置
に関し、前記素子領域を構成する各層をそれぞれ成膜す
る素子成膜室と、前記有機保護膜を成膜する有機保護膜
成膜室と、前記無機保護膜を成膜する無機保護膜成膜室
と、を備える。そして、少なくとも、前記素子領域を覆
って先に形成される前記有機又は無機保護膜を成膜する
前記有機又は無機保護膜成膜室と、前記素子成膜室とが
直接又は搬送用真空室を介して連結されている。According to another aspect of the present invention, there is provided a device region having at least one organic compound layer between electrodes, and a protective film having a laminated structure of an organic protective film and an inorganic protective film and covering the device region. A device film forming chamber for forming each layer constituting the element region, an organic protective film forming chamber for forming the organic protective film, and the inorganic protective film. An inorganic protective film forming chamber for forming a film. And, at least, the organic or inorganic protective film film forming chamber for forming the organic or inorganic protective film formed earlier to cover the element region, and the element film forming chamber is directly or a transfer vacuum chamber. Are connected via
【００２８】また、上記有機電界発光素子の製造装置に
おいて、前記無機保護膜成膜室はプラズマＣＶＤ装置に
より構成され、前記有機保護膜成膜室はプラズマ重合装
置により構成することができる。In the above-described apparatus for manufacturing an organic electroluminescent device, the inorganic protective film forming chamber may be constituted by a plasma CVD apparatus, and the organic protective film forming chamber may be constituted by a plasma polymerization apparatus.
【００２９】さらに、前記有機保護膜成膜室で形成され
る前記有機保護膜は、ヘテロ環式化合物の重合体を含
み、前記無機保護膜成膜室で形成される前記無機保護膜
は、窒化膜又は酸化膜又は炭素膜又はシリコン膜のいず
れかを含む構成を採用することができる。Further, the organic protective film formed in the organic protective film forming chamber contains a polymer of a heterocyclic compound, and the inorganic protective film formed in the inorganic protective film forming chamber is formed by nitriding. A configuration including any of a film, an oxide film, a carbon film, and a silicon film can be employed.
【００３０】このような構成とすることで、既に有機Ｅ
Ｌ素子が形成された基板を大気に晒さずに保護膜の成膜
装置まで搬送することができる。有機ＥＬ素子を大気に
晒さずに保護膜形成装置に搬送することが可能となるこ
とで、in-situでの各層の積層が可能となる。これによ
り、例えばプラズマ重合によって形成した有機保護膜中
に残存する有機化合物モノマーによる素子の浸食を防止
し、かつ特に高温駆動時に問題となる大気中の水分や酸
素の吸着による浸食を防止し、さらに吸着水分や酸素に
より、プラズマ重合体の有機保護膜の膜質が劣化するこ
とを防止して、ダークスポットのない高温耐久性を有す
る有機ＥＬ素子の製造が可能となる。With such a configuration, the organic E
The substrate on which the L element is formed can be transported to the protective film forming apparatus without exposing the substrate to the atmosphere. Since the organic EL element can be transported to the protective film forming apparatus without being exposed to the air, the layers can be stacked in-situ. Thereby, for example, erosion of the element by the organic compound monomer remaining in the organic protective film formed by plasma polymerization is prevented, and erosion due to adsorption of moisture and oxygen in the atmosphere, which is a problem particularly at the time of high temperature driving, is prevented. Deterioration of the film quality of the plasma polymer organic protective film due to the adsorbed moisture and oxygen is prevented, and an organic EL device having high temperature durability without dark spots can be manufactured.
【００３１】[0031]
【発明の実施の形態】以下、図面を用いてこの発明の好
適な実施の形態（以下実施形態という）について説明す
る。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention (hereinafter, referred to as embodiments) will be described below with reference to the drawings.
【００３２】［実施形態１］図１は、この発明の実施形
態１に係る有機ＥＬ素子の概略断面構成を示している。
基板１０上には、第１電極１２、発光層を含む有機化合
物層３０、第２電極１６が積層されて素子領域が構成さ
れており、第１電極１２と第２電極１６から電子と正孔
を発光層に注入することで発光層の有機化合物が励起さ
れ、発光が起きる。[Embodiment 1] FIG. 1 shows a schematic sectional configuration of an organic EL device according to Embodiment 1 of the present invention.
An element region is formed by laminating a first electrode 12, an organic compound layer 30 including a light emitting layer, and a second electrode 16 on the substrate 10, and electrons and holes are formed from the first electrode 12 and the second electrode 16. Is injected into the light-emitting layer to excite the organic compound in the light-emitting layer to emit light.
【００３３】図１において最上層に形成された第２電極
１６の上から、つまり、第２電極形成後、基板１０の素
子領域全体を覆って保護膜２０が形成されている。本実
施形態１において、この保護膜２０は、フラン等のヘテ
ロ環式化合物の重合体からなる有機保護膜を用いてい
る。ヘテロ環式化合物は、上記フランの他、ピロール、
チオフェンなどの五員環化合物であり、これらの五員環
化合物の１種類を材料として形成した重合膜でも、複数
種類を材料として形成した共重合膜でもよい。また、保
護膜２０は、単一のヘテロ環式化合物重合膜から構成さ
れるものに限られず、このような重合膜の多層構造であ
ってもよい。また、ヘテロ環式化合物重合膜の形成方法
としては、プラズマ重合、電解重合及び熱重合などがあ
り、特に、プラズマ重合法を用いれば、有機化合物層３
０に悪影響を与えずに簡単に重合薄膜（共重合膜も同
様）を素子領域を覆って形成できる。In FIG. 1, a protective film 20 is formed over the second electrode 16 formed on the uppermost layer, that is, over the entire element region of the substrate 10 after the formation of the second electrode. In the first embodiment, as the protective film 20, an organic protective film made of a polymer of a heterocyclic compound such as furan is used. Heterocyclic compounds, in addition to the furan, pyrrole,
It is a five-membered ring compound such as thiophene, and may be a polymer film formed of one kind of these five-membered ring materials or a copolymer film formed of a plurality of kinds of these materials. Further, the protective film 20 is not limited to a single heterocyclic compound polymer film, and may have a multilayer structure of such a polymer film. Examples of the method for forming the heterocyclic compound polymer film include plasma polymerization, electrolytic polymerization, and thermal polymerization. In particular, when the plasma polymerization method is used, the organic compound layer 3 may be formed.
A polymer thin film (the same applies to a copolymer film) can be easily formed over the element region without adversely affecting 0.
【００３４】フラン重合膜等のヘテロ環式化合物の重合
膜は、ほぼ透明で、空気中の水分や酸素の遮蔽性が高い
ため、有機ＥＬ素子の保護膜として十分な性能を有す
る。A polymer film of a heterocyclic compound such as a furan polymer film is almost transparent and has a high shielding property against moisture and oxygen in the air, and therefore has a sufficient performance as a protective film for an organic EL device.
【００３５】また、このようなヘテロ環式化合物の重合
膜は、有機ＥＬ素子用としては十分な耐熱性（例えば２
００℃程度）を備えると共に、熱伝導度が比較的高く、
有機ＥＬ素子を駆動することで発生するジュール熱は、
容易にこの重合膜へと拡散し、重合膜表面で放熱され
る。このため、素子温度上昇が防がれ温度上昇による有
機化合物層３０の変質などを防いで、素子寿命の向上を
図ることが可能となる。また、カバーガラスや缶パッケ
ージなどの封止筐体が不要であるので、ペルチェ冷却や
空冷ファン冷却などの強制冷却手段を併用すればこのヘ
テロ環化合物重合膜からなる保護膜表面の放熱を促進で
きる。このため、有機ＥＬ素子の冷却をより確実に行う
ことが可能となる。Further, such a polymer film of a heterocyclic compound has sufficient heat resistance (for example, 2
About 00 ° C) and has relatively high thermal conductivity,
Joule heat generated by driving the organic EL element is
It is easily diffused into the polymer film and is radiated on the polymer film surface. For this reason, the temperature rise of the element is prevented, and the deterioration of the organic compound layer 30 due to the temperature rise is prevented, so that the life of the element can be improved. In addition, since a sealed housing such as a cover glass or a can package is not required, the use of forced cooling means such as Peltier cooling or air cooling fan cooling can promote heat radiation on the surface of the protective film made of the heterocyclic compound polymer film. . Therefore, the organic EL element can be cooled more reliably.
【００３６】さらに、フラン重合膜等は、例えばシリコ
ン窒化膜等と比較して、熱応力が小さいため、上述のよ
うに素子駆動によってジュール熱が発生した場合にも、
応力発生によって素子内部等に与える歪みを少なくでき
る。Further, since the furan polymer film or the like has a smaller thermal stress than, for example, a silicon nitride film or the like, even when Joule heat is generated by driving the element as described above,
Distortion applied to the inside of the element or the like due to stress generation can be reduced.
【００３７】また、保護膜２０としてヘテロ環式化合物
の重合膜を用いる場合に、このヘテロ環式化合物材料は
安価で、またプラズマ重合装置など比較的安価な成膜装
置によって成膜できる。When a polymer film of a heterocyclic compound is used as the protective film 20, this heterocyclic compound material can be formed at a low cost and by a relatively inexpensive film forming apparatus such as a plasma polymerization apparatus.
【００３８】［実施形態２］次に本発明の実施形態２に
係る有機ＥＬ素子について図２を用いて説明する。Second Embodiment Next, an organic EL device according to a second embodiment of the present invention will be described with reference to FIG.
【００３９】実施形態１と相違する点は、図２に示すよ
うに、保護膜２０がフラン等のヘテロ環式化合物の重合
体を含む有機保護膜（重合膜）２２と、窒化膜、酸化
膜、カーボン膜又はシリコン膜などの無機保護膜２４と
の積層構造から構成されていることである。The difference from the first embodiment is that, as shown in FIG. 2, the protective film 20 includes an organic protective film (polymer film) 22 containing a polymer of a heterocyclic compound such as furan, a nitride film and an oxide film. , And a laminated structure with an inorganic protective film 24 such as a carbon film or a silicon film.
