JPH05101885A - Protection of electroluminescent element - Google Patents
Protection of electroluminescent elementInfo
- Publication number
- JPH05101885A JPH05101885A JP3287256A JP28725691A JPH05101885A JP H05101885 A JPH05101885 A JP H05101885A JP 3287256 A JP3287256 A JP 3287256A JP 28725691 A JP28725691 A JP 28725691A JP H05101885 A JPH05101885 A JP H05101885A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- transport layer
- light emitting
- diamond
- organic light
- 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
- 230000005525 hole transport Effects 0.000 claims abstract description 17
- 239000010408 film Substances 0.000 claims abstract description 16
- 239000010409 thin film Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007740 vapor deposition Methods 0.000 claims abstract description 5
- 238000005401 electroluminescence Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- DCZNSJVFOQPSRV-UHFFFAOYSA-N n,n-diphenyl-4-[4-(n-phenylanilino)phenyl]aniline Chemical class C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 DCZNSJVFOQPSRV-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical class C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical class C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019015 Mg-Ag Inorganic materials 0.000 description 1
- GIIWGCBLYNDKBO-UHFFFAOYSA-N Quinoline 1-oxide Chemical compound C1=CC=C2[N+]([O-])=CC=CC2=C1 GIIWGCBLYNDKBO-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- QKTRRACPJVYJNU-UHFFFAOYSA-N thiadiazolo[5,4-b]pyridine Chemical class C1=CN=C2SN=NC2=C1 QKTRRACPJVYJNU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Luminescent Compositions (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
(57)【要約】
【目的】 電界発光素子の保護を行ない耐久性を向上す
ること。
【構成】 有機発光層、正孔輸送層、電子輸送層又は電
極である基体層の表面に、ビッカース硬度３０００〜８
０００の以上を有するイオン化蒸着法によるダイヤモン
ド様薄膜を形成する。
【効果】 保護膜の遮蔽性及び熱伝導率が大きいので耐
久性の電界発光素子が得られた。
(57) [Abstract] [Purpose] To protect an electroluminescent device and improve its durability. [Structure] Vickers hardness of 3000 to 8 is formed on the surface of a substrate layer which is an organic light emitting layer, a hole transport layer, an electron transport layer or an electrode.
A diamond-like thin film is formed by an ionization vapor deposition method having 000 or more. [Effect] Since the protective film has a high shielding property and a high thermal conductivity, a durable electroluminescent device was obtained.
Description
【０００１】[0001]
【産業上の利用分野】本発明は有機電界発光素子の保護
に関し、より詳しくは基体に対して結合性の良い保護膜
を有する有機電界発光素子及び保護方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to protection of an organic electroluminescence device, and more particularly to an organic electroluminescence device having a protective film having a good bonding property to a substrate and a protection method.
【０００２】[0002]
【従来の技術】有機電界発光素子は、基本的には有機発
光層を正負電極で挟んだ形を有する。正負電極からキャ
リアーとして注入された電子と正孔が再結合する際に形
成される励起子（エキシトン）が励起状態から基底状態
に戻る時に発光を生じさせる。また、輝度を向上させる
ために更に正電極と有機発光層の間に正孔輸送層を介在
させ、あるいは負電極と有機発光層の間に電子輸送層を
介在さることも知られている（特開昭６３−２６４６９
２号、特開昭６３−２９５６９５号、特開平２−２５０
２９２号、Ｊ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．，２７，Ｌ２
６９（１９８８）等）。すなわち、図１に示した様にガ
ラス基板１、透明正電極２、正孔輸送層３、有機発光層
４、電子輸送層５及び負電極６をこの順に積層する。そ
して直流電源７から電圧を加えて発光させる。もちろ
ん、電子輸送層及び正孔輸送層の一方又は両方が省略さ
れることもある。また、電子輸送層や正孔輸送層には有
機化合物だけでなく無機化合物を用いてもよい。2. Description of the Related Art An organic electroluminescent device basically has a form in which an organic light emitting layer is sandwiched between positive and negative electrodes. Excitons (excitons) formed when electrons and holes injected as carriers from the positive and negative electrodes are recombined, and emit light when the excited state returns to the ground state. It is also known that a hole transport layer is further interposed between the positive electrode and the organic light emitting layer or an electron transport layer is interposed between the negative electrode and the organic light emitting layer in order to improve brightness (special feature). Kaisho 63-26469
2, JP-A-63-295695, JP-A-2-250.
