JPWO2006009050A1 - ORGANIC ELECTROLUMINESCENT DEVICE AND MANUFACTURING METHOD THEREOF - Google Patents
ORGANIC ELECTROLUMINESCENT DEVICE AND MANUFACTURING METHOD THEREOF Download PDFInfo
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- 239000010410 layer Substances 0.000 claims abstract description 154
- 238000002347 injection Methods 0.000 claims abstract description 67
- 239000007924 injection Substances 0.000 claims abstract description 67
- 239000002346 layers by function Substances 0.000 claims abstract description 27
- 150000003384 small molecules Chemical class 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 7
- 238000005401 electroluminescence Methods 0.000 claims abstract 3
- 125000001424 substituent group Chemical group 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 17
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- 125000003545 alkoxy group Chemical group 0.000 claims description 5
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- 239000004721 Polyphenylene oxide Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000570 polyether Chemical group 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical class [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims 1
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
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- 239000000463 material Substances 0.000 description 9
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- 230000005525 hole transport Effects 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 6
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- 230000007547 defect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- KLZHUQDVWUXWEZ-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1.C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 KLZHUQDVWUXWEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
電極間のショートが発生しにくい有機エレクトロルミネセンス素子。 本発明の有機エレクトロルミネセンス素子は、互いに対向する第１及び第２電極層と、該第１及び第２電極層によって挟持されている有機化合物を含む有機機能層とからなる。該有機機能層は該第１電極層に接して設けられている正孔注入層を含み、該正孔注入層は有機溶剤に可溶でありかつ正孔注入性を有する熱分解性の低分子量化合物を含む。該低分子量化合物は、フタロシアニン誘導体であることとしても良い。Organic electroluminescence device that is less prone to short-circuit between electrodes. The organic electroluminescent element of the present invention comprises first and second electrode layers facing each other, and an organic functional layer containing an organic compound sandwiched between the first and second electrode layers. The organic functional layer includes a hole injection layer provided in contact with the first electrode layer, and the hole injection layer is soluble in an organic solvent and has a hole injecting property and a thermally decomposable low molecular weight. Contains compounds. The low molecular weight compound may be a phthalocyanine derivative.
Description
本発明は、有機エレクトロルミネセンス素子およびその製造方法に関する。 The present invention relates to an organic electroluminescent element and a method for manufacturing the same.
有機エレクトロルミネセンス素子（以下有機ＥＬと称する）は、ガラス基板等の透明な基板の主面上に、インジウム錫酸化物（以下ＩＴＯと称する）等の導電性材料からなる透明な第１電極層と有機蛍光体を有する発光層を含む有機機能層とＡｌやＭｇなどの金属からなる第２電極層とが順に成膜されて形成されている。
有機機能層は、複数の薄膜を含み、第１電極層から正孔注入層、正孔輸送層、発光層及び電子注入層の順に成膜されて構成されている。
第１電極層と第２電極層との間に直流電界を印加すると、第１電極層から注入された正孔と第２電極層から注入された電子とが発光層内にて再結合し、そのエネルギーを受けて発光層中の蛍光体が発光し、この発光層からの光を基板からあるいは基板とは反対側から取り出すようになっている。このような有機ＥＬ素子は、自己発光であることから視認性に優れており、かつ数Ｖ〜数十Ｖの低電圧駆動が可能であることから駆動回路を含めた軽量化が可能である。
上記の如き構成の有機ＥＬ素子は、有機機能層が低分子量化合物からなる場合と高分子量化合物からなる場合とに大別されており、前者は低分子型有機ＥＬ素子と称され、後者は高分子型有機ＥＬ素子と称されている。低分子型有機ＥＬ素子の場合、低分子量化合物を蒸着して成膜する蒸着法を用いて有機機能層が形成されている。高分子型有機ＥＬ素子の場合、高分子量化合物を有機溶媒に溶解させた後にスピンコート法等の溶液を用いた成膜方法を用いて当該溶液を第１電極層上に配することによって、有機機能層が形成されている。An organic electroluminescent element (hereinafter referred to as organic EL) is a transparent first electrode layer made of a conductive material such as indium tin oxide (hereinafter referred to as ITO) on a main surface of a transparent substrate such as a glass substrate. And an organic functional layer including a light emitting layer having an organic phosphor and a second electrode layer made of a metal such as Al or Mg are sequentially formed.
