JP5086608B2 - Novel di (phenanthroline) derivative, electron transport material comprising the same, and organic electroluminescence device including the same - Google Patents
Novel di (phenanthroline) derivative, electron transport material comprising the same, and organic electroluminescence device including the same Download PDFInfo
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- JP5086608B2 JP5086608B2 JP2006302707A JP2006302707A JP5086608B2 JP 5086608 B2 JP5086608 B2 JP 5086608B2 JP 2006302707 A JP2006302707 A JP 2006302707A JP 2006302707 A JP2006302707 A JP 2006302707A JP 5086608 B2 JP5086608 B2 JP 5086608B2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 description 1
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 1
- 150000004775 coumarins Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012992 electron transfer agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 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 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 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
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 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
- 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 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
本発明は、新規なジ(フェナントロリン)誘導体、それよりなる電子輸送材料およびそれを含む有機エレクトロルミネッセンス素子に関する。 The present invention relates to a novel di (phenanthroline) derivative, an electron transport material comprising the same, and an organic electroluminescence device including the same.
有機EL素子は、電極から注入されたホールと電極の再結合によって生成した励起エネルギーが発光過程を経て基底状態に緩和されることにより自発光する。しかしながら、ホールと電子の再結合によって生成する励起状態には一重項励起状態と三重項励起状態の2種類がそれぞれ1対3の割合で存在する。これまでの多くは一重項励起状態からの発光を利用した蛍光材料が発光材料に利用されていたため、内部量子効率が最大で25%であるので、この時取り出し効率を20%とすると、最大外部量子効率は5%が理論限界であった。 The organic EL element emits light when excitation energy generated by recombination of holes injected from the electrode and the electrode is relaxed to a ground state through a light emission process. However, there are two types of excited states generated by recombination of holes and electrons, a singlet excited state and a triplet excited state, in a ratio of 1: 3. In many cases, a fluorescent material utilizing light emission from a singlet excited state has been used as a light emitting material, and therefore, the internal quantum efficiency is 25% at the maximum. The quantum efficiency was the theoretical limit of 5%.
近年、イリジウムやプラチナなどの重原子効果を利用した錯体化合物を用い三重項励起状態からの発光、すなわちリン光発光を用いることにより発光効率の向上が報告されるようになった(例えば、非特許文献1)。一重項励起状態に加え、三重項励起状態からの発光を利用することで最大内部量子効率は理論上100%に到達することが可能で、リン光材料は発光材料として注目を浴びている(非特許文献3)。 In recent years, improvement in luminous efficiency has been reported by using light emission from a triplet excited state, that is, phosphorescence emission, using a complex compound utilizing a heavy atom effect such as iridium or platinum (for example, non-patented) Reference 1). The maximum internal quantum efficiency can theoretically reach 100% by utilizing light emission from the triplet excited state in addition to the singlet excited state, and phosphorescent materials are attracting attention as light emitting materials (non Patent Document 3).
例えば緑色材料として、下記式
また安達らによる非特許文献2などにより青色発光材料である下記式
その結果最近ではS.R.Forrestらによる非特許文献1では下記式
これら発光材料を効率よく発光させるにはホールと電子の注入バランスを整えて、発光層の中で十分にこれらのキャリアーの結合が行えるようにホール輸送剤や電子輸送剤などを選択しなければならない。
特に青色リン光材料についてはエネルギーギャップが大きいためにワイドギャップ化されたホール輸送剤や電子輸送剤が必要になってくる。現在これらリン光材料については、電子輸送材料に従来から使用されているAlq3〔トリス(8−ヒドロキシキノリノラト)アルミニウム〕やBAlq2〔ビス(2−メチル−8−ヒドロキシキノリノラト)(4−フェニルフェノキシ)アルミニウム〕等が使用されているが、リン光材料に使用するには十分なエネルギーギャップを持ち合わせていないため新規なワイドギャップな電子輸送材料の開発が必要である。
In particular, since the blue phosphorescent material has a large energy gap, a hole transport agent and an electron transport agent having a wide gap are required. For these phosphorescent materials, Alq 3 [tris (8-hydroxyquinolinolato) aluminum] and BAlq 2 [bis (2-methyl-8-hydroxyquinolinolato) (which are conventionally used for electron transport materials) ( 4-phenylphenoxy) aluminum] and the like are used, but since it does not have a sufficient energy gap for use in phosphorescent materials, it is necessary to develop a new wide-gap electron transport material.
本発明の目的は、電子輸送性が高く、高効率の青蛍光素子を形成できる新規なジ(フェナントロリン)誘導体、それよりなる電子輸送材料およびそれを含む有機エレクトロルミネッセンス素子を提供する点にある。 An object of the present invention is to provide a novel di (phenanthroline) derivative that has a high electron transporting property and can form a highly efficient blue fluorescent device, an electron transport material comprising the same, and an organic electroluminescent device including the same.
本発明の第1は、下記一般式(1)
で示されるジ(フェナントロリン)誘導体に関する。
本発明の第2は、請求項1記載のジ(フェナントロリン)誘導体よりなる電子輸送材料に関する。
本発明の第3は、請求項1記載のジ(フェナントロリン)誘導体を含む有機エレクトロルミネッセンス素子に関する。
The first of the present invention is the following general formula (1)
It is related with the di (phenanthroline) derivative shown by these.