292, J. J. Appl. Phys. , 27, L2
69 (1988) etc.). That is, as shown in FIG. 1, the glass substrate 1, the transparent positive electrode 2, the hole transport layer 3, the organic light emitting layer 4, the electron transport layer 5, and the negative electrode 6 are laminated in this order. Then, a voltage is applied from the DC power supply 7 to emit light. Of course, one or both of the electron transport layer and the hole transport layer may be omitted. Further, not only an organic compound but also an inorganic compound may be used for the electron transport layer and the hole transport layer.
【０００３】[0003]
【発明が解決すべき課題】有機発光層、正孔輸送層、電
子輸送層、又は電極は、水分、酸素、その他の使用環境
中のある種の分子の影響を受けて劣化し易いので、完全
に外気から遮断する必要がある。図１に示した様に、有
機発光層、正孔輸送層、あるいは電子輸送層には電極が
積層されるが、電極も含めてこれらの層が直接露出する
部分があるので、そこから水分、酸素等が侵入して、有
機発光層、正孔輸送層、電子輸送層、又は電極の劣化が
生じて輝度、色彩等の発光特性が低下する。これを防ぐ
保護膜としては、酸化物、炭化物、窒化物等の無機被
覆、エポキシ樹脂等の樹脂被覆が考えられるが、発光時
に素子の発熱により畜熱が起こり、素子自身を劣化させ
るからこのような熱伝導率の低い物質の使用は回避しな
ければならない。従って本発明の目的は、有機電界発光
素子において、正孔輸送層、有機発光層、電子輸送層、
電極及び支持基板（例えばガラス）に対する密着耐久性
の大きい、しかも熱伝導率の高い保護膜を提供すること
にある。The organic light emitting layer, the hole transporting layer, the electron transporting layer, or the electrode is liable to be deteriorated under the influence of moisture, oxygen, or some kind of molecules in the use environment. It is necessary to shut off the outside air. As shown in FIG. 1, an electrode is laminated on the organic light emitting layer, the hole transport layer, or the electron transport layer. However, since there is a portion where these layers are directly exposed including the electrode, moisture, The entry of oxygen and the like causes deterioration of the organic light emitting layer, the hole transporting layer, the electron transporting layer, or the electrode, which deteriorates the light emitting characteristics such as brightness and color. Inorganic coatings such as oxides, carbides, and nitrides, and resin coatings such as epoxy resins can be considered as protective films to prevent this, but heat generation of the element during light emission causes storage heat and deteriorates the element itself. The use of materials with low thermal conductivity must be avoided. Therefore, an object of the present invention is to provide a hole transport layer, an organic light emitting layer, an electron transport layer,
Another object of the present invention is to provide a protective film having high adhesion durability to electrodes and a supporting substrate (for example, glass) and having high thermal conductivity.
【０００４】[0004]
【課題を解決するための手段】本発明は、有機発光層、
正孔輸送層、電子輸送層または電極である基体層の表面
に、ビッカース硬度３０００〜８０００ｋｇ／ｍｍ2 以
上のイオン化蒸着法によるダイヤモンド様薄膜を形成し
たことを特徴とする有機電界発光素子及び保護方法を提
供する。ダイヤモンド様薄膜は酸素や水分に対するすぐ
れた遮蔽体であると共に、熱伝導度が大きいのですぐれ
た排熱手段（ヒートシンク）として作用する。より具体
的には、本発明は少なくとも一方が透明である一対の電
極の間に有機発光層、正孔輸送層、及び電子輸送層を設
けた有機電界発光素子において、前記有機発光層、正孔
輸送層、電子輸送層、及び電極の露出する部分の全体
に、ビッカース硬度３０００〜８０００ｋｇ／ｍｍ2 以
上のイオン化蒸着法によるダイヤモンド様薄膜を形成し
たことを特徴とする有機電界発光素子とその保護方法を
提供する。The present invention provides an organic light emitting layer,
An organic electroluminescent device and a protection method, wherein a diamond-like thin film having a Vickers hardness of 3000 to 8000 kg / mm 2 is formed on the surface of a hole transport layer, an electron transport layer or a base layer which is an electrode by an ionization deposition method. I will provide a. The diamond-like thin film is an excellent shield against oxygen and moisture, and since it has high thermal conductivity, it acts as an excellent heat sink. More specifically, the present invention relates to an organic electroluminescent device having an organic light emitting layer, a hole transport layer, and an electron transport layer between a pair of electrodes, at least one of which is transparent, wherein the organic light emitting layer, the hole An organic electroluminescent device characterized by forming a diamond-like thin film having a Vickers hardness of 3000 to 8000 kg / mm 2 by an ionization deposition method on the entire exposed portion of the transport layer, the electron transport layer, and the electrode, and a method for protecting the same. I will provide a.