【００４０】無機保護膜２４は、窒化珪素膜、窒化硼素
膜、窒化アルミニウム膜、酸化珪素膜、酸化アルミニウ
ム膜、酸化チタン膜、ＤＬＣ膜又はアモルファスシリコ
ン膜のいずれかなどから構成することができる。有機保
護膜２２を構成するヘテロ環式化合物は上記フランの
他、ピロール、チオフェンなどの五員環化合物であり、
これらの五員環化合物の１種類を材料として形成した重
合膜でも、複数種類を材料として形成した共重合膜でも
よい。また、ヘテロ環式化合物重合膜の形成方法として
は、プラズマ重合、電解重合及び熱重合があり、特にプ
ラズマ重合法を用いれば、有機化合物層３０に悪影響を
与えずに簡単に重合膜を素子領域を覆って形成できる。
有機保護膜２２を形成後、無機保護膜２４はプラズマＣ
ＶＤ等によって形成される。有機保護２２が形成されて
いるので、一旦空気中に晒してもよく、別のＣＶＤ装置
に搬送し、無機保護膜を作製することができる。また、
ＥＣＲプラズマ等の弱いプラズマにする必要はなく通常
のＲＦプラズマを用いたＣＶＤによって作製が可能であ
る。The inorganic protective film 24 can be composed of any of a silicon nitride film, a boron nitride film, an aluminum nitride film, a silicon oxide film, an aluminum oxide film, a titanium oxide film, a DLC film and an amorphous silicon film. The heterocyclic compound constituting the organic protective film 22 is a five-membered ring compound such as pyrrole and thiophene, in addition to the above-mentioned furan,
A polymer film formed by using one of these five-membered ring compounds as a material or a copolymer film formed by using a plurality of these materials as a material may be used. As a method for forming the heterocyclic compound polymer film, there are plasma polymerization, electrolytic polymerization, and thermal polymerization. In particular, if the plasma polymerization method is used, the polymer film can be easily formed in the element region without adversely affecting the organic compound layer 30. Can be formed.
After forming the organic protective film 22, the inorganic protective film 24 is
It is formed by VD or the like. Since the organic protection layer 22 is formed, the organic protection layer 22 may be once exposed to the air and transported to another CVD device to form an inorganic protective film. Also,
It is not necessary to use weak plasma such as ECR plasma, and it can be produced by CVD using ordinary RF plasma.
【００４１】フラン等のヘテロ環式化合物の重合膜と窒
化珪素膜、酸化珪素膜、ＤＬＣ膜等の無機保護膜の積層
構造体は、透明で、空気中の水分や酸素を積層によって
完全に遮蔽することができ、有機ＥＬ素子の保護膜とし
て十分な性能を有する。The laminated structure of a polymer film of a heterocyclic compound such as furan and an inorganic protective film such as a silicon nitride film, a silicon oxide film and a DLC film is transparent and completely blocks moisture and oxygen in the air by lamination. And has sufficient performance as a protective film of the organic EL element.
【００４２】また、ヘテロ環式化合物の重合膜と窒化珪
素膜、酸化珪素膜、ＤＬＣ膜等の無機保護膜の積層構造
体は、有機ＥＬ素子として十分な耐熱性（例えば２００
℃）を備えるとともに熱伝導率が比較的高く、有機ＥＬ
素子を駆動することで発生するジュール熱は容易に拡散
し、無機保護膜表面で放熱される。このため、素子温度
上昇が防がれ、温度上昇による有機化合物層１４の変質
などを防いで、素子寿命の向上を図ることができる。ま
た、カバーガラスや缶パッケージなど封止筐体を用いて
いないので、直接ペルチェ冷却やファン冷却などの強制
冷却手段を併用すれば、このヘテロ環式化合物の重合膜
と窒化珪素膜、酸化珪素膜、ＤＬＣ膜等の無機保護膜の
積層構造体保護膜表面の放熱を促進することができる。
このため、有機ＥＬ素子の冷却をより確実に行うことが
できる。A laminated structure of a polymer film of a heterocyclic compound and an inorganic protective film such as a silicon nitride film, a silicon oxide film, and a DLC film has sufficient heat resistance (for example, 200 μm) as an organic EL device.
° C) and relatively high thermal conductivity, and organic EL
Joule heat generated by driving the element is easily diffused and radiated on the surface of the inorganic protective film. For this reason, an increase in the temperature of the element is prevented, the deterioration of the organic compound layer 14 due to the increase in the temperature is prevented, and the life of the element can be improved. In addition, since a sealed case such as a cover glass or a can package is not used, if a forced cooling means such as Peltier cooling or fan cooling is used together, a polymer film of the heterocyclic compound, a silicon nitride film, and a silicon oxide film are used. In addition, heat dissipation on the surface of the laminated structure protective film of the inorganic protective film such as a DLC film can be promoted.
Therefore, the organic EL element can be cooled more reliably.
【００４３】さらに、ヘテロ環式化合物の重合膜は、無
機薄膜と比べ熱応力が小さいため、素子駆動によってジ
ュール熱が発生した場合でも、応力を緩和する働きを有
する。また、最表面層は窒化珪素膜、酸化珪素膜、ＤＬ
Ｃ膜等の無機保護膜であるので、物理的にも保護機能を
有している。また、保護膜２０を構成するヘテロ環式化
合物の重合膜及び窒化珪素膜、酸化珪素膜、ＤＬＣ膜等
の無機保護膜は、材料的に安価であり、プロセス的に
も、カバーガラスや缶パッケージなど封止筐体を用いる
封止方法に比べ、安価に製造することができる。Further, the polymer film of the heterocyclic compound has a smaller thermal stress than the inorganic thin film, and therefore has a function of relaxing the stress even when Joule heat is generated by driving the element. The outermost layer is a silicon nitride film, a silicon oxide film, DL
Since it is an inorganic protective film such as a C film, it has a physical protective function. Further, a polymer film of a heterocyclic compound and an inorganic protective film such as a silicon nitride film, a silicon oxide film, and a DLC film, which constitute the protective film 20, are inexpensive in terms of material, and are also process-friendly. It can be manufactured inexpensively as compared with a sealing method using a sealed housing.
【００４４】［実施形態３］上記実施形態２において素
子を覆う保護膜２０は、図２に示すように素子側から有
機保護膜２２及び無機保護膜２４が順に積層された構成
である。これに対し、本実施形態３では、上記実施形態
２とは反対に、素子側に無機保護膜を形成し、これを覆
って有機保護膜を形成する構成を有する。素子領域を覆
って形成された無機保護膜は、実施形態２の有機保護膜
２２上の無機保護膜２４と同様、窒化珪素膜、酸化珪素
膜、アモルファスシリコン膜、カーボン膜等を用いて形
成する。膜厚は５００ｎｍ以下とする。この無機保護膜
２４の形成方法としては、プラズマＣＶＤ法、ＣＶＤ
法、スパッタリング法、ＥＢ蒸着法などがある。素子と
接する側にこのように無機保護膜を設けることによって
有機保護膜の有機物と素子中の有機物とが反応するのを
防ぐことができ、素子劣化の防止が可能である。また、
膜厚を５００ｎｍ以下にすることによって、上述のよう
に素子駆動によってジュール熱が発生した場合にも、応
力によって素子内部等に与える歪みを少なくできる。[Embodiment 3] The protective film 20 covering the element in the above-described embodiment 2 has a structure in which an organic protective film 22 and an inorganic protective film 24 are sequentially laminated from the element side as shown in FIG. On the other hand, in the third embodiment, contrary to the second embodiment, an inorganic protective film is formed on the element side, and an organic protective film is formed to cover the inorganic protective film. The inorganic protective film formed to cover the element region is formed using a silicon nitride film, a silicon oxide film, an amorphous silicon film, a carbon film, or the like, similarly to the inorganic protective film 24 on the organic protective film 22 of the second embodiment. . The thickness is set to 500 nm or less. As a method for forming the inorganic protective film 24, plasma CVD, CVD
Method, sputtering method, EB evaporation method, and the like. By providing such an inorganic protective film on the side in contact with the element, it is possible to prevent the organic substance in the organic protective film from reacting with the organic substance in the element, and to prevent element deterioration. Also,
By setting the film thickness to 500 nm or less, even when Joule heat is generated by driving the element as described above, distortion applied to the inside of the element or the like due to stress can be reduced.
【００４５】また、保護膜が素子側から上記のように無
機保護膜、有機保護膜の順に積層された構造を備え、そ
の有機保護膜の上層、つまり素子領域の最外層に、無機
保護膜（図２の符号２４）を形成した多層（ここでは３
層）構造としても良い。Further, the protective film has a structure in which the inorganic protective film and the organic protective film are laminated in this order from the element side as described above, and the inorganic protective film (the outermost layer in the element region) is formed on the organic protective film. The multilayer (here, 3 in FIG. 2) on which the reference numeral 24 is formed is formed.
It may be a layer) structure.
【００４６】［実施形態４］次に本発明の実施形態４と
して、実施形態２又は３のような保護膜に覆われた有機
ＥＬ素子を製造する装置について図３〜図６を参照して
説明する。図３〜図６に示す各装置に共通する点は、電
極間に有機層を備えて構成される有機ＥＬ素子の各層を
それぞれ成膜する素子成膜室と、少なくとも、有機又は
無機保護膜成膜室のうち少なくとも素子形成領域上に形
成される保護膜用の成膜室とが直接又は搬送用真空室を
介して連結されていることである。なお各室の間には、
各室内を独立させるためゲートバルブが設けられてい
る。このような構成を採用することで、素子を構成する
有機膜形成後に、外気に全くさらされることなく素子領
域を有機保護膜及び無機保護膜で覆うことができ、大気
にされられることで劣化しやすい素子有機膜を確実に保
護することができる。[Embodiment 4] Next, as Embodiment 4 of the present invention, an apparatus for manufacturing an organic EL element covered with a protective film as in Embodiment 2 or 3 will be described with reference to FIGS. I do. A common feature of the devices shown in FIGS. 3 to 6 is that an element film forming chamber for forming each layer of an organic EL element having an organic layer between electrodes is provided, and at least an organic or inorganic protective film forming device. At least a film forming chamber for a protective film formed on the element formation region in the film chamber is connected directly or via a transfer vacuum chamber. In addition, between each room,
A gate valve is provided to make each room independent. By adopting such a configuration, after forming the organic film constituting the element, the element region can be covered with the organic protective film and the inorganic protective film without being exposed to the outside air at all, and is deteriorated by being exposed to the atmosphere. The element organic film which is easy to be protected can be surely protected.