The second of the present invention relates to an electron transport material comprising the di (phenanthroline) derivative according to
3rd of this invention is related with the organic electroluminescent element containing the di (phenanthroline) derivative of
本発明のジ(フェナントロリン)誘導体は、下記の反応により製造することができる。
また前記R1〜R7およびR 22 〜R 62 における炭素数1〜6の直鎖または分岐のアルキル基としては、メチル、エチル、プロピル、イソプロピル、n−ブチル、イソブチル、t−ブチル、ヘプチル、イソヘプチル、n−ヘキシル等を挙げることができる。
The di (phenanthroline) derivative of the present invention can be produced by the following reaction.
Further Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in R 1 to R 7 and R 22 to R 62, methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, t- butyl, heptyl, Examples include isoheptyl and n-hexyl.
以下に本発明化合物の具体例を示す。
本発明のジ(フェナントロリン)誘導体は高い電子輸送性能を有する。従って、電子注入材料及び電子輸送材料として使用することができる。
本発明のジ(フェナントロリン)誘導体を有機エレクトロルミネッセンス素子に使用する場合、適当な発光材料(ドーパント)と組み合わせて使用することもできる。
本発明のジ(フェナントロリン)誘導体を電子輸送層に用いる場合、本発明の化合物は電子注入材料や電子輸送材料として使用できる。また他の電子輸送材料と組み合わせて使用することもできる。
The di (phenanthroline) derivative of the present invention has high electron transport performance. Therefore, it can be used as an electron injection material and an electron transport material.
When the di (phenanthroline) derivative of the present invention is used in an organic electroluminescence device, it can be used in combination with a suitable light emitting material (dopant).
When the di (phenanthroline) derivative of the present invention is used for an electron transport layer, the compound of the present invention can be used as an electron injection material or an electron transport material. It can also be used in combination with other electron transport materials.
次に本発明の有機エレクトロルミネッセンス素子について説明する。本発明の有機エレクトロルミネッセンス素子は、陽極と陰極間に一層もしくは多層の有機化合物を積層した素子であり、該有機化合物層の少なくとも一層が本発明のジ(フェナントロリン)誘導体を含有する。有機エレクトロルミネッセンス素子が一層の場合、陽極と陰極間に発光層を設けている。発光層は、発光材料を含有しそれに加えて陽極から注入した正孔もしくは陰極から注入した電子を発光材料まで輸送するのが目的で、正孔注入材料もしくは電子注入材料を含有していても良い。多層型の有機エレクトロルミネッセンス素子の構成例としては、例えばITO/ホール輸送層/発光層/電子輸送層/陰極、ITO/ホール注入層/ホール輸送層/発光層/電子輸送層/陰極、ITO/ホール輸送層/発光層/電子輸送層/電子注入層/陰極、ITO/ホール輸送層/発光層/ホールブロック層/電子輸送層/陰極、ITO/ホール注入層/ホール輸送層/発光層/ホールブロック層/電子輸送層/陰極、ITO/ホール輸送層/発光層/ホールブロック層/電子輸送層/電子注入層/陰極、ITO/ホール注入層/ホール輸送層/発光層/ホールブロック層/電子輸送層/電子注入層/陰極等の多層構成で積層されたものがあげられる。また、必要に応じて陰極上に封止層を有していても良い。 Next, the organic electroluminescence element of the present invention will be described. The organic electroluminescence device of the present invention is a device in which a single layer or a multilayer organic compound is laminated between an anode and a cathode, and at least one layer of the organic compound layer contains the di (phenanthroline) derivative of the present invention. When the organic electroluminescence element is a single layer, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material and may contain a hole injecting material or an electron injecting material for the purpose of transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. . Examples of the configuration of the multi-layer organic electroluminescence element include, for example, ITO / hole transport layer / light-emitting layer / electron transport layer / cathode, ITO / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / cathode, ITO / Hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / cathode, ITO / hole injection layer / hole transport layer / light emitting layer / hole Block layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection layer / cathode, ITO / hole injection layer / hole transport layer / light emitting layer / hole block layer / electron Examples thereof include those laminated in a multilayer structure such as a transport layer / electron injection layer / cathode. Moreover, you may have a sealing layer on a cathode as needed.
正孔輸送層、電子輸送層、および発光層のそれぞれの層は、一層構造であっても、多層構造であっても良い。また正孔輸送層、電子輸送層はそれぞれの層で注入機能を受け持つ層(正孔注入層及び電子注入層)と輸送機能を受け持つ層(正孔輸送層および電子輸送層)を別々に設けることもできる。
本発明の有機エレクトロルミネッセンス素子は、上記構成例に限らず、種々の構成とすることができる。必要に応じて、正孔輸送層成分と発光層成分、あるいは電子輸送層成分と発光層成分を混合した層を設けても良い。
Each of the hole transport layer, the electron transport layer, and the light emitting layer may have a single layer structure or a multilayer structure. In addition, the hole transport layer and the electron transport layer should be provided separately with a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer). You can also.
The organic electroluminescence element of the present invention is not limited to the above configuration example, and can have various configurations. If necessary, a layer in which a hole transport layer component and a light emitting layer component or an electron transport layer component and a light emitting layer component are mixed may be provided.
以下、本発明の有機エレクトロルミネッセンス素子の構成要素に関し、陽極/正孔輸送層/発光層/電子輸送層/陰極からなる素子構成を例として取り上げて詳細に説明する。本発明の有機エレクトロルミネッセンス素子は、基板に支持されていることが好ましい。
基板の素材については特に制限はなく、従来の有機エレクトロルミネッセンス素子に慣用されているものであれば良く、例えばガラス、石英ガラス、透明プラスチックなどからなるものを用いることができる。
Hereinafter, the constituent elements of the organic electroluminescence element of the present invention will be described in detail by taking as an example an element configuration comprising an anode / hole transport layer / light emitting layer / electron transport layer / cathode. The organic electroluminescence device of the present invention is preferably supported on a substrate.