【０００５】必須ではないが、場合により前記基体層の
表面をプラズマ又は逆スパッタした後、空気に露呈する
ことなく引き続いて前記基体層の表面にダイヤモンド様
薄膜を気相成膜する。Although not essential, the surface of the substrate layer is optionally plasma- or reverse-sputtered, and subsequently a diamond-like thin film is vapor-deposited on the surface of the substrate layer without being exposed to air.
【０００６】図２は本発明の適用例を示す図であり、ガ
ラス基板１の表面に透明正電極（例えばＩＴＯ）２、正
孔輸送層（例えばトリフェニルジアミン誘導体）３、有
機発光層（例えばペリレン誘導体或いはキノリンオキサ
イドとＡｌの錯体）４よりなり、場合により更に電子輸
送層（例えばオキサジアゾール誘導体）５（図１参照）
を順に従来の方法により形成した後、負電極（例えばＭ
ｇ−Ａｇ合金）６を形成する。更に、全面にダイヤモン
ド様薄膜８を保護膜として形成する。あるいは単に層
３、４または５の露出部分にダイヤモンド様薄膜保護膜
を形成してもよい。FIG. 2 is a diagram showing an application example of the present invention. A transparent positive electrode (eg ITO) 2, a hole transport layer (eg triphenyldiamine derivative) 3, an organic light emitting layer (eg Perylene derivative or a complex of quinoline oxide and Al) 4 and optionally an electron transport layer (eg oxadiazole derivative) 5 (see FIG. 1)
Are sequentially formed by a conventional method, and then a negative electrode (for example, M
g-Ag alloy) 6. Further, a diamond-like thin film 8 is formed on the entire surface as a protective film. Alternatively, the diamond-like thin film protective film may be simply formed on the exposed portion of the layers 3, 4 or 5.
【０００７】必須ではないが、必要に応じて前処理とし
てプラズマ処理を行なっても良い。この場合には、公知
のダイヤモンド成膜装置の内部にこの積層体を収容し、
電子輸送層５、または電子輸送層がない場合には有機発
光層４、あるいは負電極６を所定の負電源８に接続す
る。しかし積層体の一部の層の導電性は充分でないから
更にメッシュ状等のグリッド（図示せず）を負電極６あ
るいは層５（または層５がない場合には層４）に近接さ
せて配置し同じ負電位にする。グリッドと基体層との距
離は数ｍｍが好ましく、又電位は例えば約−１５０ボル
ト以下〜−１０ｋＶ程度の負電位を加える。使用するプ
ラズマガスとしてはＨｅ、Ａｒ、Ｎｅ、Ｘｅ等の不活性
ガスや、水素、窒素等のガスをプラズマ化する。プラズ
マガス中の正イオンはグリッドに印加された負電位によ
り加速されて負電極あるいは有機発光層または電子輸送
層の表面を活性化することにより、次に形成される保護
膜との結合力を向上させる。プラズマ処理の代わりに同
じ配置で周知の逆スパッタ法により基体の表面を活性化
しても良い。同様の処理を各層の形成時に行なっても良
い。Although not essential, plasma treatment may be performed as a pretreatment, if necessary. In this case, the laminate is housed inside a known diamond film forming apparatus,
The electron transport layer 5 or the organic light emitting layer 4 or the negative electrode 6 when there is no electron transport layer is connected to a predetermined negative power source 8. However, since the conductivity of a part of the layers of the laminate is not sufficient, a mesh-shaped grid (not shown) is further arranged close to the negative electrode 6 or the layer 5 (or the layer 4 if the layer 5 is not present). Then set the same negative potential. The distance between the grid and the base layer is preferably several millimeters, and the potential is, for example, a negative potential of about −150 V or less to about −10 kV. As a plasma gas to be used, an inert gas such as He, Ar, Ne and Xe, or a gas such as hydrogen and nitrogen is made into plasma. The positive ions in the plasma gas are accelerated by the negative potential applied to the grid to activate the surface of the negative electrode or the organic light emitting layer or the electron transport layer, thereby improving the binding force with the protective film to be formed next. Let Instead of the plasma treatment, the surface of the substrate may be activated by the well-known reverse sputtering method with the same arrangement. You may perform the same process at the time of forming each layer.