【００４７】図３は、本実施形態４に係る有機ＥＬ素子
の製造装置の第１の例を示している。この第１の例で
は、有機ＥＬ素子部の各膜を形成する成膜室と、保護膜
を形成する成膜室が全て膜形成順に間にゲートバルブ
（以下ＧＶ）を介して連結されたいわゆるインライン構
造を備える。外部より成膜対象である基板を導入する基
板導入室１０１、有機ＥＬ素子の有機層（発光層等）を
成膜する有機薄膜成膜室１０２、Ａｌなどの金属電極か
らなる陰極を成膜する陰極成膜室１０３がそれぞれＧＶ
を介してこの順に連結されている。さらに、陰極成膜室
１０３には、ＧＶを介し、ここでは、素子を覆って先に
形成される無機保護膜用の成膜室２０１が連結され、該
無機保護膜成膜室２０１には、ＧＶを介して有機保護膜
を形成する有機保護膜成膜室２０２が連結されている。
また、有機保護膜成膜室２０２にはさらにＧＶを介して
素子取出室２０３が連結されている。FIG. 3 shows a first example of an organic EL device manufacturing apparatus according to the fourth embodiment. In the first example, a so-called film forming chamber for forming each film of the organic EL element portion and a film forming chamber for forming the protective film are all connected via a gate valve (hereinafter referred to as GV) in the order of film formation. It has an inline structure. A substrate introduction chamber 101 for introducing a substrate to be formed from outside, an organic thin film deposition chamber 102 for forming an organic layer (emission layer, etc.) of an organic EL element, and a cathode made of a metal electrode such as Al are formed. Each of the cathode film forming chambers 103 has a GV
Are connected in this order. Further, a film forming chamber 201 for an inorganic protective film formed first over the element is connected to the cathode film forming chamber 103 via a GV here. An organic protective film forming chamber 202 for forming an organic protective film is connected via a GV.
Further, an element extraction chamber 203 is further connected to the organic protective film deposition chamber 202 via a GV.
【００４８】なお、上記実施形態２のように素子側に先
に有機保護膜２２を形成する場合には、図３において、
陰極成膜室１０３と素子取出室２０３との間の成膜室２
０１、２０２の連結順を逆とする。In the case where the organic protective film 22 is formed first on the element side as in the second embodiment, in FIG.
Film forming chamber 2 between cathode film forming chamber 103 and element extraction chamber 203
The connection order of 01 and 202 is reversed.
【００４９】図３の例において、基板導入室１０１に導
入される基板には既に陽極として機能する透明電極（Ｉ
ＴＯ）が形成されており、基板導入室１０１の室内にこ
の基板を導入した後、図示しない排気手段によって室内
を排気する。室内が十分な真空状態になったところで、
有機薄膜成膜室１０２との間のＧＶを開け、基板を成膜
室１０２に搬送する。ここで、有機薄膜及び陰極はそれ
ぞれ蒸着（もちろんこれには限られないが）によって形
成でき、この場合各成膜室１０２及び１０３は、それぞ
れ蒸着装置によって構成されている。有機薄膜成膜室１
０２では、搬入された基板のＩＴＯの上に、素子構成に
応じて発光層を含む有機膜を順に蒸着形成する。なお、
有機膜が多層（例えば正孔輸送層、発光層、電子輸送層
など）構造である場合には、各層ごとにこの成膜室１０
２が設けられる。成膜室１０２において有機膜を形成し
た後、基板はＧＶを介して陰極成膜室１０３に送られ、
ここで有機膜の上にさらに陰極が形成され、これらの工
程を経て基板上には有機ＥＬ素子部が形成される。In the example of FIG. 3, the substrate introduced into the substrate introduction chamber 101 has a transparent electrode (I) already functioning as an anode.
TO) is formed, and after introducing the substrate into the chamber of the substrate introduction chamber 101, the interior of the chamber is evacuated by exhaust means (not shown). When the room has a sufficient vacuum,
The GV between the organic thin film forming chamber 102 is opened, and the substrate is transferred to the film forming chamber 102. Here, the organic thin film and the cathode can each be formed by vapor deposition (of course, not limited to this), and in this case, each of the film forming chambers 102 and 103 is constituted by a vapor deposition device. Organic thin film deposition chamber 1
In 02, an organic film including a light emitting layer is sequentially deposited and formed on ITO of the loaded substrate according to the element configuration. In addition,
When the organic film has a multilayer structure (for example, a hole transport layer, a light emitting layer, an electron transport layer, etc.), the film forming chamber 10 is provided for each layer.
2 are provided. After forming the organic film in the film forming chamber 102, the substrate is sent to the cathode film forming chamber 103 via the GV,
Here, a cathode is further formed on the organic film, and through these steps, an organic EL element portion is formed on the substrate.
【００５０】次にこの基板はＧＶを介して無機保護膜成
膜室２０１に搬送される。ここで、無機保護膜は、例え
ばプラズマＣＶＤ（化学気相成長）法によって形成する
ことができ、この場合、無機保護膜成膜室２０１は、プ
ラズマＣＶＤ装置によって構成される。ＧＶを介して外
気に晒されることなく陰極成膜室１０３からこの無機保
護膜成膜室２０１に搬入された素子部形成済みの基板に
対し、プラズマＣＶＤによって、該素子領域を覆う窒化
珪素膜などの無機保護膜が形成される。また、無機保護
膜形成後、基板は外気に晒されることなくＧＶを介して
次の有機保護膜成膜室２０２に搬入される。有機保護膜
としてヘテロ環式化合物をプラズマ重合法にて形成する
場合、有機保護膜成膜装置２０２はプラズマ重合装置に
よって構成される。そして、既に素子領域を覆って形成
された無機保護膜を覆ってヘテロ環式化合物のプラズマ
重合膜が有機保護膜として形成される。図３の構成で
は、素子の全ての成膜工程を基板が外気に晒されること
なく連続して実行することができ、有機ＥＬ素子の有機
層の劣化を防止しながら保護膜を形成することができ
る。Next, the substrate is transferred to the inorganic protective film forming chamber 201 via the GV. Here, the inorganic protective film can be formed by, for example, a plasma CVD (chemical vapor deposition) method. In this case, the inorganic protective film forming chamber 201 is configured by a plasma CVD apparatus. A silicon nitride film or the like covering the element region is formed on the substrate on which the element portion has been formed, which is carried into the inorganic protective film deposition chamber 201 from the cathode deposition chamber 103 without being exposed to the outside air through the GV by plasma CVD. Is formed. After the formation of the inorganic protective film, the substrate is carried into the next organic protective film forming chamber 202 via the GV without being exposed to the outside air. When a heterocyclic compound is formed as an organic protective film by a plasma polymerization method, the organic protective film forming apparatus 202 is configured by a plasma polymerization apparatus. Then, a plasma polymerized film of a heterocyclic compound is formed as an organic protective film covering the inorganic protective film already formed covering the element region. In the configuration of FIG. 3, all the film forming steps of the element can be continuously performed without exposing the substrate to the outside air, and the protective film can be formed while preventing the organic layer of the organic EL element from deteriorating. it can.
【００５１】図４に示す有機ＥＬ素子の製造装置の第２
の例では、有機ＥＬ素子部の各膜を形成する成膜室（１
０１，１０２及び１０３）は、上記図３と同様にインラ
イン構造であり、各成膜室が膜形成順にＧＶを介して連
結されている。一方、無機及び有機保護膜の成膜室２０
１及び２０２、及び基板取出室２０３は、共通の搬送用
真空装置２０４にＧＶを介してそれぞれ連結されたいわ
ゆるクラスタ構造となっている。The second embodiment of the organic EL device manufacturing apparatus shown in FIG.
In the example of (1), a film forming chamber (1) for forming each film of the organic EL element portion is formed.
Nos. 01, 102 and 103) have an in-line structure as in FIG. 3, and the respective film forming chambers are connected via GVs in the order of film formation. On the other hand, a film forming chamber 20 for inorganic and organic protective films
1 and 202 and the substrate unloading chamber 203 have a so-called cluster structure connected to a common transfer vacuum device 204 via a GV.
【００５２】また、搬送用真空装置２０４は、ＧＶを介
して陰極成膜室１０３と連結されており、陰極まで形成
された基板は、陰極成膜室１０３からＧＶを介して一旦
搬送用真空装置２０４内に搬入される。保護膜として先
に無機保護膜を形成する場合には、陰極成膜室１０３か
ら搬入された基板は無機保護膜成膜室２０１にＧＶを介
して運ばれる。成膜室２０１で無機保護膜が形成された
後、基板は再び搬送用真空装置２０４に搬入され、次に
この真空装置２０４からＧＶを介して基板は有機保護膜
成膜室２０２に搬入され、ここで有機保護膜が成膜され
る。The transfer vacuum device 204 is connected to the cathode film forming chamber 103 via a GV, and the substrate formed up to the cathode is temporarily transferred from the cathode film formation chamber 103 via the GV to the transfer vacuum device. It is carried into 204. When an inorganic protective film is formed first as a protective film, the substrate carried in from the cathode film forming chamber 103 is transferred to the inorganic protective film forming chamber 201 via a GV. After the inorganic protective film is formed in the film forming chamber 201, the substrate is again carried into the transfer vacuum device 204, and then the substrate is carried from the vacuum device 204 to the organic protective film forming room 202 via the GV, Here, an organic protective film is formed.