The organic functional layer includes a plurality of thin films, and is formed by sequentially forming a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection layer from the first electrode layer.
When a DC electric field is applied between the first electrode layer and the second electrode layer, holes injected from the first electrode layer and electrons injected from the second electrode layer recombine in the light emitting layer, Upon receiving the energy, the phosphor in the light emitting layer emits light, and light from the light emitting layer is extracted from the substrate or from the side opposite to the substrate. Such an organic EL element is excellent in visibility because it is self-luminous, and can be driven at a low voltage of several V to several tens V, and thus can be reduced in weight including a drive circuit.
The organic EL device having the above-described configuration is roughly divided into a case where the organic functional layer is made of a low molecular weight compound and a case where the organic functional layer is made of a high molecular weight compound. It is called a molecular organic EL element. In the case of a low molecular weight organic EL device, the organic functional layer is formed using a vapor deposition method in which a low molecular weight compound is vapor deposited. In the case of a polymer-type organic EL device, a high molecular weight compound is dissolved in an organic solvent, and then the solution is disposed on the first electrode layer by using a film forming method using a solution such as a spin coating method. A functional layer is formed.
上記の有機機能層のうち、正孔注入層の材料が銅フタロシアニンなどの低分子量化合物からなる場合、正孔注入層を成膜する際に異物が第１電極層上に付着していると、該異物が第１電極層のマスクとして作用してしまう。換言すれば、蒸着法を用いて低分子量化合物からなる正孔注入層を形成すると、該異物が蒸着材料流のマスクとなり、異物と第１電極層とが接触している部分およびその近傍に正孔注入層が成膜されない部分、すなわち正孔注入層の欠陥部が形成されてしまう。その結果、発光層への正孔の注入効率が低下し、画素の発光効率が低下してしまう。
また、正孔注入層が第１電極層と隣接していることから、正孔注入層に上記の如き欠陥部が形成された場合、該欠陥部において、第１電極層と第２電極層とがショート（短絡）する恐れがある。
正孔注入層の材料が導電性ポリマー等の高分子量化合物からなる場合、正孔注入層は高分子量化合物の溶液を配することによって成膜できることから、第１電極層上に異物が付着していたとしても該溶液が該異物を被覆してしまう。その結果、正孔注入層の膜欠陥や第１電極層と第２電極層とのショートが発生しにくくなる。しかしながら、正孔注入層に使用できる特性を呈する高分子量化合物の種類は限定されている。
また、高分子量化合物を含む正孔注入層用材料の精製が困難であることから当該材料の不純物の含有量が大であり、正孔注入層の正孔注入能力が安定しない。さらに当該材料における高分子量化合物の分子量分布が製造ロット毎に異なっていることから、複数の有機ＥＬ素子を形成した場合に、各有機ＥＬ素子における正孔注入層の正孔注入能力が一定しない。
さらにまた、高分子量化合物からなる薄膜は、該薄膜中に溶剤が残留し易くかつ水分を吸着し易いことから、溶剤および水分によって有機ＥＬ素子が劣化するなどの有機ＥＬ素子の保存安定性が悪いという問題がある。
本発明は、上記した問題が１例として挙げられる諸問題を解決する手段を提供することを目的とする。
本発明の特徴による有機ＥＬ素子は、互いに対向する第１及び第２電極層と、該第１及び第２電極層によって挟持されている有機化合物を含む有機機能層とからなる有機エレクトロルミネセンス素子であって、該有機機能層は該第１電極層に接して設けられている正孔注入層を含み、該正孔注入層は有機溶剤に可溶でありかつ正孔注入性を有する熱分解性の低分子量化合物を含むことを特徴とする。
本発明の特徴による有機ＥＬ素子の製造方法は、基板上に第１電極層を形成する工程と、該第１電極層上に有機化合物を含む有機機能層を形成する工程と、該有機機能層上に第２電極層を形成する工程と、を含む有機ＥＬ素子の製造方法であって、該有機機能層を形成する工程は該第１電極層に接する正孔注入層を形成する工程を含み、該正孔注入層を形成する工程は有機溶剤に可溶でありかつ正孔注入性を有する熱分解性の低分子量化合物を含む溶液を作製する工程と該溶液を該第１電極層上に配する工程とを含む、ことを特徴とする。Among the organic functional layers described above, when the material of the hole injection layer is made of a low molecular weight compound such as copper phthalocyanine, when the foreign material adheres to the first electrode layer when forming the hole injection layer, The foreign matter acts as a mask for the first electrode layer. In other words, when a hole injection layer made of a low molecular weight compound is formed using the vapor deposition method, the foreign matter serves as a mask for the flow of the vapor deposition material, and the foreign matter and the first electrode layer are in contact with and in the vicinity thereof. A portion where the hole injection layer is not formed, that is, a defective portion of the hole injection layer is formed. As a result, the efficiency of hole injection into the light emitting layer is lowered, and the light emission efficiency of the pixel is lowered.