There is no restriction | limiting in particular about the raw material of a board | substrate, What is necessary is just used for the conventional organic electroluminescent element, For example, what consists of glass, quartz glass, a transparent plastic etc. can be used.
本発明の有機エレクトロルミネッセンス素子の陽極としては、仕事関数の大きな金属単体(4eV以上)、仕事関数の大きな金属同士の合金(4eV以上)または導電性物質およびこれらの混合物を電極材料とすることが好ましい。このような電極材料の具体例としては、金、銀、銅等の金属、ITO(インジウム−スズオキサイド)、酸化スズ(SnO2)、酸化亜鉛(ZnO)などの導電性透明材料、ポリピロール、ポリチオフェン等の導電性高分子材料が挙げられる。陽極はこれらの電極材料を、例えば蒸着、スパッタリング、塗布などの方法により基板上に形成することができる。陽極のシート電気抵抗は数百Ω/cm2以下が好ましい。陽極の膜厚は材料にもよるが、一般に5〜1,000nm程度、好ましくは10〜500nmである。 As an anode of the organic electroluminescence device of the present invention, an electrode material may be a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof. preferable. Specific examples of such electrode materials include metals such as gold, silver, and copper, conductive transparent materials such as ITO (indium-tin oxide), tin oxide (SnO 2 ), and zinc oxide (ZnO), polypyrrole, and polythiophene. Examples thereof include conductive polymer materials such as For the anode, these electrode materials can be formed on the substrate by a method such as vapor deposition, sputtering, or coating. The sheet electrical resistance of the anode is preferably several hundred Ω / cm 2 or less. The thickness of the anode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm.
陰極としては、仕事関数の小さな金属単体(4eV以下)、仕事関数の小さな金属同士の合金(4eV以下)または導電性物質およびこれらの混合物を電極材料とすることが好ましい。このような電極材料の具体例としては、リチウム、リチウム−インジウム合金、ナトリウム、ナトリウム−カリウム合金、マグネシウム、マグネシウム−銀合金、マグネシウム−インジウム合金、アルミニウム、アルミニウム−リチウム合金、アルミニウム−マグネシウム合金などが挙げられる。陰極はこれらの電極材料を、例えば蒸着、スパッタリングなどの方法により、薄膜を形成させることにより作製することができる。陰極のシート電気抵抗は数百Ω/cm2以下が好ましい。陰極の膜厚は材料にもよるが、一般に5〜1,000nm程度、好ましくは10〜500nmである。本発明の有機エレクトロルミネッセンス素子の発光を効率良く取り出すために、陽極または陰極の少なくとも一方の電極は、透明もしくは半透明であることが好ましい。 As the cathode, an electrode material is preferably a single metal having a small work function (4 eV or less), an alloy of metals having a small work function (4 eV or less), a conductive substance, or a mixture thereof. Specific examples of such electrode materials include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy. Can be mentioned. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet electrical resistance of the cathode is preferably several hundred Ω / cm 2 or less. The thickness of the cathode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm. In order to efficiently extract light emitted from the organic electroluminescence device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent.
本発明の有機エレクトロルミネッセンス素子の正孔輸送層は、正孔伝達化合物からなるもので、陽極より注入された正孔を発光層に伝達する機能を有している。電界が与えた2つの電極間に正孔伝達化合物が配置されて陽極から正孔が注入された場合、少なくとも10−6cm2/V・秒以上の正孔移動度を有する正孔伝達物質が好ましい。本発明の有機エレクトロルミネッセンス素子の正孔輸送層に使用する正孔伝達物質は、前記の好ましい性質を有するものであれば特に制限はない。従来から光導電材料において正孔の電荷注入輸送材料として慣用されているものや有機エレクトロルミネッセンス素子の正孔輸送層に使用されている公知の材料の中から任意のものを選択して用いることができる。 The hole transport layer of the organic electroluminescence device of the present invention is made of a hole transfer compound and has a function of transferring holes injected from the anode to the light emitting layer. When a hole transport compound is disposed between two electrodes to which an electric field is applied and holes are injected from the anode, a hole transport material having a hole mobility of at least 10 −6 cm 2 / V · second or more is obtained. preferable. The hole transport material used for the hole transport layer of the organic electroluminescence device of the present invention is not particularly limited as long as it has the above-mentioned preferable properties. It is possible to select and use any of the materials conventionally used as hole charge injection / transport materials in photoconductive materials and known materials used for the hole transport layer of organic electroluminescent devices. it can.
前記の正孔伝達物質としては、例えば銅フタロシアニンなどのフタロシアニン誘導体、N,N,N′,N′−テトラフェニル−1,4−フェニレンジアミン、N,N′−ジ(m−トリル)−N,N′−ジフェニル−4,4′−ジアミノビフェニル(TPD)、N,N′−ジ(1−ナフチル)−N,N′−ジフェニル−4,4′−ジアミノビフェニル(α−NPD)、等のトリアリールアミン誘導体、ポリフェニレンジアミン誘導体、ポリチオフェン誘導体、および水溶性のPEDOT:PSS(ポリエチレンジオキサチオフェン−ポリスチレンスルホン酸)が挙げられる。正孔輸送層は、これらの他の正孔伝達化合物一種または二種以上からなる一層で構成されたもので良く、前記の正孔伝達物質とは別の化合物からなる正孔輸送層を積層したものでもよい。 Examples of the hole transfer material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, and N, N′-di (m-tolyl) -N. , N′-diphenyl-4,4′-diaminobiphenyl (TPD), N, N′-di (1-naphthyl) -N, N′-diphenyl-4,4′-diaminobiphenyl (α-NPD), etc. And triarylamine derivatives, polyphenylenediamine derivatives, polythiophene derivatives, and water-soluble PEDOT: PSS (polyethylenedioxathiophene-polystyrenesulfonic acid). The hole transport layer may be composed of one or more of these other hole transport compounds, and a hole transport layer composed of a compound different from the hole transport material is laminated. It may be a thing.
