WO2010104349A2 - 정공주입층 및 정공수송층 재료로 사용가능한 화합물 및 이를 이용한 유기발광소자 - Google Patents

정공주입층 및 정공수송층 재료로 사용가능한 화합물 및 이를 이용한 유기발광소자 Download PDF

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WO2010104349A2
WO2010104349A2 PCT/KR2010/001538 KR2010001538W WO2010104349A2 WO 2010104349 A2 WO2010104349 A2 WO 2010104349A2 KR 2010001538 W KR2010001538 W KR 2010001538W WO 2010104349 A2 WO2010104349 A2 WO 2010104349A2
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compound
formula
injection layer
imidazolium
hole injection
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English (en)
French (fr)
Korean (ko)
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WO2010104349A3 (ko
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서광석
김종은
김태영
이태희
서민원
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Priority to CN2010800112168A priority Critical patent/CN102348705A/zh
Priority to JP2011553958A priority patent/JP2012520373A/ja
Priority to US13/255,456 priority patent/US20110315976A1/en
Publication of WO2010104349A2 publication Critical patent/WO2010104349A2/ko
Publication of WO2010104349A3 publication Critical patent/WO2010104349A3/ko
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings

Definitions

  • the present invention relates to a compound which can be used as a hole injection layer or a hole transporting layer material in connection with an organic light emitting diode or an electrode of an electrical device.
  • the compound of the present invention is prepared by synthesizing a conductive polymer using a polymer ionic liquid, which can be used as a hole layer material of an organic light emitting device, and the hole injection layer of an organic light emitting device using the compound according to the present invention maintains its performance. The service life is much better than existing materials.
  • the CRT which is an imaging device using an electron gun
  • This liquid crystal display device is a technology for directing light by directing a liquid crystal by applying a voltage from the outside, and almost all imaging devices have recently used this technology.
  • An imaging device capable of overcoming these disadvantages is an organic light emitting device, which is formed by stacking several materials to a few tens of nanometers thickness without the need for a separate light source, and then applying light thereto to generate light between the layers. Since there is no need for this, there is a great advantage of not having to use a plurality of functional films used in an imaging apparatus using liquid crystal alignment technology.
  • tin oxide doped with indium element is used as a transparent electrode layer, which is a layer to which voltage can be applied.
  • ITO indium element
  • a hole transport layer such as' -diamine (NPB)
  • a light emitting layer such as aluminum tris (8-hydroxyquinoline) (Alq 3 )
  • Alq 3 an electron injection layer
  • LiF lithium fluoride
  • metal electrode layer such as aluminum to apply a voltage thereon Element.
  • poly (3,4-ethylenedioxythiophene): polystyrenesulfonate (hereinafter referred to as PEDOT: PSS and type: AI4083 from HC Starck, Germany), which is a kind of conductive polymer of HC Starck, Germany, was used as a hole injection layer material.
  • PEDOT polystyrenesulfonate
  • AI4083 is a kind of conductive polymer of HC Starck, Germany
  • PEDOT: PSS is used as the hole injection layer material
  • the acidity of the material is too high, and when used and applied on the indium tin oxide (ITO) layer, which is a transparent electrode, the organic material is extracted over time by extracting the indium of the transparent electrode layer. It is known to shorten the life of a light emitting element.
  • ITO indium tin oxide
  • An object of the present invention is to provide a new compound that can be used as a hole layer-related material, such as a new hole injection or an organic material for a hole transport layer that can improve the life of the organic light emitting device.
  • R 1 and R 3 are the same as or different from each other, and each represent hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and may optionally include one or more hetero atoms.
  • R 2 is a group containing 0 to 16 carbon atoms and may optionally include one or more hetero atoms.
  • Y ⁇ -> represents the anion of the imidazolium type polymer ionic liquid.
  • R 4 and R 5 are each hydrogen, halogen, or a hydrocarbon having 1 to 15 carbon atoms and are composed of a group optionally containing at least one hetero atom, or R 4 and R 5 together are a 3 to 8 membered aromatic ring or Alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy, forming an aliphatic ring compound, consisting of groups optionally containing one or more heteroatoms.
  • X represents any one selected from NH, NR, S, O, Se, and Te.
  • the compound of Formula 1 may be used as a hole injection layer or a hole transport layer material, such as an organic light emitting device.
  • the compound prepared according to the present invention has the advantage that the conductive polymer is dispersed in an organic solvent using an imidazolium-based polymer ionic liquid compound and has a very low acidity.
  • Conventional conductive polymers are dispersed in water and have a very high acidity, so when used as a hole injection layer of an organic light emitting device, the device life is abruptly shortened. On the other hand, when the compound of the present invention is used as a hole injection layer, The life of the light emitting device can be significantly increased.
  • the compound according to the present invention has the advantage of easily forming a large area layer using an inkjet printing or spin coating method when used as a hole layer material.
  • 1 is a cross-sectional view showing the structure of an organic light emitting device using the compound of the present invention.
  • a conductive polymer is synthesized by mixing a conductive polymer synthesis monomer, an oxidizing agent, and an imidazolium polymer ionic liquid dissolved in an organic solvent.
  • the synthesized conductive polymer may be washed with water or an aqueous solvent and dried to obtain a final conductive polymer in the form of particles, or washed with an organic solvent to obtain a final conductive polymer solution in which the conductive polymer is dispersed in an organic solvent.
  • the imidazolium-based polymer ionic liquid is a compound in a polymer form composed of an organic cation and an organic or inorganic anion including an imidazolium group as shown in the following Formula 2.
  • R 1 and R 3 are the same or different, and each represent hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and may optionally include one or more heteroatoms.