In addition, since the hole injection layer is adjacent to the first electrode layer, when the above-described defect portion is formed in the hole injection layer, the first electrode layer and the second electrode layer are formed in the defect portion. May short circuit.
In the case where the material of the hole injection layer is made of a high molecular weight compound such as a conductive polymer, the hole injection layer can be formed by arranging a solution of the high molecular weight compound, so that foreign matter is adhered on the first electrode layer. Even so, the solution covers the foreign matter. As a result, film defects in the hole injection layer and short circuit between the first electrode layer and the second electrode layer are less likely to occur. However, the types of high molecular weight compounds that exhibit properties that can be used in the hole injection layer are limited.
In addition, since it is difficult to purify a hole injection layer material containing a high molecular weight compound, the content of impurities in the material is large, and the hole injection capability of the hole injection layer is not stable. Furthermore, since the molecular weight distribution of the high molecular weight compound in the material differs for each production lot, when a plurality of organic EL elements are formed, the hole injection capability of the hole injection layer in each organic EL element is not constant.
Furthermore, a thin film made of a high molecular weight compound has a poor storage stability of an organic EL element such as a deterioration of the organic EL element due to the solvent and moisture because the solvent is likely to remain in the thin film and moisture is easily absorbed. There is a problem.
An object of the present invention is to provide a means for solving various problems mentioned above as an example.
An organic EL device according to a feature of the present invention includes an organic electroluminescent device comprising first and second electrode layers facing each other and an organic functional layer containing an organic compound sandwiched between the first and second electrode layers. The organic functional layer includes a hole injection layer provided in contact with the first electrode layer, and the hole injection layer is soluble in an organic solvent and has a hole injection property. It is characterized by containing a low molecular weight compound.
An organic EL device manufacturing method according to the features of the present invention includes a step of forming a first electrode layer on a substrate, a step of forming an organic functional layer containing an organic compound on the first electrode layer, and the organic functional layer. And a step of forming a second electrode layer thereon, wherein the step of forming the organic functional layer includes a step of forming a hole injection layer in contact with the first electrode layer. The step of forming the hole injection layer is a step of preparing a solution containing a thermally decomposable low molecular weight compound that is soluble in an organic solvent and has a hole injection property, and the solution is formed on the first electrode layer. And a step of arranging.
図１は本発明の有機ＥＬ素子の概略断面図である。 FIG. 1 is a schematic sectional view of an organic EL device of the present invention.