【００５３】有機保護膜形成後、基板は再度真空装置２
０４に戻され、その後、基板取出室２０３にＧＶを介し
て送られ、外部に搬出される。このように保護膜の形成
装置部分がクラスタ構造であることから、保護膜とし
て、無機保護膜及び有機保護膜のいずれを先に形成する
プロセスを採用する場合にも、搬送用真空装置２０４か
らの搬送順序を変えるだけで対応できる。従って、例え
ば上記実施形態２及び３のいずれの保護膜積層構造につ
いても図４に示す装置で対応することができる。After the formation of the organic protective film, the substrate is again placed in the vacuum device 2
04, and then sent to the substrate unloading chamber 203 via the GV and carried out. Since the protective film forming apparatus has a cluster structure in this manner, even when a process of forming an inorganic protective film or an organic protective film first is adopted as a protective film, the transfer vacuum device 204 is not used. It can be handled simply by changing the transport order. Therefore, for example, the apparatus shown in FIG. 4 can cope with any of the protective film laminated structures of the second and third embodiments.
【００５４】図５は本実施形態に係る有機ＥＬ素子製造
装置の第３の例を示す。上記第２の例と相違する点は、
有機ＥＬ素子部の各膜の成膜室が搬送用真空装置１０４
にそれぞれＧＶを介して連結されたクラスタ構造が採用
されていることである。また素子成膜側の搬送用真空装
置１０４にはＧＶを介して保護膜形成側の上記図４と同
様の搬送用真空装置２０４が連結されている。図５のよ
うな装置構成とすることで、より一層、形成工程順の変
更に対して許容度の高い製造装置を提供することが可能
となる。FIG. 5 shows a third example of the organic EL device manufacturing apparatus according to this embodiment. The difference from the second example is that
The film forming chamber for each film of the organic EL element portion is provided with a transfer vacuum device 104.
Are connected to each other via a GV. A transfer vacuum device 204 similar to that of FIG. 4 on the protective film formation side is connected to the transfer vacuum device 104 on the element film formation side via a GV. With the apparatus configuration shown in FIG. 5, it is possible to provide a manufacturing apparatus having a higher tolerance to a change in the order of the forming steps.
【００５５】図６は、有機ＥＬ素子の製造装置の第４の
例を示している。この例では、各成膜室が全て共通の搬
送用真空装置３００にそれぞれＧＶを介して連結され、
装置全体がクラスタ構造を備えている。また、図６にお
いて、基板導入室と基板取出室とは共通の室１００とし
て構成することができる。このようなクラスタ構造を採
用することで、製造装置の形成工程変更への許容度は大
きく、さらに、装置の設置面積を縮小することも容易で
ある。FIG. 6 shows a fourth example of an apparatus for manufacturing an organic EL device. In this example, all the film forming chambers are connected to the common transfer vacuum apparatus 300 via the GVs, respectively.
The entire device has a cluster structure. In FIG. 6, the substrate introduction chamber and the substrate unloading chamber can be configured as a common chamber 100. By employing such a cluster structure, the tolerance for changing the manufacturing process of the manufacturing apparatus is large, and the installation area of the apparatus can be easily reduced.
【００５６】以上図４〜６に示したクラスタ構造では、
搬送用真空装置が別途必要となるが、インライン構造の
ように成膜速度の遅い工程により全体の処理速度が律速
されにくく、製造速度を向上することが容易となる。例
えば、図４〜図６の各図において、それぞれの成膜室と
して１室づつ示したが、成膜速度の遅い装置はこれを実
行する部屋を複数設け、それぞれを搬送用真空装置に連
結することが容易である。或いは成膜速度が遅くても、
一度に多数の基板を処理（バッチ処理）できる装置につ
いて、バッチ方式を採用し、成膜速度の差を調整して製
造効率の向上を図ることも可能である。In the cluster structure shown in FIGS.
Although a transfer vacuum device is separately required, the overall processing speed is hardly limited by a process having a low film forming speed, such as an in-line structure, and the manufacturing speed can be easily improved. For example, in each of FIGS. 4 to 6, each of the film forming chambers is shown one by one, but a device having a low film forming speed is provided with a plurality of chambers for performing the film forming, and each of them is connected to a vacuum device for conveyance. It is easy. Or even if the deposition rate is slow,
For an apparatus capable of processing a large number of substrates at one time (batch processing), a batch method can be employed to adjust the difference in film forming speed to improve the manufacturing efficiency.
【００５７】ここで、無機保護膜の製造方法について説
明する。半導体装置などにおいて利用される無機膜とし
て酸化シリコンや窒化シリコン膜などは、スパッタリン
グ法などを用いて形成でき、本発明でも無機保護膜の成
膜法としてスパッタリング法を採用することも可能であ
る。しかし、本発明のように有機ＥＬ素子の保護膜とし
ての無機保護膜は、上述のようにプラズマＣＶＤ方法に
よって成膜することがより好ましい。その理由は、ま
ず、スパッタ法では、半導体デバイスなどと比較して損
傷を受けやすい有機ＥＬ素子に与えるダメージが大き
く、また保護膜の重要な存在意義が外気から素子を遮蔽
することであるにも関わらず、プラズマＣＶＤと比較す
ると得られる膜密度及びカバレッジが劣る為である。Here, a method for manufacturing the inorganic protective film will be described. A silicon oxide film, a silicon nitride film, or the like as an inorganic film used in a semiconductor device or the like can be formed by a sputtering method or the like. In the present invention, a sputtering method can be used as a method of forming an inorganic protective film. However, the inorganic protective film as the protective film of the organic EL element as in the present invention is more preferably formed by the plasma CVD method as described above. The reason is that, first, the sputtering method causes a large damage to the organic EL element which is easily damaged as compared with a semiconductor device or the like, and the important existence significance of the protective film is that the element is shielded from the outside air. Regardless, the obtained film density and coverage are inferior to those of plasma CVD.
【００５８】また、プラズマＣＶＤ方法及びスパッタリ
ング法の成膜レートは、８ｎｍ／ｍｉｎ程度であり、こ
れに対して、有機ＥＬ素子部の有機膜及び陰極の成膜
（蒸着）レートは、１０ｎｍ／ｍｉｎ程度であるが、保
護膜の厚さは、素子の各層の合計膜厚の２倍程度かまた
はそれ以上が要求される場合もある。従って、保護膜を
形成するには、単純に計算しても有機ＥＬ素子部の成膜
時間の２倍以上を要する場合があることになる。プラズ
マＣＶＤは装置内で多数を一度に処理できるが、スパッ
タリング法は１枚毎にしか処理できない。従って、製造
装置として、例えば上記図３のようなインライン方式を
採用した場合はもちろん、図６のようなクラスタ方式を
用いた場合においても、スパッタリング法を用いて無機
保護膜を形成したのでは、この無機保護膜成膜工程が律
速となる（但し、速度だけであれば１装置内にスパッタ
装置のみ複数台並列することで対応することは可能）。
これに対し、プラズマＣＶＤ法では、一度に複数枚を処
理できる。従って、例えば図６の構成において、無機保
護膜成膜室２０１にバッチ式プラズマＣＶＤ装置を採用
することで、成膜速度の差を吸収することが容易とな
る。この場合、搬送用真空装置３００の内部に、真空を
維持しながら（外気に晒されることなく）、プラズマＣ
ＶＤ処理待ちの基板を一時保管する場所を設け、保管場
所に一定数基板がたまったところで、それらを一括して
プラズマＣＶＤ装置内に搬入して各基板に無機保護膜を
一度に形成する。The film forming rate of the plasma CVD method and the sputtering method is about 8 nm / min, whereas the film forming (deposition) rate of the organic film and the cathode of the organic EL element is 10 nm / min. In some cases, the thickness of the protective film is required to be about twice or more the total thickness of each layer of the device. Therefore, in some cases, it takes more than twice as long as the film formation time of the organic EL element portion even if it is simply calculated to form the protective film. Plasma CVD can process a large number of devices at once, but sputtering can only process one by one. Therefore, not only when the in-line method as shown in FIG. 3 is adopted as the manufacturing apparatus but also when the cluster method as shown in FIG. 6 is used, if the inorganic protective film is formed by using the sputtering method, The inorganic protective film forming process is rate-determining (however, if only the speed is used, it is possible to cope with a plurality of sputtering devices in parallel in one device).
On the other hand, the plasma CVD method can process a plurality of sheets at a time. Therefore, for example, in the configuration of FIG. 6, by adopting a batch-type plasma CVD apparatus in the inorganic protective film deposition chamber 201, it becomes easy to absorb the difference in deposition rate. In this case, the plasma C is maintained inside the transfer vacuum device 300 while maintaining the vacuum (without being exposed to the outside air).
A place for temporarily storing substrates waiting for VD processing is provided, and when a certain number of substrates are accumulated in the storage place, they are collectively carried into a plasma CVD apparatus to form an inorganic protective film on each substrate at once.
【００５９】[0059]
【実施例】［実施例１］実施例１として、フラン重合膜
を有機ＥＬ素子の保護膜として用いた場合の具体的な構
成の一例及びその特性について以下に説明する。[Example 1] As Example 1, an example of a specific structure in the case where a furan polymer film is used as a protective film of an organic EL element and its characteristics will be described below.
【００６０】図７は、本実施例１に係る有機ＥＬ素子の
断面構成を表している。この有機ＥＬ素子の素子部分は
ガラス基板１０上に、第１電極（ホール注入電極）１
２、有機化合物層３０、電子注入層１８及び第２電極
（電子注入電極）１６の積層構造で、有機化合物層３０
は第１電極側から順にホール注入層３２、ホール輸送層
３４、有機発光層３６が積層されて構成されている。FIG. 7 shows a cross-sectional structure of the organic EL device according to the first embodiment. The element portion of the organic EL element is provided on a glass substrate 10 with a first electrode (hole injection electrode) 1.