【０００８】なお、負電極の材料は４ｅＶ以下の仕事関
数を有する金属又は少なくとも１種が４ｅＶ以下の仕事
関数を有する金属を含有する合金より選択される。例え
ば、Ｍｇ、Ａｌ、及びＭｇ−Ａｇ合金等が使用出来る。
電極の成膜は蒸着、スパッタ等の任意の手法が使用出来
る。透明正電極としてはＩｎ−Ｓｎ酸化物、正孔輸送層
としてトリフェニルジアミン誘導体、スチルベン誘導
体、ピラゾリン誘導体等があり、電子輸送層としてはオ
キサジアゾール誘導体等がある。有機発光層としては縮
合多環型芳香族炭化水素色素、Ｏ、Ｎ、Ｓ等のヘテロ原
子を含む縮合多環型色素、金属錯体色素等がある。その
例としては、ペリノン誘導体、キノリン錯体誘導体、チ
アジアゾロピリジン誘導体、テトラフェニルブタジエン
類、ビススチリルベンゼン誘導体等が挙げられる（特開
平１−２４５０８７号、同２−８８６８９号、同２−２
５０２９２号、同２−２６１８８９号参照）。The material of the negative electrode is selected from a metal having a work function of 4 eV or less or an alloy containing at least one metal having a work function of 4 eV or less. For example, Mg, Al, and Mg-Ag alloy can be used.
Any method such as vapor deposition and sputtering can be used for forming the electrodes. The transparent positive electrode is an In—Sn oxide, the hole transport layer is a triphenyldiamine derivative, a stilbene derivative, a pyrazoline derivative, and the like, and the electron transport layer is an oxadiazole derivative. Examples of the organic light emitting layer include a condensed polycyclic aromatic hydrocarbon dye, a condensed polycyclic dye containing a hetero atom such as O, N and S, and a metal complex dye. Examples thereof include perinone derivatives, quinoline complex derivatives, thiadiazolopyridine derivatives, tetraphenylbutadienes, bisstyrylbenzene derivatives and the like (JP-A-1-245087, JP-A-2-88689, JP-A-2-88689).
50292, 2-261889).
【０００９】ダイヤモンド様薄膜を形成するためのイオ
ン化蒸着法は特開平１−２３４３９６号、同１−２３４
３９６号等で周知であり、低分子量炭化水素ガスを熱フ
ィラメントで熱分解し同時に電界を加えてイオン化し、
蒸着基板との間で加速電界を加えて加速し、基板上にダ
イヤモンドを析出させる。この方法によるとビッカース
硬度Ｈｖが保護目的に適する約３０００〜８０００ｋｇ
／ｍｍ2 の比較的大きい硬度で緻密な膜が得られる。３
０００ｋｇ／ｍｍ2 未満では緻密性に欠けるので酸素や
水分の遮蔽が十分でない。また８０００ｋｇ／ｍｍ2 は
成膜可能な上限である。The ionization vapor deposition method for forming a diamond-like thin film is described in JP-A-1-234396 and 1-234.
No. 396, etc., a low molecular weight hydrocarbon gas is thermally decomposed with a hot filament and at the same time an electric field is applied to ionize it.