以下、本発明による有機ＥＬ素子およびその製造方法を、添付図面を参照しつつ詳細に説明する。
図１に示す如く、有機ＥＬ素子１は、ガラスや樹脂などの透明材料からなる基板２と、基板上に設けられたＩＴＯ等の導電性材料からなる第１電極層３と、を有する。第１電極層３は、スパッタリング法等の成膜方法を用いて形成される。
第１電極層３上には、正孔注入層４が形成されている。正孔注入層４は、有機溶剤に可溶でありかつ正孔注入性を有する低分子量化合物からなる。かかる低分子量化合物の分子量は、略１０００以下である。該低分子量化合物は加熱されることによって分解する特性、すなわち熱分解性を有する化合物であり、該化合物は例えば５００℃以下の比較的低い温度で熱分解を生じることが好ましい。
かかる低分子量化合物として、例えば有機溶剤に可溶であるフタロシアニン誘導体がある。かかる可溶性のフタロシアニン誘導体は、下記一般式〔化１〕で表される。
Ｒ２は、置換基を有していても良いアルキル基、置換基を有していても良いアルコキシ基、置換基を有していても良い複素環基、ハロゲン原子、ニトロ基、シアノ基若しくはスルホン酸基を表す。
上記一般式〔化１〕に示す如き化学構造を有するフタロシアニン誘導体は、Ｒ１の置換基が加熱によって分解されやすくなっており、Ｒ２の置換基が有機溶媒への溶解特性に特に寄与している。すなわち、銅フタロシアニンなどのフタロシアニン化合物に比べて、上記フタロシアニン誘導体は、低温で分解できて有機溶媒に可溶となるのである。
正孔注入層４は、上記したフタロシアニン誘導体などの低分子量化合物を有機溶剤に溶解せしめた有機溶液を作製した後、例えばスピンコート法などの成膜方法を用いて該有機溶液を第１電極層上に配し、乾燥せしめて溶媒を除去することによって形成することができる。
正孔注入層４上には、正孔輸送層５が設けられている。正孔輸送層５は、ＮＰＢ（Ｎ，Ｎ’−ジ（ナフタレン−１−イル）−Ｎ，Ｎ’−ジフェニル−ベンジジン（Ｎ，Ｎ’−Ｄｉ（ｎａｐｈｔｈ ａｌｅｎｅ−１−ｙｌ）−Ｎ，Ｎ’−ｄｉｐｈｅｎｙｌ−ｂｅｎｚｉｄｉｎｅ））、ＭＴＤＡＴＡ（４，４’，４’’−トリス（３−メチルフェニルフェニルアミノ）トリフェニルアミン（４，４’，４’’−ｔｒｉｓ（３−ｍｅｔｈｙｌｐ ｈｅｎｙｌｐｈｅｎｙｌａｍｉｎｏ）ｔｒｉｐｈｅｎｙｌａｍｉｎｅ））、ＴＰＤ（Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（３−メチルフェニル）−１，１’−ビフェニル−４，４’−ジアミン（Ｎ，Ｎ’−ｄｉｐｈｅｎｙ １−Ｎ，Ｎ’−ｄｉ（３−ｍｅｔｈｙｌｐｈｅｎｙｌ）−１，１’−ｂｉｐｈｅｎｙｌ−４，４’−ｄｉａｍｉｎｅ））などの正孔輸送性に優れた材料を含み、蒸着法などの成膜方法を用いて形成することができる。
正孔輸送層５上には、発光層６が設けられている。発光層６は、Ａｌｑ３（トリス（８−ヒドロキシキノリン）アルミニウム（ｔｒｉｓ（８−ｈｙｄｒｏｘｙｑｕｉｎｏｌｉｎｅ）ａｌｕｍｉｎｕｍ））等の発光特性を呈する材料を含み、蒸着法などの成膜方法を用いて形成することができる。
発光層６上には電子注入層７が設けられている。電子注入層７は、例えば酸化リチウムを含み、蒸着法などの成膜方法を用いて形成することができる。上記の如く正孔注入層４、正孔輸送層５、発光層６および電子注入層７が順に形成されて有機機能層８が構成されている。
電子注入層７上には、第２電極層９が設けられている。第２電極層９は、例えばアルミニウム、アルミニウムリチウム合金、マグネシウムインジウム合金、マグネシウム銀合金等の導電材料からなり、蒸着法などの成膜方法を用いて形成できる。
上記の如き構成の有機ＥＬ素子は、第１電極層と第２電極層との間に電界を印加すると、第１電極層から注入された正孔と第２電極層から注入された電子とが発光層内にて再結合して発光層が発光する。第１電極層と第２電極層との間がショートしていた場合、当該ショート部分およびこの近傍がショートによって発生するジュール熱によって加熱され、この熱によって正孔注入層の低分子量化合物が分解して気化する。すなわち、正孔注入層に含まれる低分子量化合物がフタロシアニン誘導体の場合、上記した構造式（〔化１〕）におけるＲ１置換基の部分が分解されて気化するのである。この結果、ショート部分の近傍の正孔注入層は気化して体積膨張し、ショートしていた第１電極層と第２電極層とが離れる。換言すれば、上記の如き構成の有機ＥＬ素子は、第１電極層と第２電極層との間がショートしていたとしても第１電極層と第２電極層との間に電界を印加することによって正孔注入層が比較的低い温度で加熱分解されて膨張することによってショート部分が修復される自己修復機能を有する。また、安価で高純度のフタロシアニン誘導体が得られることから、有機ＥＬ素子の製造コストを低減させることができる。