2, the organic compound layer 30, the electron injection layer 18, and the second electrode (electron injection electrode) 16 have a laminated structure,
Is formed by sequentially stacking a hole injection layer 32, a hole transport layer 34, and an organic light emitting layer 36 from the first electrode side.
【００６１】より具体的には、本実施例１では、ガラス
基板１０上に、第１電極１２としてＩＴＯ（Indium Tin
Oxide）を１５０ｎｍ、ホール注入層３２として銅フタ
ロシアニン（ＣｕＰｃ）を１０ｎｍ、ホール輸送層３４
としてトリフェニルアミン４量体（ＴＰＴＥ）を５０ｎ
ｍ、発光層３６としてキノリノールアルミ錯体（Ａｌｑ
3）を６０ｎｍ、電子注入層１８としてフッ化リチウム
（ＬｉＦ）を０．５ｎｍ、第２電極１６としてアルミニ
ウム（Ａｌ）を１００ｎｍ形成した。なお、ＩＴＯは、
ＩＴＯが予め形成されているガラス基板を用い、ＩＴＯ
以外の各層は、真空蒸着法によりそれぞれ同じ場所（in
-situ）に重ねて形成した。More specifically, in the first embodiment, an ITO (Indium Tin) is formed on the glass substrate 10 as the first electrode 12.
Oxide) is 150 nm, copper phthalocyanine (CuPc) is 10 nm as the hole injection layer 32, and the hole transport layer 34 is
50n of triphenylamine tetramer (TPTE)
m, quinolinol aluminum complex (Alq
3 ) 60 nm, lithium fluoride (LiF) 0.5 nm as the electron injection layer 18, and aluminum (Al) 100 nm as the second electrode 16. In addition, ITO
Using a glass substrate on which ITO is formed in advance, ITO
Layers except for the same place (in
-situ).
【００６２】第２電極１６を形成した後、本実施例１
は、有機ＥＬ素子の保護膜２０として、フラン重合膜を
プラズマ重合法によって形成した。フラン重合膜成膜中
のフランモノマー圧力は２００mTorr（１Torr≒１３３p
a）、フランモノマー流量２０sccm（standard cc per m
inute）、プラズマ投入電力２０Ｗとし、基板温度は室
温に設定してフラン重合膜を２μｍの厚さ形成した。After forming the second electrode 16, the first embodiment
Formed a furan-polymerized film by a plasma polymerization method as the protective film 20 of the organic EL element. The furan monomer pressure during the formation of the furan polymer film is 200 mTorr (1 Torr @ 133p)
a), furan monomer flow rate 20sccm (standard cc per m
inute), the plasma input power was 20 W, the substrate temperature was set to room temperature, and a furan polymer film was formed to a thickness of 2 μm.
【００６３】また、比較例として、図９に示すように、
有機ＥＬ素子構成は図３の実施例と同じで、フラン重合
膜ではなく、第２電極形成後、素子を乾燥窒素雰囲気中
に置いて、第２電極側からカバーガラスを被せ、基板１
０にこのカバーガラスを接着して封止した素子を作製し
た。As a comparative example, as shown in FIG.
The structure of the organic EL device is the same as that of the embodiment of FIG. 3. Instead of forming a furan polymer film, after forming the second electrode, the device is placed in a dry nitrogen atmosphere, and a cover glass is covered from the second electrode side.
In this way, an element in which the cover glass was adhered and sealed at 0 was produced.
【００６４】本実施例１に係る有機ＥＬ素子は、大気中
に１ヶ月以上放置しても駆動の有無に関わらずダークス
ポットの増加は見られなかった。このため有機ＥＬ素子
の保護膜２０として、フラン重合膜は、空気中の水分や
酸素に対する遮蔽性が十分高く、保護膜として十分な機
能を有していることが分かった。In the organic EL device according to Example 1, no increase in dark spots was observed even when the organic EL device was left in the air for one month or more, regardless of whether the device was driven. For this reason, it was found that the furan polymerized film as the protective film 20 of the organic EL element had sufficiently high shielding properties against moisture and oxygen in the air, and had a sufficient function as a protective film.
【００６５】実施例１に係る有機ＥＬ素子の保護膜２０
の表面、及び比較例の有機ＥＬ素子のカバーガラス側
に、それぞれ熱伝導性グリース等でペルチェ素子の冷却
側を貼り付け、実施例及び比較例の有機ＥＬ素子を駆動
し冷却効果を評価した。ペルチェ素子には１Ａの一定電
流を流すことにより、実施例及び比較例を一定の冷却状
態に保ち、この条件下で有機ＥＬ素子を初期輝度２４０
０cd/m2にて定電流駆動し、輝度の時間変化を測定し
た。The Protective Film 20 of the Organic EL Device According to Example 1
The cooling side of the Peltier device was adhered to the surface of the Peltier device and the cover glass side of the organic EL device of the comparative example with heat conductive grease, respectively, and the organic EL devices of the example and the comparative example were driven to evaluate the cooling effect. A constant current of 1 A was applied to the Peltier device to keep the example and the comparative example in a constant cooling state.
A constant current drive was performed at 0 cd / m 2 , and the time change of luminance was measured.
【００６６】その結果、実施例１及び比較例の有機ＥＬ
素子の半減寿命（輝度が初期輝度の半分、ここでは１２
００cd/m2となるまでの時間）は、それぞれ、１５０時
間、１００時間であり、実施例１の素子において半減寿
命が延びていることが分かった。As a result, the organic ELs of Example 1 and Comparative Example
The half life of the device (the brightness is half of the initial brightness, here 12
(Time required to reach 00 cd / m 2 ) was 150 hours and 100 hours, respectively, and it was found that the device of Example 1 had a longer half-life.
【００６７】このことから、本実施例１のようにフラン
重合膜などを保護膜として用いることにより、大きな冷
却効果が得られ、素子の温度上昇による劣化が抑えられ
て素子寿命を延ばすことが可能であることが分かった。Thus, by using a furan polymer film or the like as the protective film as in the first embodiment, a large cooling effect can be obtained, and deterioration due to a rise in temperature of the element can be suppressed to extend the life of the element. It turned out to be.
【００６８】なお、有機ＥＬ素子部の構成は、図７のよ
うな構成に限らず、例えば、電子注入層やホール注入層
を設けない構成等、様々な例が考えられ、いずれの素子
でも上記実施例のようなフラン重合膜を保護膜として用
いることで同様の効果が得られる。The configuration of the organic EL element section is not limited to the configuration shown in FIG. 7, and various examples are conceivable, such as a configuration in which an electron injection layer and a hole injection layer are not provided. The same effect can be obtained by using a furan polymer film as in the embodiment as a protective film.
【００６９】［実施例２］実施例２として、有機保護膜
にフラン重合膜、無機保護膜に窒化珪素膜を採用した積
層構造体を有機ＥＬ素子の保護膜として用いた場合の具
体的な構成の一例及びその特性について以下に説明す
る。Example 2 As Example 2, a specific configuration in which a laminated structure employing a furan polymer film as an organic protective film and a silicon nitride film as an inorganic protective film was used as a protective film for an organic EL device. An example and its characteristics will be described below.
【００７０】図８は本実施例に係る有機ＥＬ素子の断面
構成を表している。この有機ＥＬ素子の素子部分は上記
実施例１と同じで、ガラス基板１０上に、第１電極（ホ
ール注入電極）１２、有機化合物層３０、電子注入層１
８及び第２電極（電子注入電極）１６の積層構造で、有
機化合物層３０は、第１電極側から順にホール注入層３
２、ホール輸送層３４、有機発光層３６が積層されて構
成されている。FIG. 8 shows a cross-sectional structure of the organic EL device according to this embodiment. The element portion of this organic EL element is the same as that of the first embodiment, and a first electrode (hole injection electrode) 12, an organic compound layer 30, and an electron injection layer 1 are formed on a glass substrate 10.
8 and a second electrode (electron injection electrode) 16 having a laminated structure, the organic compound layer 30 is formed of the hole injection layer 3 in order from the first electrode side.
2, a hole transport layer 34 and an organic light emitting layer 36 are laminated.
【００７１】より具体的には、本実施例では、ガラス基
板上に第１電極１２としてＩＴＯ（Indium Tin Oxide）
を１５０ｎｍ、ホール注入層として銅フタロシアニン
（ＣｕＰc）を１０ｎｍ、ホール輸送層としてトリフェ
ニルアミン４量体を５０ｎｍ、発光層３６としてキノリ
ノールアルミ錯体（Alq3）を６０ｎｍ、電子注入層とし
てフッ化リチウム（LiF）を０．５ｎｍ、第２電極とし
てアルミニウム（Al）を１００ｎｍ形成した。なお、Ｉ
ＴＯは、ＩＴＯがあらかじめ形成されているガラス基板
を用い、ＩＴＯ以外の各層は真空蒸着法によりそれぞれ
同じ場所（in-situ）に重ねて蒸着した。More specifically, in the present embodiment, ITO (Indium Tin Oxide) is used as the first electrode 12 on the glass substrate.
Is 150 nm, copper phthalocyanine (CuPc) is 10 nm as the hole injection layer, triphenylamine tetramer is 50 nm as the hole transport layer, quinolinol aluminum complex (Alq 3 ) is 60 nm as the light emitting layer 36, and lithium fluoride (Alq 3 ) is used as the electron injection layer. LiF) was formed to a thickness of 0.5 nm, and aluminum (Al) was formed to a thickness of 100 nm as a second electrode. Note that I
As for TO, a glass substrate on which ITO was formed in advance was used, and layers other than ITO were deposited on the same place (in-situ) by vacuum deposition.