正孔注入材料としては、下記化学式に示すPEDOT:PSS(ポリマー混合物)やDNTPDを挙げることができる。
本発明の有機エレクトロルミネッセンス素子の発光層の発光物質については特に制限されることはなく、従来の公知の化合物の中から任意のものを選択して用いることができる。
発光材料としては、ペリレン誘導体、ナフタセン誘導体、キナクリドン誘導体、クマリン誘導体(例えばクマリン1、クマリン540、クマリン545など)、ピラン誘導体(例えばDCM−1、DCM−2、DCJTBなど)、有機金属錯体{トリス(8−ヒドロキシキノリノラト)アルミニウム(Alq3)、トリス(4−メチル−8−ヒドロキシキノリノラト)アルミニウム(Almq3)等の蛍光材料やビス[2−(4,6−ジフルオロフェニル)ピリジル−N,C2′]イリジウム(III)ピコリレート(FIrpic)、トリス{1−〔4−(トリフルオロメチル)フェニル〕−1H−ピラゾラート,N,C2′}イリジウム(III)(Irtfmppz3)、ビス[2−(4′,6′−ジフルオロフェニル)ピリジネート−N,C2′]テトラキス(1−ピラゾリル)ボレート(Fir6)、トリス(2−フェニルピリジナト)イリジウム(III)[Ir(PPy)3]などのリン光材料}などを挙げることができる。
The light emitting material of the light emitting layer of the organic electroluminescence device of the present invention is not particularly limited, and any one of conventionally known compounds can be selected and used.
Examples of the light-emitting material include perylene derivatives, naphthacene derivatives, quinacridone derivatives, coumarin derivatives (eg,
発光層は、ホスト材料とゲスト材料(ドーパント)から形成することもできる[Appl.Phys.Lett.,65 3610(1989)]。特にリン光材料を発光層に使用する場合、ホスト材料の使用が必要でありこの時使用されるホスト材料としては4,4′−ジ(N−カルバゾリル)−1,1′−ビフェニル(CBP)、1,4−ジ(N−カルバゾリル)ベンゼン、2,2′−ジ〔4″−(N−カルバゾリル)フェニル〕−1,1′−ビフェニル(4CzPBP)等があげられる。
ゲスト材料は、ホスト材料に対して、好ましくは0.01〜40重量%であり、より好ましくは0.1〜20重量%である。ゲスト材料としては、従来公知のFIrpic(化4)、Ir(PPy)3(化3)、Fir6(化6)などを挙げることができる。
The light-emitting layer can also be formed of a host material and a guest material (dopant) [Appl. Phys. Lett. 65 3610 (1989)]. In particular, when a phosphorescent material is used for the light emitting layer, it is necessary to use a host material, and the host material used at this time is 4,4'-di (N-carbazolyl) -1,1'-biphenyl (CBP). 1,2-di (N-carbazolyl) benzene, 2,2′-di [4 ″-(N-carbazolyl) phenyl] -1,1′-biphenyl (4CzPBP) and the like.
The guest material is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight, based on the host material. Examples of guest materials include conventionally known FIrpic (Chemical Formula 4), Ir (PPy) 3 (Chemical Formula 3), and Fir6 (Chemical Formula 6).
本発明の有機エレクトロルミネッセンス素子の電子輸送層の材料としては、本発明のヘテロアリール系化合物が好ましい。このものは単独で使用できるが他の電子輸送材料と併用しても構わない。 As the material for the electron transport layer of the organic electroluminescence device of the present invention, the heteroaryl compound of the present invention is preferred. Although this thing can be used independently, you may use together with another electron transport material.
本発明の有機エレクトロルミネッセンス素子は、電子注入性をさらに向上させる目的で、陰極と有機層の間に絶縁体で構成される電子注入層をさらに設けても良い。ここで使用される導電体としては、アルカリ金属ハロゲン化物、アルカリ土類金属ハロゲン化物から選択される少なくとも一つの金属化合物を使用することが好ましい。アルカリ金属ハロゲン化物としては、フッ化リチウム、フッ化ナトリウム、フッ化カリウム、フッ化セシウム、塩化リチウム等が挙げられる。アルカリ土類金属ハロゲン化物としては、フッ化マグネシウム、フッ化カルシウム、フッ化バリウム、フッ化ストロンチウム等が挙げられる。 The organic electroluminescent device of the present invention may further include an electron injection layer composed of an insulator between the cathode and the organic layer for the purpose of further improving the electron injection property. As the conductor used here, it is preferable to use at least one metal compound selected from alkali metal halides and alkaline earth metal halides. Examples of the alkali metal halide include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride. Examples of the alkaline earth metal halide include magnesium fluoride, calcium fluoride, barium fluoride, and strontium fluoride.