An acceleration electric field is applied between the vapor deposition substrate and the substrate to accelerate the deposition and deposit diamond on the substrate. According to this method, the Vickers hardness Hv is about 3000 to 8000 kg suitable for protection purposes.
A dense film can be obtained with a relatively large hardness of / mm 2 . Three
If it is less than 000 kg / mm 2 , the denseness is insufficient, so that the shielding of oxygen and water is not sufficient. 8000 kg / mm 2 is the upper limit of film formation.
【００１０】[0010]
【実施例の説明】以下に実施例を説明する。以下の例で
は図２の構成に従いガラス基板の面にＩＴＯ層（インジ
ウム−錫合金層）、トリフェニルジアミン誘導体よりな
る正孔輸送層、トリキノリンオキサイド−アルミニウム
錯体よりなる有機発光層を形成し、更に負電極としてＭ
ｇ−Ａｇ合金膜を形成した後、ダイヤモンド様薄膜をこ
れらの層の面に成膜した。成膜は、真空室を１０-6Ｔｏ
ｒｒに排気してからメタンガスを導入しガス圧を１０-1
Ｔｏｒｒとし、フィラメント電流Ｉｆ＝２５Ａ、基体電
圧Ｖａ＝−５００Ｖ、フィラメント電圧Ｖｄ＝−３０
Ｖ、電磁コイルの磁束密度４００ガウスの条件で成膜を
行った。フィラメントはコイル状としその幅３ｍｍ、そ
の周りを取り囲む陽極電極との隙間８ｍｍとした。比較
のため、従来の熱硬化性エポキシ樹脂被覆の場合を併記
する。耐久性を大気中にて２５℃、５０％ＲＨの条件で
輝度が１００ｃｄ／ｍ2 以上が得られる時間長を測定し
た。また水分透過性をＪＩＳ Ｚ０２０８に規定された
条件で試験した。比較例を１００とした場合の相対評価
を表１に示す。Description of Embodiments Embodiments will be described below. In the following example, an ITO layer (indium-tin alloy layer), a hole transport layer made of a triphenyldiamine derivative, and an organic light-emitting layer made of a triquinoline oxide-aluminum complex are formed on the surface of a glass substrate according to the configuration of FIG. Furthermore, as a negative electrode, M
After forming the g-Ag alloy film, diamond-like thin films were formed on the surfaces of these layers. The film is formed in a vacuum chamber at 10 -6 To
After exhausting to rr, introduce methane gas and adjust the gas pressure to 10 -1.
Torr, filament current If = 25 A, substrate voltage Va = -500 V, filament voltage Vd = -30
The film formation was performed under the conditions of V and the magnetic flux density of the electromagnetic coil of 400 gauss. The filament had a coil shape with a width of 3 mm and a gap of 8 mm with the surrounding anode electrode. For comparison, the case of the conventional thermosetting epoxy resin coating is also shown. The durability was measured in the atmosphere under the conditions of 25 ° C. and 50% RH, and the time length over which a luminance of 100 cd / m 2 or more was obtained was measured. Further, the water permeability was tested under the conditions specified in JIS Z0208. Table 1 shows the relative evaluation when the comparative example was set to 100.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【発明の効果】本発明によると、有機電界発光素子が保
護され、耐久性の向上及び水分透過性の低下が達成でき
た。耐久性の向上は有機電界発光素子が水分や酸素等の
影響を受けないほか、ダイヤモンド様薄膜の保護膜が熱
伝導性が良いことと電極の剥離を抑えることが出来たこ
とによる。According to the present invention, the organic electroluminescent device is protected, and the durability and the moisture permeability can be improved. The improvement in durability is due to the fact that the organic electroluminescent element is not affected by moisture, oxygen, etc., and that the diamond-like thin protective film has good thermal conductivity and that peeling of the electrode can be suppressed.
【図１】有機電界発光素子の構成の一例を示す断面図で
ある。FIG. 1 is a cross-sectional view showing an example of the configuration of an organic electroluminescent device.
【図２】本発明の実施例を説明する図である。FIG. 2 is a diagram illustrating an example of the present invention.