【００７２】第２電極１６を形成した後、本実施例は、
有機ＥＬ素子の保護膜２０として、フラン重合膜２２を
プラズマ重合法によって形成した。フラン重合膜成膜中
のフランモノマー圧力は２００mTorr、フランモノマー
流量２０sccm、プラズマ投入電力２０Ｗとし、基板温度
は室温に設定しフラン重合膜２２を２μｍの厚さ形成し
た。さらに、フラン重合膜２２が形成された有機ＥＬ素
子を、プラズマＣＶＤ装置にセットし、基板温度１００
℃、プラズマ投入電力１０Ｗとし、シラン、アンモニア
及び窒素を導入し、窒化珪素膜２４を１μｍの厚さ形成
した。After forming the second electrode 16, the present embodiment
As the protective film 20 of the organic EL element, a furan polymer film 22 was formed by a plasma polymerization method. During the formation of the furan polymer film, the furan monomer pressure was 200 mTorr, the flow rate of the furan monomer was 20 sccm, the plasma input power was 20 W, the substrate temperature was set to room temperature, and the furan polymer film 22 was formed to a thickness of 2 μm. Further, the organic EL element on which the furan polymer film 22 was formed was set in a plasma CVD apparatus, and the substrate temperature was set to 100 ° C.
C., a plasma input power of 10 W, silane, ammonia and nitrogen were introduced to form a silicon nitride film 24 having a thickness of 1 μm.
【００７３】比較例は、上記実施例１において比較例と
して説明した有機ＥＬ素子を用いた（図９参照）。In the comparative example, the organic EL device described as a comparative example in Example 1 was used (see FIG. 9).
【００７４】本実施例２に係る有機ＥＬ素子は、大気中
に１ヶ月以上放置しても、素子にダークスポットは見ら
れず、空気中の水分や酸素に対し遮蔽性が高いことが示
された。また、本実施例において、保護膜２０と素子領
域の間、特に重合膜２２と素子領域の間に膜厚１００ｎ
ｍの窒化珪素膜もしくは酸化珪素膜もしくはアモルファ
スシリコン膜もしくはカーボン膜を、プラズマＣＶＤ法
により形成することで、さらに長期間ダークスポットの
増加は見られなかった。すなわち、このような無機層を
設けることによって保護膜中の有機物と素子中の有機物
とが反応するのを防ぐことができることが分かった。The organic EL device according to Example 2 did not show dark spots even after being left in the air for one month or more, indicating that the device has a high shielding property against moisture and oxygen in the air. Was. Further, in this embodiment, a film thickness of 100 nm is formed between the protective film 20 and the element region, particularly, between the polymer film 22 and the element region.
By forming a silicon nitride film, a silicon oxide film, an amorphous silicon film, or a carbon film of m by the plasma CVD method, no increase in dark spots was observed for a longer period. That is, it was found that by providing such an inorganic layer, it was possible to prevent the organic substance in the protective film from reacting with the organic substance in the element.
【００７５】また、実施例２に係る有機ＥＬ素子の保護
膜２０の表面、及び比較例の有機ＥＬ素子のカバーガラ
スに熱伝導性グリースでペルチェ素子の冷却側を取り付
け、実施例及び比較例の有機ＥＬ素子を駆動し、冷却効
果を調べた。ペルチェ素子には一定電流を流すことによ
り、実施例及び比較例を一定の冷却状態に保ち、この条
件下で有機ＥＬ素子を初期輝度２４００cd/m2にて低電
流駆動し、輝度の時間変化を測定した。Further, the cooling side of the Peltier element was attached to the surface of the protective film 20 of the organic EL element according to Example 2 and the cover glass of the organic EL element of Comparative Example with thermal conductive grease. The organic EL element was driven and the cooling effect was examined. By applying a constant current to the Peltier element, the embodiment and the comparative example were kept in a constant cooling state. Under this condition, the organic EL element was driven at a low current at an initial luminance of 2400 cd / m 2 , and the time change of the luminance was observed. It was measured.
【００７６】その結果、実施例２及び比較例の有機ＥＬ
素子の半減寿命は、それぞれ、１５０時間、１００時間
であり、実施例の素子において半減寿命が延びているこ
とが分かった。As a result, the organic EL devices of Example 2 and Comparative Example
The half-life of the device was 150 hours and 100 hours, respectively, and it was found that the half-life was extended in the device of Example.
【００７７】さらに、本実施例について、室温と１００
℃のサイクル試験を２０回行い、素子特性を調べたが正
常に動作した。比較例では、非発光部が生じ、劣化し
た。Further, in the present embodiment, the room temperature and 100
The cycle test at 20 ° C. was performed 20 times, and the device characteristics were examined. In the comparative example, a non-light emitting portion was generated and deteriorated.
【００７８】このことから、本実施例のように、フラン
重合膜と窒化珪素膜からなる積層構造等を保護膜として
用いることにより、大きな冷却効果が得られ、素子の温
度上昇による劣化が抑えられて素子寿命を延ばすことが
できることが分かった。From the above, by using a laminated structure including a furan polymer film and a silicon nitride film as a protective film as in this embodiment, a large cooling effect can be obtained, and deterioration due to an increase in the temperature of the element can be suppressed. It was found that the device life could be extended.
【００７９】なお、有機ＥＬ素子部の構成は、図８のよ
うな構成に限らず、例えば電子注入層やホール注入層を
設けない構成、また、高分子化合物層を形成する構成
等、様々な例が考えられ、いずれの場合にも上記実施例
のようなフラン重合膜を保護膜として用いることで同様
の効果を得ることができる。The configuration of the organic EL element portion is not limited to the configuration shown in FIG. 8, and various configurations such as a configuration in which an electron injection layer and a hole injection layer are not provided, a configuration in which a polymer compound layer is formed, and the like. Examples are conceivable, and in any case, similar effects can be obtained by using a furan polymer film as in the above-described embodiment as a protective film.
【００８０】また、フラン重合膜の代わりに、ピロール
重合膜、チオフェン重合膜を、窒化珪素膜の代わりに酸
化珪素膜、ＤＬＣ膜を積層した構造体による保護膜の場
合でも、同様な効果が得られた。The same effect can be obtained when a pyrrole polymer film or a thiophene polymer film is used instead of the furan polymer film, and a silicon oxide film or a DLC film is used instead of the silicon nitride film. Was done.
【００８１】［実施例３］実施例３では、まずガラス基
板上に有機ＥＬ素子を成膜し、次に有機ＥＬ素子全体を
覆うように無機保護膜を真空一環で形成し、最後に有機
化合物のプラズマ重合膜を同じく真空一環で形成した。
なお、素子構成は、上述の図８において有機保護膜２２
を無機保護膜とし、無機保護膜２４を有機保護膜とした
ものと同じである。Example 3 In Example 3, first, an organic EL element was formed on a glass substrate, then an inorganic protective film was formed so as to cover the entire organic EL element in a vacuum, and finally, an organic compound was formed. Was formed in the same vacuum.
The element configuration is the same as that of the organic protective film 22 shown in FIG.
Is an inorganic protective film, and the inorganic protective film 24 is the same as an organic protective film.
【００８２】本実施例３で用いた有機ＥＬ素子はガラス
基板の上にホール注入電極、ホール注入層、ホール輸送
層、発光層、電子注入層、電子注入電極を積層させた構
造とした（但し、本発明が実際に適用される有機ＥＬ素
子はこのような構造でなくてもよく、例えば電子注入層
やホール注入層のない構造など様々な構造のものが考え
られる）。本実施例３では、ホール注入電極としてＩＴ
Ｏ、ホール注入層として銅フタロシアニン（ＣｕＰ
ｃ）、ホール輸送層としてトリフェニルアミン４量体
（ＴＰＴＥ）、発光層としてキノリノールアルミ錯体
（Alq3）、電子注入層としてフッ化リチウム（Ｌｉ
Ｆ）、電子注入電極としてアルミニウム（Ａｌ）を用い
た。成膜は、ＩＴＯ以外は真空蒸着法によりin-situで
行った。なお、ＩＴＯは基板として市販されているもの
を用いた。また、各層の膜厚はＩＴＯ：１５０ｎｍ、銅
フタロシアニン：１０ｎｍ、トリフェニルアミン４量
体：５０ｎｍ、キノリノールアルミ錯体：６０ｎｍ、フ
ッ化リチウム：０．５ｎｍ、Ａｌ：１００ｎｍとした。The organic EL device used in Example 3 had a structure in which a hole injection electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron injection electrode were laminated on a glass substrate (however, The organic EL device to which the present invention is actually applied may not have such a structure, and various structures such as a structure without an electron injection layer or a hole injection layer are conceivable. In the third embodiment, an IT is used as a hole injection electrode.
O, copper phthalocyanine (CuP
c), triphenylamine tetramer (TPTE) as a hole transport layer, quinolinol aluminum complex (Alq 3 ) as a light emitting layer, and lithium fluoride (Li) as an electron injection layer.
F) Aluminum (Al) was used as the electron injection electrode. The film was formed in-situ by a vacuum deposition method except for ITO. The ITO used was a commercially available substrate. The thickness of each layer was ITO: 150 nm, copper phthalocyanine: 10 nm, triphenylamine tetramer: 50 nm, quinolinol aluminum complex: 60 nm, lithium fluoride: 0.5 nm, and Al: 100 nm.