正孔輸送層、発光層の形成方法については特に限定されるものではない。例えば乾式成膜法(例えば真空蒸着法、イオン化蒸着法など)、湿式成膜法〔溶液塗布法(例えば、スピンコート法、キャスト法、インクジェット法など)〕を使用することができる。本発明のジ(フェナントロリン)誘導体の電子輸送層の形成方法については、乾式成膜法(例えば真空蒸着法、イオン化蒸着法)が好ましい。また素子の作製については上記の成膜方法を併用しても構わない。 The method for forming the hole transport layer and the light emitting layer is not particularly limited. For example, a dry film forming method (for example, a vacuum deposition method, an ionization vapor deposition method, etc.) or a wet film forming method [a solution coating method (for example, a spin coating method, a casting method, an ink jet method, etc.)] can be used. As a method for forming the electron transport layer of the di (phenanthroline) derivative of the present invention, a dry film forming method (for example, a vacuum evaporation method or an ionization evaporation method) is preferable. In addition, the above-described film formation method may be used in combination for manufacturing the element.
真空蒸着法により正孔輸送層、発光層、電子輸送層等の各層を形成する場合、真空蒸着条件は、特に限定されるものではない。通常10−4Pa程度以下の真空下で50〜500℃程度のボート温度(蒸着源温度)、−50〜300℃程度の基板温度で、0.01〜50nm/sec.程度蒸着することが好ましい。正孔輸送層、発光層、電子輸送層の各層を複数の化合物を使用して形成する場合、化合物を入れた各ボートをそれぞれ温度制御しながら共蒸着することが好ましい。 When forming each layer such as a hole transport layer, a light emitting layer, and an electron transport layer by a vacuum deposition method, the vacuum deposition conditions are not particularly limited. Usually, a boat temperature (deposition source temperature) of about 50 to 500 ° C. under a vacuum of about 10 −4 Pa or less, a substrate temperature of about −50 to 300 ° C., and 0.01 to 50 nm / sec. Vapor deposition is preferred. When forming each layer of a positive hole transport layer, a light emitting layer, and an electron carrying layer using a some compound, it is preferable to co-evaporate each boat which put the compound, temperature-controlling each.
正孔輸送層、発光層を溶媒塗布法で形成する場合、各層を構成する成分を溶媒に溶解または分散させて塗布液とする。溶媒としては、炭化水素系溶媒(例えば、ヘプタン、トルエン、キシレン、シクロヘキサン等)、ケトン系溶媒(例えばアセトン、メチルエチルケトン、メチルイソブチルケトン等)、ハロゲン系溶媒(例えばジクロロメタン、クロロホルム、クロロベンゼン、ジクロロベンゼン等)、エステル系溶媒(例えば酢酸エチル、酢酸ブチル等)、アルコール系溶媒(例えばメタノール、エタノール、ブタノール、メチルセロソルブ、エチルセロソルブ等)、エーテル系溶媒(例えばジブチルエーテル、テトラヒドロフラン、1,4−ジオキサン、1,2−ジメトキシエタン等)、非プロトン性溶媒(例えばN,N′−ジメチルアセトアミド、ジメチルスルホキシド等)、水等が挙げられる。溶媒は単独で使用しても良く、複数の溶媒を併用しても良い。 When forming the hole transport layer and the light emitting layer by a solvent coating method, the components constituting each layer are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) ), Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like), aprotic solvents (for example, N, N'-dimethylacetamide, dimethyl sulfoxide and the like), water and the like. The solvent may be used alone, or a plurality of solvents may be used in combination.
正孔輸送層、発光層、電子輸送層等の各層の膜厚は、特に限定されるものではないが、通常5〜5,000nmになるようにする。 The thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited, but is usually 5 to 5,000 nm.
本発明の有機エレクトロルミネッセンス素子は、酸素や水分等との接触を遮断する目的で保護層(封止層)を設けたり、不活性物質中に素子を封入して保護することができる。不活性物質としては、パラフィン、シリコンオイル、フルオロカーボン等が挙げられる。保護層に使用する材料としては、フッ素樹脂、エポキシ樹脂、シリコーン樹脂、ポリエステル、ポリカーボネート、光硬化性樹脂等が挙げられる。 The organic electroluminescence device of the present invention can be protected by providing a protective layer (sealing layer) for the purpose of blocking contact with oxygen, moisture, or the like, or by encapsulating the device in an inert substance. Examples of the inert substance include paraffin, silicon oil, and fluorocarbon. Examples of the material used for the protective layer include fluorine resin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.
本発明の有機エレクトロルミネッセンス素子は、通常直流駆動の素子として使用できる。直流電圧を印加する場合、陽極をプラス、陰極をマイナスの極性として電圧を通常1.5〜20V程度印加すると発光が観測される。また、本発明の有機エレクトロルミネッセンス素子は交流駆動の素子としても使用できる。交流電圧を印加する場合には、陽極がプラス、陰極がマイナスの状態になった時に発光する。本発明の有機エレクトロルミネッセンス素子は、例えば電子写真感光体、フラットパネルディスプレイなどの平面発光体、複写機、プリンター、液晶ディスプレイのバックライト、計器等の光源、各種発光素子、各種表示素子、各種標識、各種センサー、各種アクセサリーなどに使用することができる。 The organic electroluminescence device of the present invention can be used as a normal DC drive device. When a DC voltage is applied, light emission is observed when a voltage of about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. Moreover, the organic electroluminescent element of this invention can be used also as an element of an alternating current drive. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state. The organic electroluminescence device of the present invention includes, for example, a flat light emitter such as an electrophotographic photosensitive member and a flat panel display, a copying machine, a printer, a backlight of a liquid crystal display, a light source such as an instrument, various light emitting devices, various display devices, and various signs. It can be used for various sensors and various accessories.