上記の如き正孔注入層は低分子量化合物の溶液を第１電極層上に配して形成できることから、第１電極層上に異物が付着していたとしてもこれを覆って正孔注入層が形成できる。この結果、異物と第１電極層とが接している部分およびその近傍において正孔注入層の欠陥部が形成されにくくなる。また、上記成膜方法によれば、蒸着法を用いた成膜方法に比べて薄膜におけるピンホールの発生を抑制することができる。従って、第１電極層と第２電極層とのショートが発生しにくくなる。さらに、低分子量化合物を含む薄膜は残留溶媒の除去や吸着水分の除去が容易であることから、安定性が高い有機ＥＬ素子を得ることができる。
なお、正孔注入層に使用できる低分子量化合物は可溶性のフタロシアニン誘導体に限定されるものではなく、例えば、可溶性のナフタロシアニン誘導体、可溶性のシアニン誘導体、可溶性の多官能アミン誘導体が正孔注入層の材料として使用できる。多官能アミン誘導体としては、例えばトリフェニルアミン誘導体などのアリールアミン誘導体が使用できる。
また、正孔注入層は、上記したフタロシアニン誘導体のみからなる場合に限定されず、正孔注入性に優れた化合物をドーパントとして含むこととしても良い。
有機ＥＬ素子に含まれる有機機能層は、上記の如き４層構造に限定されるものではなく、少なくとも正孔注入層を含む構造であれば良い。例えば、有機機能層は、正孔注入層、正孔輸送層、発光層、電子輸送層及び電子注入層からなる５層構造を有することとしても良い。
互いに対向する第１及び第２電極層と、該第１及び第２電極層によって挟持されている有機化合物を含む有機機能層とからなる有機エレクトロルミネセンス素子であって、該有機機能層は該第１電極層に接して設けられている正孔注入層を含み、該正孔注入層は有機溶剤に可溶でありかつ正孔注入性を有する熱分解性の低分子量化合物を含むことを特徴とする本発明の有機ＥＬ素子によれば、正孔注入層の欠陥部を介して第１電極層と第２電極層とが接触している場合、ショートによるジュール熱が正孔注入層を分解および膨張せしめると、正孔注入層が第１電極層と隣接していることから第１電極層と第２電極層との間を効果的に分離することができる。これによって、ショート部を自己修復することができる。
基板上に第１電極層を形成する工程と、該第１電極層上に有機化合物を含む有機機能層を形成する工程と、該有機機能層上に第２電極層を形成する工程と、を含む有機ＥＬ素子の製造方法であって、該有機機能層を形成する工程は該第１電極層に接する正孔注入層を形成する工程を含み、該正孔注入層を形成する工程は有機溶剤に可溶でありかつ正孔注入性を有する熱分解性の低分子量化合物を含む溶液を作製する工程と該溶液を該第１電極層上に配する工程とを含む、ことを特徴とする本発明の有機ＥＬ素子の製造方法によれば、低分子量化合物を含む溶液を第１電極層上に配することによって正孔注入層を形成することができることから、異物等によって形成された第１電極層の凹凸に起因する正孔注入層の欠陥が発生しにくい故、第１電極層と第２電極層とのショートが発生する恐れが低減する。Hereinafter, an organic EL device and a manufacturing method thereof according to the present invention will be described in detail with reference to the accompanying drawings.
As shown in FIG. 1, the
A hole injection layer 4 is formed on the
Examples of such low molecular weight compounds include phthalocyanine derivatives that are soluble in organic solvents. Such a soluble phthalocyanine derivative is represented by the following general formula [Chemical Formula 1].
R2 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom, a nitro group, a cyano group or a sulfone. Represents an acid group.