【００８３】本実施例３では、無機保護膜としてシリコ
ン窒化膜をプラズマＣＶＤ装置にて作成した。無機保護
膜としては窒化シリコン膜の他に酸化シリコン膜、窒酸
化シリコン膜、ＤＬＣ膜（ダイアモンド状カーボン
膜）、アモルファスカーボン膜、酸化アルミニウム膜、
アモルファスシリコン膜等があげられる。また成膜装置
として、プラズマＣＶＤ装置の他にＣＶＤ装置、真空蒸
着装置、スパッタ装置、ＡＬＥ装置等があげられる（但
し、上述の通りスパッタよりもＣＶＤ或いは真空蒸着法
がより優れている）。原料ガスとしてＳｉＨ4、ＮＨ3、
Ｎ2を用い、成膜中の真空度は４００mTorr、プラズマ投
入電力は１０Ｗ、基板温度は１００℃の条件にて成膜を
行った。シリコン窒化膜の膜厚は２００ｎｍとした。ま
た、有機化合物のプラズマ重合膜としてフランプラズマ
重合膜をプラズマ重合装置にて作製した。プラズマ重合
膜としてはヘテロ環式化合物の重合膜が望ましい。さら
に該ヘテロ環式化合物は五員環化合物が望ましい。さら
には該五員環化合物はフラン、ピロール、チオフェンの
いずれかの重合体または２つ以上を含む重合体であるこ
とが望ましい。成膜中のフランモノマー圧力は２００mT
orr、フランモノマー流量２０sccm、プラズマ投入電力
２０Ｗ、基板温度は室温の条件にて成膜を行った。フラ
ン重合膜の膜厚は２μｍとした。In the third embodiment, a silicon nitride film was formed as an inorganic protective film using a plasma CVD apparatus. As an inorganic protective film, in addition to a silicon nitride film, a silicon oxide film, a silicon oxynitride film, a DLC film (diamond-like carbon film), an amorphous carbon film, an aluminum oxide film,
An amorphous silicon film or the like can be given. Examples of the film forming apparatus include a CVD apparatus, a vacuum evaporation apparatus, a sputtering apparatus, and an ALE apparatus in addition to the plasma CVD apparatus (however, as described above, the CVD or the vacuum evaporation method is superior to the sputtering method). SiH 4 , NH 3 ,
Using N 2 , the film was formed under the conditions of a vacuum degree of 400 mTorr, a plasma input power of 10 W, and a substrate temperature of 100 ° C. during the film formation. The thickness of the silicon nitride film was 200 nm. Further, a furan plasma polymerized film was prepared as a plasma polymerized film of an organic compound using a plasma polymerization apparatus. As the plasma polymerized film, a polymerized film of a heterocyclic compound is preferable. Further, the heterocyclic compound is preferably a five-membered ring compound. Further, the five-membered ring compound is preferably a polymer of one of furan, pyrrole, and thiophene, or a polymer containing two or more. Furan monomer pressure during film formation is 200mT
Film formation was performed under the conditions of orr, a flow rate of furan monomer of 20 sccm, plasma input power of 20 W, and a substrate temperature of room temperature. The thickness of the furan polymerized film was 2 μm.
【００８４】比較例１として有機ＥＬ素子作成後、一旦
大気に晒した後、シリコン窒化膜およびフランプラズマ
重合膜を真空一環で形成した。また、比較例２として有
機ＥＬ素子およびシリコン窒化膜を真空一環で形成した
後、一旦大気に晒した後、フランプラズマ重合膜を成膜
した。As Comparative Example 1, after the organic EL device was prepared, it was once exposed to the air, and then a silicon nitride film and a furan plasma polymerized film were formed in a vacuum. Further, as Comparative Example 2, an organic EL element and a silicon nitride film were formed in a vacuum, and once exposed to the atmosphere, a furan plasma polymerized film was formed.
【００８５】このようにして作製された実施例および比
較例１、比較例２を８５℃の高温下で初期輝度４００ｃ
ｄ／ｍ2にて定電流駆動を行い、５００時間後の発光面
を観察した。実施例３ではダークスポットは１０個／ｃ
ｍ2以下と少なく、しかもそのサイズは全て１００μｍ
以下であった。これに対して比較例１ではダークスポッ
トは２５０個／ｃｍ2と多く、そのサイズは５０％以上
が１００μｍ以上であり５００μｍ以上のものも存在し
た。また、比較例２ではダークスポットは５０個／ｃｍ
2とそれほど多くなかったが、剥離する場所が存在した
り、パーティクルによる巨大なダークスポットが発生し
たり不安定な特性であった。すなわち、本特許にある装
置を用いることにより、高温において耐久性及び良好な
ダークスポット特性双方を兼ね備えたような保護膜を得
ることが可能であることが示された。The thus manufactured Examples and Comparative Examples 1 and 2 were tested at a high temperature of 85.degree.
A constant current drive was performed at d / m 2 , and the light emitting surface after 500 hours was observed. In Example 3, the number of dark spots was 10 / c.
m 2 or less and less, yet all its size 100μm
It was below. On the other hand, in Comparative Example 1, the number of dark spots was as large as 250 spots / cm 2, and the size was 50 μm or more, 100 μm or more, and 500 μm or more. In Comparative Example 2, the number of dark spots was 50 / cm.
Although it was not as many as 2 , it had unstable properties such as exfoliation areas, huge dark spots due to particles, and the like. That is, it was shown that by using the apparatus described in this patent, it is possible to obtain a protective film having both durability and good dark spot characteristics at high temperatures.
【００８６】また、本実施例３において、素子側に形成
した無機保護膜の膜厚を１００ｎｍ程度とし、これを覆
って有機保護膜を形成し、さらにこの有機保護膜を覆っ
て無機保護膜を形成した構成においても、長期間ダーク
スポットの増加は見られなかった。従って、保護膜を素
子側及び最外側側がそれぞれ無機保護膜とする３層構造
とすることで、保護膜中の有機物と素子中の有機物との
反応を防ぎ、かつ放熱効果の向上を図ることができる。Further, in Example 3, the thickness of the inorganic protective film formed on the element side was set to about 100 nm, an organic protective film was formed so as to cover the same, and the inorganic protective film was further formed so as to cover the organic protective film. Even in the formed configuration, no increase in dark spots was observed for a long period of time. Therefore, by forming the protective film into a three-layer structure in which the element side and the outermost side are each an inorganic protective film, it is possible to prevent a reaction between an organic substance in the protective film and an organic substance in the element, and to improve a heat radiation effect. it can.
【００８７】[0087]
【発明の効果】以上説明したように、この発明によれ
ば、有機ＥＬ素子の素子領域をヘテロ環式化合物の重合
膜を含む保護膜によって覆うので、素子領域を空気中の
水分や酸素から確実に遮蔽でき、かつ、この重合膜の熱
伝導度が比較的高いので、駆動により発熱する有機ＥＬ
素子冷却効果が高い。さらに、このような重合膜を有す
る保護膜は低コストで成膜することができる。As described above, according to the present invention, the device region of the organic EL device is covered with the protective film including the polymer film of the heterocyclic compound, so that the device region is reliably protected from moisture and oxygen in the air. Organic EL that generates heat when driven because the polymer film has relatively high thermal conductivity
High element cooling effect. Further, a protective film having such a polymer film can be formed at low cost.
【００８８】また、保護膜として、上記のような重合体
を含む有機保護膜に加え、さらに窒化珪素膜、酸化珪素
膜、又はＤＬＣ膜等の無機保護膜を用いることによって
も優れた冷却効果と、有機ＥＬ素子領域を水分、酸素か
ら遮蔽する効果が得られる。保護膜が積層構造体である
ためプロセス上重合膜にピンホールが存在したり無機保
護膜として例えば窒化珪素膜に粒界が発生している場合
でも、互いの膜構造の欠陥を相補するので非常に優れた
遮蔽性を発揮することが可能となる。また、有ＥＬ素子
は有機薄膜を有し、応力に弱く熱サイクル等によって歪
みがかかると剥離などの問題を起こしやすいが、重合膜
と無機保護膜の積層構造とすることで、素子最外部は強
固なガラス基板と窒化珪素膜等で覆うこととなり、一方
内部はプラズマ重合膜の比較的柔軟な膜が存在すること
となり、耐久性の向上に寄与することができる。Further, by using an inorganic protective film such as a silicon nitride film, a silicon oxide film or a DLC film in addition to the above-mentioned organic protective film containing a polymer as the protective film, an excellent cooling effect can be obtained. The effect of shielding the organic EL element region from moisture and oxygen can be obtained. Since the protective film is a laminated structure, even if a pinhole is present in the polymerized film in the process or even if a grain boundary is generated in the silicon nitride film as an inorganic protective film, for example, defects in the film structure of each other are complemented. It is possible to exhibit excellent shielding properties. In addition, the EL device has an organic thin film, and is susceptible to stress and is liable to cause problems such as peeling when subjected to distortion due to thermal cycling or the like, but the outermost portion of the device has a laminated structure of a polymer film and an inorganic protective film. It is covered with a strong glass substrate and a silicon nitride film or the like. On the other hand, a relatively flexible film of a plasma polymerized film exists inside, which can contribute to improvement in durability.
【００８９】さらに、このような有機ＥＬ素子の製造装
置として、素子形成部と保護膜形成部とを直接又は搬送
用真空室を介して連結することで、形成した素子を大気
に晒すことなく保護膜を形成することができ、一層の素
子寿命向上を図ることができる。Further, in such an apparatus for manufacturing an organic EL element, the element forming section and the protective film forming section are connected directly or via a transfer vacuum chamber to protect the formed element without exposing it to the atmosphere. A film can be formed, and the element life can be further improved.
【図１】 本発明の実施形態１に係る有機ＥＬ素子の概
略断面構成を示す図である。FIG. 1 is a diagram showing a schematic cross-sectional configuration of an organic EL device according to a first embodiment of the present invention.
【図２】 本発明の実施形態２に係る有機ＥＬ素子の概
略断面構成を示す図である。FIG. 2 is a diagram illustrating a schematic cross-sectional configuration of an organic EL device according to a second embodiment of the present invention.
【図３】 本発明の有機ＥＬ素子製造装置の第１の例を
示す図である。FIG. 3 is a view showing a first example of an organic EL device manufacturing apparatus of the present invention.
【図４】 本発明の有機ＥＬ素子製造装置の第２の例を
示す図である。FIG. 4 is a view showing a second example of the organic EL device manufacturing apparatus of the present invention.
【図５】 本発明の有機ＥＬ素子製造装置の第３の例を
示す図である。FIG. 5 is a diagram showing a third example of the organic EL device manufacturing apparatus of the present invention.
【図６】 本発明の有機ＥＬ素子製造装置の第４の例を
示す図である。FIG. 6 is a view showing a fourth example of the organic EL device manufacturing apparatus of the present invention.
【図７】 実施例１に係る有機ＥＬ素子の概略断面構成
を示す図である。FIG. 7 is a view showing a schematic cross-sectional configuration of the organic EL element according to Example 1.