図20〜33に、本発明の有機エレクトロルミネッセンス素子の好ましい例を示す。
図20は、本発明の有機エレクトロルミネッセンス素子の一例を示す断面図である。図20は、基板1上に陽極2、発光層3および陰極4を順次設けた構成のものである。ここで使用する発光素子は、それ自体が正孔輸送性、電子輸送性及び発光性の機能を単一で有している場合や、それぞれの機能を有する化合物を混合して使用する場合に有用である。
図21は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図21は、基板1上に、陽極2、正孔輸送層5、発光層3及び陰極4を順次設けた構成のものである。この場合、発光層は電子輸送性の機能を有している場合に有用である。
図22は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図22は、基板1上に、陽極2、発光層3、電子輸送層6及び陰極4を順次設けた構成のものである。この場合、発光層は正孔輸送性の機能を有している場合に有用である。
20 to 33 show preferred examples of the organic electroluminescence element of the present invention.
FIG. 20 is a cross-sectional view showing an example of the organic electroluminescence element of the present invention. FIG. 20 shows a configuration in which an
FIG. 21 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 21 shows a configuration in which an
FIG. 22 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 22 shows a structure in which an
図23は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図23は、基板1上に、陽極2、正孔輸送層5、発光層3、電子輸送層6及び陰極4を順次設けた構成のものである。これは、キャリア輸送と発光の機能を分離したものであり、材料選択の自由度が増すために、発光の高効率化や発光色の自由度が増すことになる。
図24は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図24は、基板1上に、陽極2、正孔注入層7、正孔輸送層5、発光層3、電子輸送層6及び陰極4を順次設けた構成のものである。この場合、正孔注入層7を設けることにより、陽極2と正孔輸送層5の密着性を高めたり、陽極から正孔の注入を良くし、発光素子の低電圧駆動に効果がある。
FIG. 23 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 23 shows a structure in which an
FIG. 24 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 24 shows a configuration in which an
図25は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図25は、基板1上に、陽極2、正孔輸送層5、発光層3、電子輸送層6、電子注入層8及び陰極4を順次設けた構成のものである。この場合、陰極4から電子の注入を良くし、発光素子の低電圧駆動に効果がある。
図26は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図26は、基板1上に、陽極2、正孔注入層7、正孔輸送層5、発光層3、電子輸送層6、電子注入層8及び陰極4を順次設けた構成のものである。この場合、陽極2から正孔の注入を良くし、陰極4からは電子の注入を良くし、最も低電圧駆動に効果がある構成である。
FIG. 25 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 25 shows a structure in which an
FIG. 26 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 26 shows a structure in which an
図27〜33は、素子の中に正孔ブロック層を挿入したものの断面図である。正孔ブロック層は、陽極から注入された正孔、あるいは発光層3で再結合により生成した励起子が陰極4に抜けることを防止する効果があり、エレクトロルミネッセンス素子の発光効率の向上に効果がある。正孔ブロック層9については、発光層3と陰極4の間もしくは発光層3と電子輸送層6の間あるいは発光層3と電子注入層8の間に挿入することができる。より好ましいものは発光層3と電子輸送層6の間である。
図27〜33で、正孔輸送層5、正孔注入層7、電子輸送層6、電子注入層8、発光層3、正孔ブロック層9のそれぞれの層は、一層構造であっても、多層構造であってもよい。
27 to 33 are cross-sectional views of a device in which a hole blocking layer is inserted. The hole blocking layer has an effect of preventing holes injected from the anode or excitons generated by recombination in the
27 to 33, each of the
図20〜33は、あくまで基本的な素子構成であり、本発明の化合物を用いた有機エレクトロルミネッセンス素子の構成は、これに限定されるものではない。 20 to 33 are basic device configurations to the last, and the configuration of the organic electroluminescence device using the compound of the present invention is not limited thereto.
前記電子注入層に用いる電子注入材料としては本出願人の特願2006−292032号にかかる化合物、例えば下記化合物群を例示することができる。
本発明化合物は、電子の移動度が従来の電子輸送剤、例えばAlq3に比べ非常に大きい。そのため発光開始電圧が1V以上低減でき、また単位電圧における電流密度も大きい。よって本発明の電子輸送材料を使用することによって、素子の低電圧駆動化が図れ、素子の長寿命化にも寄与する。 The compound of the present invention has a very high electron mobility compared to a conventional electron transfer agent such as Alq 3 . Therefore, the light emission start voltage can be reduced by 1 V or more, and the current density in unit voltage is large. Therefore, by using the electron transport material of the present invention, the device can be driven at a low voltage, which contributes to a longer life of the device.