In the phthalocyanine derivative having the chemical structure represented by the above general formula [Chemical Formula 1], the substituent of R1 is easily decomposed by heating, and the substituent of R2 particularly contributes to the solubility property in an organic solvent. That is, compared to phthalocyanine compounds such as copper phthalocyanine, the phthalocyanine derivative can be decomposed at a low temperature and becomes soluble in an organic solvent.
The hole injection layer 4 is prepared by preparing an organic solution in which a low molecular weight compound such as the phthalocyanine derivative described above is dissolved in an organic solvent, and then using the organic solution as a first electrode layer by using a film forming method such as a spin coating method. It can be formed by placing on top and drying to remove the solvent.
A hole transport layer 5 is provided on the hole injection layer 4. The hole transport layer 5 is composed of NPB (N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine (N, N′-Di (naphthalene-1-yl) -N, N '-Diphenyl-benzidine)), MTDATA (4,4', 4 "-tris (3-methylphenylphenylamino) triphenylamine (4,4 ', 4" -tris (3-methylphenylphenylamino) triphenylamine) ), TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine (N, N′-diphenyl 1-N, N ′) -Di (3-methylphenyl) -1,1'-biphenyl-4,4'-diaminine)), and the like. It can be formed using a deposition method such as law.
A light emitting layer 6 is provided on the hole transport layer 5. The light-emitting layer 6 includes a material exhibiting light-emitting characteristics such as Alq3 (tris (8-hydroxyquinoline) aluminum) and can be formed using a film formation method such as an evaporation method. .
An electron injection layer 7 is provided on the light emitting layer 6. The electron injection layer 7 contains, for example, lithium oxide and can be formed using a film forming method such as a vapor deposition method. As described above, the hole injection layer 4, the hole transport layer 5, the light emitting layer 6, and the electron injection layer 7 are sequentially formed to constitute the organic functional layer 8.
A second electrode layer 9 is provided on the electron injection layer 7. The second electrode layer 9 is made of a conductive material such as aluminum, an aluminum lithium alloy, a magnesium indium alloy, or a magnesium silver alloy, and can be formed using a film forming method such as a vapor deposition method.
In the organic EL device having the above-described configuration, when an electric field is applied between the first electrode layer and the second electrode layer, holes injected from the first electrode layer and electrons injected from the second electrode layer are generated. The light emitting layer emits light by recombination in the light emitting layer. When the first electrode layer and the second electrode layer are short-circuited, the short portion and the vicinity thereof are heated by Joule heat generated by the short-circuit, and this heat decomposes the low molecular weight compound in the hole injection layer. Vaporize. That is, when the low molecular weight compound contained in the hole injection layer is a phthalocyanine derivative, the R1 substituent portion in the above structural formula ([Chemical Formula 1]) is decomposed and vaporized. As a result, the hole injection layer in the vicinity of the shorted portion is vaporized and volume-expanded, and the shorted first electrode layer and second electrode layer are separated. In other words, the organic EL element configured as described above applies an electric field between the first electrode layer and the second electrode layer even if the first electrode layer and the second electrode layer are short-circuited. Accordingly, the hole injection layer has a self-repairing function in which the short portion is repaired by being thermally decomposed and expanded at a relatively low temperature. Moreover, since a cheap and highly pure phthalocyanine derivative is obtained, the manufacturing cost of an organic EL element can be reduced.
Since the hole injection layer as described above can be formed by arranging a solution of a low molecular weight compound on the first electrode layer, even if foreign matter is adhered on the first electrode layer, Can be formed. As a result, it is difficult to form a defective portion of the hole injection layer at a portion where the foreign substance and the first electrode layer are in contact with each other and in the vicinity thereof. Moreover, according to the film forming method, the generation of pinholes in the thin film can be suppressed as compared with the film forming method using the vapor deposition method. Therefore, a short circuit between the first electrode layer and the second electrode layer is less likely to occur. Furthermore, since a thin film containing a low molecular weight compound can easily remove residual solvent and adsorbed moisture, an organic EL element with high stability can be obtained.
The low molecular weight compounds that can be used in the hole injection layer are not limited to soluble phthalocyanine derivatives. For example, soluble naphthalocyanine derivatives, soluble cyanine derivatives, and soluble polyfunctional amine derivatives are used in the hole injection layer. Can be used as material. As the polyfunctional amine derivative, for example, an arylamine derivative such as a triphenylamine derivative can be used.