１ ガラス基板 ２ 透明正電極 ３ 正孔輸送層 ４ 有機発光層 ５ 電子輸送層 ８ ダイヤモンド様薄膜による保護膜 1 Glass Substrate 2 Transparent Positive Electrode 3 Hole Transport Layer 4 Organic Light Emitting Layer 5 Electron Transport Layer 8 Diamond-like Thin Film Protective Film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中山 正俊 東京都中央区日本橋一丁目13番１号テイー デイーケイ株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Masatoshi Nakayama 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDK Corporation
Claims (5)
は電極である基体層の表面に、ビッカース硬度３０００
〜８０００ｋｇ／ｍｍ2 以上のダイヤモンド様薄膜を形
成したことを特徴とする有機電界発光素子。1. A Vickers hardness of 3000 is formed on the surface of a substrate layer which is an organic light emitting layer, a hole transport layer, an electron transport layer or an electrode.
An organic electroluminescence device characterized in that a diamond-like thin film of 8000 kg / mm 2 or more is formed.
の間に有機発光層、正孔輸送層、及び電子輸送層を設け
た有機電界発光素子において、前記有機発光層、正孔輸
送層、電子輸送層、及び電極の露出する部分に、ビッカ
ース硬度３０００〜８０００ｋｇ／ｍｍ2 以上のイオン
化蒸着法によるダイヤモンド様薄膜を形成したことを特
徴とする有機電界発光素子。2. An organic electroluminescent device comprising an organic light emitting layer, a hole transport layer, and an electron transport layer provided between a pair of electrodes, at least one of which is transparent, wherein the organic light emitting layer, the hole transport layer, and the electron. An organic electroluminescent device comprising a diamond-like thin film having a Vickers hardness of 3000 to 8000 kg / mm 2 and formed by an ionization deposition method on the exposed portion of the transport layer and the electrode.
層である基体層の表面に、ビッカース硬度３０００〜８
０００ｋｇ／ｍｍ2 以上のダイヤモンド様薄膜を成膜す
ることを特徴とする有機電界発光素子の保護方法。3. Vickers hardness of 3000 to 8 on the surface of a substrate layer which is an organic light emitting layer, a hole transport layer or an electron transport layer.
A method for protecting an organic electroluminescence device, which comprises forming a diamond-like thin film of 000 kg / mm 2 or more.
の間に有機発光層、正孔輸送層、及び電子輸送層を設け
た有機電界発光素子において、前記有機発光層、正孔輸
送層、電子輸送層、及び電極の露出する全ての部分に、
ビッカース硬度３０００〜８０００ｋｇ／ｍｍ2 以上の
イオン化蒸着法によるダイヤモンド様薄膜を形成するこ
とを特徴とする有機電界発光素子の保護方法。4. An organic electroluminescent device comprising an organic light emitting layer, a hole transporting layer, and an electron transporting layer between a pair of electrodes, at least one of which is transparent, wherein the organic light emitting layer, the hole transporting layer, and the electron are provided. On the transport layer and all exposed parts of the electrode,
A method for protecting an organic electroluminescence device, which comprises forming a diamond-like thin film having a Vickers hardness of 3000 to 8000 kg / mm 2 or more by an ionization vapor deposition method.
記基体層の表面をプラズマ処理又は逆スパッタ処理した
後、空気に露呈することなく引き続いて前記基体層の表
面にダイヤモンド様薄膜を気相成膜することを特徴とす
る、請求項３又は４に記載の有機電界発光素子の保護方
法。5. Before forming the diamond-like thin film, the surface of the base layer is plasma-treated or reverse-sputtered, and then the diamond-like thin film is vapor-phased on the surface of the base layer without being exposed to air. The method for protecting an organic electroluminescence device according to claim 3, wherein the organic electroluminescence device is protected by a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28725691A JP3197305B2 (en) | 1991-10-08 | 1991-10-08 | Protection of electroluminescent element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28725691A JP3197305B2 (en) | 1991-10-08 | 1991-10-08 | Protection of electroluminescent element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05101885A true JPH05101885A (en) | 1993-04-23 |
| JP3197305B2 JP3197305B2 (en) | 2001-08-13 |
Family
ID=17715049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28725691A Expired - Fee Related JP3197305B2 (en) | 1991-10-08 | 1991-10-08 | Protection of electroluminescent element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3197305B2 (en) |
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