以下に実施例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例1
2,6−ビス[(3−フェナンスロリン−2−イル)フェニル]ピリジン{2,6−Bis[(3−phenanthrolin−2−yl)phenyl]pyridine}(BPnPhPy)の合成
Synthesis of 2,6-bis [(3-phenanthrolin-2-yl) phenyl] pyridine {2,6-Bis [(3-phenanthrolin-2-yl) phenyl]} (BPnPhPy)
実施例2
1,3−ビス[(6−フェナンスロリン−2−イル)ピリジル−2−イル]ベンゼン{1,3−Bis[(6−phenanthrolin−2−yl)pyridyl−2−yl]benzene}(BPyPnB)の合成
1,3-bis [(6-phenanthrolin-2-yl) pyridyl-2-yl] benzene {1,3-Bis [(6-phenanthrolin-2-yl) pyridine-2-yl] benzene} (BPyPnB ) Synthesis
実施例3
4,6−ビス(3−フェナントロ−2−イルフェニル)ピリミジン(PmDPhPn)の合成
Synthesis of 4,6-bis (3-phenanthro-2-ylphenyl) pyrimidine (PmDPhPn)
実施例4
2−メチル−4,6−ビス(3−フェナントロ−2−イルフェニル)ピリミジン(MPmDPhPn)の合成
Synthesis of 2-methyl-4,6-bis (3-phenanthro-2-ylphenyl) pyrimidine (MPmDPhPn)
実施例1で得られた2,6−ビス[(3−フェナンスロリン−2−イル)フェニル]ピリジン(BPnPhPy)、
実施例2で得られた1,3−ビス[(6−フェナンスロリン−2−イル)ピリジル−2−イル]ベンゼン(BPyPnB)、
実施例4で得られた2−メチル−4,6−ビス(3−フェナントロ−2−イルフェニル)ピリミジン(MPmDPhPn)
の電気化学的特性および熱特性を下記表1に、UVスペクトル、PLスペクトルをそれぞれ図1〜図4に示す。
1,3-bis [(6-phenanthrolin-2-yl) pyridyl-2-yl] benzene (BPyPnB) obtained in Example 2 ;
2-Methyl-4,6-bis (3-phenanthro-2-ylphenyl) pyrimidine (MPmDPhPn) obtained in Example 4
The electrochemical characteristics and thermal characteristics are shown in Table 1 below, and the UV spectrum and PL spectrum are shown in FIGS.
Td:分解温度、Tg:二次転移温度、Tm:融点、Ip:イオン化ポテンシャル、Eg:エネルギーギャップ、Ea:エレクトロアフィニティ(電子親和力)、n.d.:検出されず。
Tg(二次転移温度)については、DSC(Diffirential Scanning Calorimeter 示差熱量計)中にサンプルを加え、溶融させたものを急冷し、2〜3回繰り返すとガラス転移を表すカーブがチャート上に現れるので、そのカーブを接線で結び、その交点の温度をTgとして採用する。
Tm(融点)は、同じくDSCにサンプルを加え、昇温していくと吸熱カーブが現れるのでその極大のところとの温度を読んで、その温度をTmとする。
Td(分解温度)は、DTA(Differential thermal analyzer 示差熱分析装置)にサンプルを加え、加熱していくとサンプルが熱によって分解し、重量が減少しだす。その減少が開始しだしたところの温度を読んで、その温度をTdとする。
エネルギーギャップ(Eg)については、蒸着機で作成した薄膜を紫外−可視吸光度計で薄膜の吸収曲線を測定する。その薄膜の短波長側の立ち上がりの所に接線を引き、求まった交点の波長W(nm)を次の式に代入し目的の値を求める。それによって得た値がEgになる。
Eg=1240÷W
例えば接線を引いて求めた値W(nm)が470nmだったとしたらこの時のEgの値は
Eg=1240÷470=2.63(eV)
と言うことになる。
Ip(イオン化ポテンシャル)は、イオン化ポテンシャル測定装置(例えば理研計器AC−1)を使用して測定し、測定するサンプルがイオン化を開始しだしたところの電圧(eV)の値を読む。
Ea(電子親和力)は、IpからEgを引いた値である。
本明細書における波長に対する強度(intensity a.u.)の測定は、浜松ホトニクス社製ストリークカメラを用いて、クライオスタット中で4.2Kにおいて測定した。
Td: decomposition temperature, Tg: secondary transition temperature, Tm: melting point, Ip: ionization potential, Eg: energy gap, Ea: electroaffinity (electron affinity), n. d. : Not detected.
As for Tg (secondary transition temperature), a sample is added to DSC (Differential Scanning Calorimeter), the melted sample is rapidly cooled, and a curve representing the glass transition appears on the chart when repeated 2-3 times. The curves are connected by tangent lines, and the temperature at the intersection is adopted as Tg.
As for Tm (melting point), an endothermic curve appears when a sample is added to the DSC and the temperature is raised, so the temperature at the maximum is read and the temperature is defined as Tm.
As for Td (decomposition temperature), when a sample is added to DTA (Differential Thermal Analyzer) and heated, the sample is decomposed by heat and the weight starts to decrease. The temperature at which the decrease starts is read and the temperature is defined as Td.
Regarding the energy gap (Eg), an absorption curve of the thin film prepared with a vapor deposition machine is measured with an ultraviolet-visible absorptiometer. A tangent line is drawn at the rising edge of the thin film on the short wavelength side, and the wavelength W (nm) at the obtained intersection is substituted into the following equation to obtain the target value. The value obtained thereby becomes Eg.
Eg = 1240 ÷ W
For example, if the value W (nm) obtained by drawing a tangent is 470 nm, the value of Eg at this time is Eg = 1240 ÷ 470 = 2.63 (eV)
Would be said.
Ip (ionization potential) is measured using an ionization potential measuring apparatus (for example, Riken Keiki AC-1), and the value of the voltage (eV) at which the sample to be measured starts ionization is read.
Ea (electron affinity) is a value obtained by subtracting Eg from Ip.
Intensity au in this specification was measured at 4.2K in a cryostat using a streak camera manufactured by Hamamatsu Photonics.
実施例5〜6、比較例1
実施例1で得られた2,6−ビス[(3−フェナンスロリン−2−イル)フェニル]ピリジン(BPnPhPy)、
実施例2で得られた1,3−ビス[(6−フェナンスロリン−2−イル)ピリジル−2−イル]ベンゼン(BPyPnB)を用いて、下記有機EL素子を作った。
<有機EL素子の構成>
比較例1:ITO/α−NPD(50nm)/Alq3(70nm)/LiF(0.5nm)/Al
実施例5:ITO/α−NPD(50nm)/Alq3(40nm)/BPnPhPy(30nm)/LiF(0.5nm)/Al
実施例6:ITO/α−NPD(50nm)/Alq3(40nm)/BPyPnB(30nm)/LiF(0.5nm)/Al
2,6-bis [(3-phenanthrolin-2-yl) phenyl] pyridine (BPnPhPy) obtained in Example 1 ,
The following organic EL device was produced using 1,3-bis [(6-phenanthrolin-2-yl) pyridyl-2-yl] benzene (BPyPnB) obtained in Example 2 .