In addition, the hole injection layer is not limited to the case of being made of only the above phthalocyanine derivative, and may contain a compound having excellent hole injection properties as a dopant.
The organic functional layer included in the organic EL element is not limited to the four-layer structure as described above, and may be a structure including at least a hole injection layer. For example, the organic functional layer may have a five-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
An organic electroluminescent element comprising first and second electrode layers facing each other and an organic functional layer containing an organic compound sandwiched between the first and second electrode layers, wherein the organic functional layer comprises A hole injection layer provided in contact with the first electrode layer, wherein the hole injection layer contains a thermally decomposable low molecular weight compound that is soluble in an organic solvent and has a hole injection property; According to the organic EL device of the present invention, when the first electrode layer and the second electrode layer are in contact with each other through the defective portion of the hole injection layer, Joule heat due to a short circuit decomposes the hole injection layer. When expanded, since the hole injection layer is adjacent to the first electrode layer, the first electrode layer and the second electrode layer can be effectively separated. Thereby, the short part can be self-repaired.
Forming a first electrode layer on the substrate; forming an organic functional layer containing an organic compound on the first electrode layer; and forming a second electrode layer on the organic functional layer. A method of manufacturing an organic EL element including the step of forming the organic functional layer includes a step of forming a hole injection layer in contact with the first electrode layer, and the step of forming the hole injection layer includes an organic solvent. Comprising a step of preparing a solution containing a thermally decomposable low molecular weight compound that is soluble in water and has a hole injection property, and a step of disposing the solution on the first electrode layer According to the method for producing an organic EL element of the invention, the hole injection layer can be formed by arranging a solution containing a low molecular weight compound on the first electrode layer, so that the first electrode formed by foreign matter or the like is formed. Since defects in the hole injection layer due to the unevenness of the layer are less likely to occur, the first Electrode layer and the short between the second electrode layer may have reduced occur.
Claims (4)
前記正孔注入層は有機溶剤に可溶でありかつ正孔注入性を有する熱分解性の低分子量化合物を含むことを特徴とする有機エレクトロルミネセンス素子。An organic electroluminescent element comprising a first and second electrode layer facing each other and an organic functional layer containing an organic compound sandwiched between the first and second electrode layers, wherein the organic functional layer is A hole injection layer provided in contact with the first electrode layer;
The organic electroluminescent device, wherein the hole injection layer contains a thermally decomposable low molecular weight compound that is soluble in an organic solvent and has a hole injection property.
前記有機機能層を形成する工程は前記第１電極層に接する正孔注入層を形成する工程を含み、
前記正孔注入層を形成する工程は有機溶剤に可溶でありかつ正孔注入性を有する熱分解性の低分子量化合物を含む溶液を作製する工程と前記溶液を前記第１電極層上に配する工程とを含む、ことを特徴とする有機エレクトロルミネセンス素子の製造方法。Forming a first electrode layer on the substrate; forming an organic functional layer containing an organic compound on the first electrode layer; and forming a second electrode layer on the organic functional layer. A method for producing an organic electroluminescent device comprising:
Forming the organic functional layer includes forming a hole injection layer in contact with the first electrode layer;
The step of forming the hole injection layer includes a step of producing a solution containing a thermally decomposable low molecular weight compound that is soluble in an organic solvent and has a hole injection property, and the solution is disposed on the first electrode layer. A process for producing an organic electroluminescent device, comprising:
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| PCT/JP2005/012974 WO2006009050A1 (en) | 2004-07-16 | 2005-07-07 | Organic electroluminescent device and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07331237A (en) * | 1994-06-10 | 1995-12-19 | Toyo Ink Mfg Co Ltd | Hole transport material and its use |
| JP2001291587A (en) * | 2000-02-01 | 2001-10-19 | Canon Inc | Method of manufacturing organic light emitting device and organic light emitting device manufactured by the method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07331237A (en) * | 1994-06-10 | 1995-12-19 | Toyo Ink Mfg Co Ltd | Hole transport material and its use |
| JP2001291587A (en) * | 2000-02-01 | 2001-10-19 | Canon Inc | Method of manufacturing organic light emitting device and organic light emitting device manufactured by the method |
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Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100928 |