【図８】 実施例２に係る有機ＥＬ素子の概略断面構成
を示す図である。FIG. 8 is a view showing a schematic sectional configuration of an organic EL element according to Example 2.
【図９】 比較例に係る有機ＥＬ素子の概略断面構成を
示す図である。FIG. 9 is a diagram illustrating a schematic cross-sectional configuration of an organic EL element according to a comparative example.
１０ ガラス基板、１２ 第１電極、１６ 第２電極、
１８ 電子注入層、２０ 保護膜、２２ 有機保護膜
（重合膜，ヘテロ環式化合物）、２４ 無機保護膜（窒
化珪素膜、酸化珪素膜もしくはＤＬＣ膜等）、３０ 有
機化合物層、３２ホール注入層、３４ ホール輸送層、
３６ 有機発光層、１００ 基板導入・取出室、１０１
基板導入室、１０２ 有機薄膜成膜室、１０３ 陰極
成膜室、１０４，２０４，３００ 搬送用真空装置、２
０１ 無機保護膜成膜室、２０２有機保護膜成膜室、２
０３ 基板取出室。10 glass substrate, 12 first electrode, 16 second electrode,
18 electron injection layer, 20 protective film, 22 organic protective film (polymer film, heterocyclic compound), 24 inorganic protective film (silicon nitride film, silicon oxide film or DLC film, etc.), 30 organic compound layer, 32 hole injection layer , 34 hole transport layer,
36 organic light emitting layer, 100 substrate introduction / extraction room, 101
Substrate introduction chamber, 102 Organic thin film deposition chamber, 103 Cathode deposition chamber, 104, 204, 300 Vacuum device for transport, 2
01 Inorganic protective film deposition chamber, 202 Organic protective film deposition chamber, 2
03 Substrate unloading room.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大脇 健史 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 多賀 康訓 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 Ｆターム(参考） 3K007 AB11 AB13 AB14 AB18 BB00 CA01 CB01 DA01 DB03 EA01 EB00 FA01 FA02 4K029 AA09 AA24 BC07 BD00 CA12 GA03 KA09 4K030 BA02 BA28 BA30 BA38 BA39 BA40 BA43 BA46 CA06 CA12 DA02 FA01 LA18 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeshi Owaki Takeuchi Ochimichi, Aichi-gun, Aichi-gun No. 41 at Yokomichi 1 F-term in Toyota Central R & D Laboratories Co., Ltd. F-term (reference) CA12 DA02 FA01 LA18
Claims (14)
域と、 該素子領域を覆って形成された保護膜と、を備え、 前記保護膜はヘテロ環式化合物の重合体を含む有機保護
膜を有することを特徴とする有機電界発光素子。1. An organic electroluminescent device, comprising: an element region having at least one organic compound layer between electrodes; and a protective film formed to cover the element region, wherein the protective film is a heterocyclic type. An organic electroluminescent device having an organic protective film containing a polymer of a compound.
いて、 前記ヘテロ環式化合物は、五員環化合物であることを特
徴とする有機電界発光素子。2. The organic electroluminescent device according to claim 1, wherein the heterocyclic compound is a five-membered ring compound.
発光素子において、 前記ヘテロ環式化合物の重合体は、フラン、ピロール、
チオフェンのいずれかの重合体又は２つ以上を含む共重
合体であることを特徴とする有機電界発光素子。3. The organic electroluminescent device according to claim 1, wherein the polymer of the heterocyclic compound is furan, pyrrole,
An organic electroluminescent device, which is any polymer of thiophene or a copolymer containing two or more thiophenes.
有機電界発光素子において、 前記有機保護膜は、前記ヘテロ環式化合物をプラズマ重
合して得た重合膜を有することを特徴とする有機電界発
光素子。4. The organic electroluminescent device according to claim 1, wherein the organic protective film has a polymer film obtained by plasma-polymerizing the heterocyclic compound. Organic electroluminescent device.
有機電界発光素子において、 前記保護膜は、前記有機保護膜と、無機保護膜とを含む
積層構造であることを特徴とする有機電界発光素子。5. The organic electroluminescent device according to claim 1, wherein the protective film has a laminated structure including the organic protective film and an inorganic protective film. Organic electroluminescent device.
いて、 前記無機保護膜は、窒化膜又は酸化膜又は炭素膜又はシ
リコン膜のいずれかを含むことを特徴とする有機電界発
光素子。6. The organic electroluminescent device according to claim 5, wherein the inorganic protective film includes one of a nitride film, an oxide film, a carbon film, and a silicon film.
いて、 前記有機保護膜は、ヘテロ環式化合物をプラズマ重合し
て得られた重合膜であり、 前記無機保護膜は、窒化珪素膜、窒化硼素膜、窒化アル
ミニウム膜、酸化珪素膜、酸化アルミニウム膜、酸化チ
タン膜、アモルファスシリコン膜又はダイアモンド状カ
ーボン膜のいずれかであり、プラズマＣＶＤ法によって
形成された膜であることを特徴とする有機電界発光素
子。7. The organic electroluminescent device according to claim 6, wherein the organic protective film is a polymer film obtained by plasma-polymerizing a heterocyclic compound, wherein the inorganic protective film is a silicon nitride film, Any one of a boron nitride film, an aluminum nitride film, a silicon oxide film, an aluminum oxide film, a titanium oxide film, an amorphous silicon film, and a diamond-like carbon film, which is a film formed by a plasma CVD method. Electroluminescent device.
有機電界発光素子において、 前記有機保護膜が、前記素子領域側に形成され、前記無
機保護膜が前記重合膜を覆って形成されていることを特
徴とする有機電界発光素子。8. The organic electroluminescent device according to claim 5, wherein the organic protective film is formed on the device region side, and the inorganic protective film is formed to cover the polymer film. An organic electroluminescent device, comprising:
有機電界発光素子において、 前記無機保護膜が、前記素子領域側に形成され、前記有
機保護膜が前記無機保護膜を覆って形成されていること
を特徴とする有機電界発光素子。9. The organic electroluminescent device according to claim 5, wherein the inorganic protective film is formed on the element region side, and the organic protective film covers the inorganic protective film. An organic electroluminescent device, which is formed.
おいて、 前記有機保護膜を覆ってさらに、無機保護膜が形成され
ていることを特徴とする有機電界発光素子。10. The organic electroluminescent device according to claim 9, wherein an inorganic protective film is further formed so as to cover the organic protective film.
電界発光素子において、 前記素子領域側に形成された前記無機保護膜は、膜厚５
００ｎｍ以下であることを特徴とする有機電界発光素
子。11. The organic electroluminescent device according to claim 9, wherein the inorganic protective film formed on the device region has a thickness of 5 nm.
An organic electroluminescent device having a thickness of not more than 00 nm.
層を備えた素子領域と、有機保護膜及び無機保護膜の積
層構造を備え該素子領域を覆って形成された保護膜と、
を備える有機電界発光素子の製造装置であって、 前記素子領域を構成する各層をそれぞれ成膜する素子成
膜室と、 前記有機保護膜を成膜する有機保護膜成膜室と、 前記無機保護膜を成膜する無機保護膜成膜室と、を備
え、 少なくとも、前記素子領域を覆って先に形成される前記
有機又は無機保護膜を成膜する前記有機又は無機保護膜
成膜室と、前記素子成膜室とが直接又は搬送用真空室を
介して連結されていることを特徴とする有機電界発光素
子の製造装置。12. An element region having at least one organic compound layer between electrodes, a protective film having a laminated structure of an organic protective film and an inorganic protective film and covering the element region,
An organic electroluminescent device manufacturing apparatus comprising: an element deposition chamber for depositing each layer constituting the element region; an organic protective film deposition chamber for depositing the organic protective film; An inorganic protective film deposition chamber for depositing a film, and at least, the organic or inorganic protective film deposition chamber for depositing the organic or inorganic protective film formed earlier covering the element region, An organic electroluminescent device manufacturing apparatus, wherein the device film forming chamber is connected directly or via a transfer vacuum chamber.
の製造装置において、 前記無機保護膜成膜室はプラズマＣＶＤ装置により構成
され、前記有機保護膜成膜室はプラズマ重合装置により
構成されていることを特徴とする有機電界発光素子の製
造装置。13. The apparatus for manufacturing an organic electroluminescent device according to claim 12, wherein the inorganic protective film forming chamber is constituted by a plasma CVD apparatus, and the organic protective film forming chamber is constituted by a plasma polymerization apparatus. An apparatus for manufacturing an organic electroluminescent device.
機電界発光素子の製造装置において、 前記有機保護膜成膜室で形成される前記有機保護膜は、
ヘテロ環式化合物の重 合体を含み、前記無機保護膜成膜室で形成される前記無
機保護膜は、窒化膜又は酸化膜又は炭素膜又はシリコン
膜のいずれかを含むことを特徴とする有機電界発光素子
の製造装置。14. The apparatus for manufacturing an organic electroluminescent device according to claim 12, wherein the organic protective film formed in the organic protective film deposition chamber is:
An organic electric field comprising a polymer of a heterocyclic compound, wherein the inorganic protective film formed in the inorganic protective film forming chamber includes a nitride film, an oxide film, a carbon film or a silicon film. Light emitting element manufacturing equipment.
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| JP2001146910A JP3783099B2 (en) | 2000-05-16 | 2001-05-16 | Organic electroluminescence device |
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|---|---|---|---|
| JP2000143840 | 2000-05-16 | ||
| JP2000-143840 | 2000-08-03 | ||
| JP2000-235919 | 2000-08-03 | ||
| JP2000235919 | 2000-08-03 | ||
| JP2001146910A JP3783099B2 (en) | 2000-05-16 | 2001-05-16 | Organic electroluminescence device |
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| JP2002117973A true JP2002117973A (en) | 2002-04-19 |
| JP3783099B2 JP3783099B2 (en) | 2006-06-07 |
Family
ID=27343391
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