<Configuration of organic EL element>
Comparative Example 1: ITO / α-NPD (50 nm) / Alq 3 (70 nm) / LiF (0.5 nm) / Al
Example 5 : ITO / α-NPD (50 nm) / Alq 3 (40 nm) / BPnPhPy (30 nm) / LiF (0.5 nm) / Al
Example 6 : ITO / α-NPD (50 nm) / Alq 3 (40 nm) / BPyPnB (30 nm) / LiF (0.5 nm) / Al
上記有機EL素子の特性は、下記表2に示す。
電流密度−電圧特性を図5に、
輝度 −電圧特性を図6に、
電流効率−電圧特性を図7に、
ELスペクトル を図8に示す。
The characteristics of the organic EL element are shown in Table 2 below.
The luminance-voltage characteristics are shown in FIG.
Figure 7 shows the current efficiency vs. voltage characteristics.
The EL spectrum is shown in FIG.
実施例7〜8
実施例1で得られた2,6−ビス[(3−フェナンスロリン−2−イル)フェニル]ピリジン(BPnPhPy)、
実施例2で得られた1,3−ビス[(6−フェナンスロリン−2−イル)ピリジル−2−イル]ベンゼン(BPyPnB)を用いて、下記有機EL素子を作った。
<有機EL素子の構成>
実施例7:ITO/Buffer(20nm)/α−NPD(20nm)/TBADN:4%Sty−NPD(30nm)/BPnPhPy(40nm)/LiF(0.5nm)/Al
実施例8:ITO/Buffer(20nm)/α−NPD(20nm)/TBADN:4%Sty−NPD(30nm)/BPyPnB(40nm)/LiF(0.5nm)/Al
2,6-bis [(3-phenanthrolin-2-yl) phenyl] pyridine (BPnPhPy) obtained in Example 1 ,
The following organic EL device was produced using 1,3-bis [(6-phenanthrolin-2-yl) pyridyl-2-yl] benzene (BPyPnB) obtained in Example 2 .
<Configuration of organic EL element>
Example 7 : ITO / Buffer (20 nm) / α-NPD (20 nm) / TBADN: 4% Sty-NPD (30 nm) / BPnPhPy (40 nm) / LiF (0.5 nm) / Al
Example 8 : ITO / Buffer (20 nm) / α-NPD (20 nm) / TBADN: 4% Sty-NPD (30 nm) / BPyPnB (40 nm) / LiF (0.5 nm) / Al
前記有機EL素子の特性は、下記表3、表4に示す。
電流密度−電圧特性を図9に、
輝度 −電圧特性を図10に、
視感効率−電圧特性を図11に、
電流効率−電圧特性を図12に、
電流効率−輝度特性を図13に、
ELスペクトル を図14に
示す。
The characteristics of the organic EL element are shown in Tables 3 and 4 below.
The luminance-voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The current efficiency-luminance characteristics are shown in FIG.
The EL spectrum is shown in FIG.
実施例9
実施例4で得られた2−メチル−4,6−ビス(3−フェナントロ−2−イルフェニル)ピリミジン(MPmDPhPn)を用いて有機EL素子をつくり、比較例1および実施例5の有機EL素子とその性能を比較した。
<有機EL素子の構成>
比較例1:ITO/α−NPD(50nm)/Alq3(70nm)/LiF(0.5nm)/Al
実施例5:ITO/α−NPD(50nm)/Alq3(40nm)/BPnPhPy(30nm)/LiF(0.5nm)/Al
実施例9:ITO/α−NPD(50nm)/Alq3(40nm)/MPmDPhPn(30nm)/LiF(0.5nm)/Al
また、これらの素子の
電流密度−電圧特性を図15に、
輝度 −電圧特性を図16に、
視感効率−電圧特性を図17に、
電流効率−電圧特性を図18に、
ELスペクトル を図19に
示す。
Example 9
An organic EL device was prepared using 2-methyl-4,6-bis (3-phenanthro-2-ylphenyl) pyrimidine (MPmDPhPn) obtained in Example 4 , and the organic EL devices of Comparative Example 1 and Example 5 were used. And its performance was compared.
<Configuration of organic EL element>
Comparative Example 1: ITO / α-NPD (50 nm) / Alq 3 (70 nm) / LiF (0.5 nm) / Al
Example 5 : ITO / α-NPD (50 nm) / Alq 3 (40 nm) / BPnPhPy (30 nm) / LiF (0.5 nm) / Al
Example 9 : ITO / α-NPD (50 nm) / Alq 3 (40 nm) / MPmDPhPn (30 nm) / LiF (0.5 nm) / Al
The current density-voltage characteristics of these elements are shown in FIG.
The luminance-voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The EL spectrum is shown in FIG.
前記有機EL素子の特性を下記表5に示す。
1 基板
2 陽極(ITO)
3 発光層
4 陰極
5 正孔輸送層(ホール輸送層)
6 電子輸送層
7 正孔注入層(ホール注入層)
8 電子注入層
9 正孔ブロック層(ホールブロック層)
1
3
6
8
Claims (3)
で示されるジ(フェナントロリン)誘導体。 The following general formula (1)
A di (phenanthroline) derivative represented by:
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