  • R 2 is a group containing 0 to 16 carbon atoms and may optionally include one or more hetero atoms.
  • Y ⁇ -> represents the anion of the imidazolium type polymer ionic liquid.
  • the imidazolium-based polymer ionic liquid may be a material having various physical and chemical properties according to a combination of cations and anions.
  • the imidazolium-based polymer ionic liquid has high solubility in organic solvents and stably disperses conductive polymers in organic solvents. It is advantageous to use one.
  • cationic component of the compound including the imidazolium group represented by Formula 2 include poly (1-vinyl-3-alkylimidazolium), poly (1-allyl-3-alkylimidazolium), and poly ( 1- (meth) acryloyloxy-3-alkylimidazolium), and the like.
  • CH 3 COO as an anion represented by Y in the general formula (2) is not particularly limited in solubility side in an organic solvent -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, (CF 3 CF 2 SO 2) 2 N -, C 4 F 9 SO 3 -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 it is preferable to use such as - CO) N.
  • the imidazolium-based polymer ionic liquid may first prepare a monomolecular compound, and then use the conventional radical polymerization reaction to make a compound of a polymer form, or may use a compound made of a polymer.
  • the monomer for synthesizing a conductive polymer that can be used in the present invention is represented by the following formula (3).
  • R 4 and R 5 are each hydrogen, halogen, or a hydrocarbon of 1 to 15 carbon atoms, consisting of a group optionally containing one or more hetero atoms, or R 4 and R 5 together are a 3 to 8 membered aromatic ring or aliphatic Alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy, forming a ring compound, consisting of a group optionally containing one or more heteroatoms.
  • X represents any one selected from NH, NR, S, O, Se, and Te.
  • the monomer of Chemical Formula 3 is an organic material having a conjugated double bond having a cyclic structure containing a hetero atom, and the polymer produced through the polymerization reaction shows electrical conductivity and facilitates hole injection.
  • Two methods may be used to synthesize the conductive polymer using the imidazolium-based polymer ionic liquid compound.
  • One method can obtain a conductive polymer solution dispersed in an organic solvent by dissolving the organic solvent imidazolium polymer ionic liquid of Formula 2, the monomer of Formula 3, and the oxidizing agent in an organic solvent and then polymerizing.
  • the second method is to prepare a water-based conductive polymer solution by mixing a water-soluble imidazolium-based polymer ionic liquid, a monomer of Formula 3, and an oxidizing agent in an aqueous system, and then anion of the imidazolium-based polymer ionic liquid contained therein.
  • anion of the imidazolium-based polymer ionic liquid contained therein By inducing a substitution reaction with an organic solvent soluble anion, Y - so that the conductive polymer can be dispersed in an organic solvent.
  • an organic solvent dispersible conductive polymer solution having high purity and high acidity, which is uniformly dispersed in an organic solvent can be obtained through an appropriate washing process.
  • the oxidizing agent for polymerizing the conductive polymer monomer is not particularly limited as long as it can induce a conductive polymer polymerization reaction, for example hydrogen peroxide, organic or inorganic peroxide, persulfates, peracids, peroxidation Acids (peroxyacids), bromics, chlorates, perchlorates, and iron (III), chromium (IV), chromium (VI), manganese (VII), manganese (V), manganese (IV) ), Vanadium (V), ruthenium (IV), organic or inorganic salts of copper (II) and the like can be used.
  • a conductive polymer polymerization reaction for example hydrogen peroxide, organic or inorganic peroxide, persulfates, peracids, peroxidation Acids (peroxyacids), bromics, chlorates, perchlorates, and iron (III), chromium (IV), chromium (VI), manganese (VII), manganese (V),
  • the conductive polymer synthesized as described above, that is, the compound according to the present invention may be dispersed in an organic solvent and used as a hole injection layer or a hole transport layer material of an organic light emitting device.
  • the conductive polymer of the present invention is preferably dispersed in the following organic solvents can be used.
  • Representative organic solvents include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol and isobutanol, ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, tetrahydrofuran, ethylene glycol and propylene Alcohol ether solvents, such as glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether, ketone solvents, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, N-methyl-2- Amide solvents such as
  • Nitrile solvents such as sulfone solvents, acetonitrile, benzonitrile, amine solvents such as alkylamines, cyclic amines, aromatic amines, methyl butylate, Ester solvents such as butyl butyrate and propyl propionate, carboxylic acid ester solvents such as ethyl acetate and butyl acetate, aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene and xylene, hexane, heptane and cyclohexane Aliphatic hydrocarbon solvents, such as chloroform, tetrachloroethylene, halogenated hydrocarbon solvents such as carbon tetrachloride, dichloromethane, dichloroethane, propylene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, ethylmethyl carbonate, dibutyl carbonate
  • the organic light emitting device of FIG. 1 is an example in which a hole injection layer is formed of the compound of the present invention, and a hole injection layer may be formed of the compound of the present invention to make organic light emitting devices having various structures.
  • the hole injection layer 15 is formed by forming PEDOT, which is the compound of the present invention (Formula 1), on the surface of the ITO film 16, which is a transparent electrode, as a positive electrode. It is made by forming a hole transport layer 14 on the hole injection layer 15, and then again forming the light emitting layer 13 and the electron injection layer 12 thereon, and finally to form a cathode electrode 11 again .
  • a hole injection layer is formed to a thickness of 5-100 nanometers by the spin coating method of the conductive polymer solution dispersed in the organic solvent on the surface of the ITO film, which is a transparent electrode.
  • the organic light emitting device may be manufactured by sequentially forming the necessary layers as shown in FIG. 1.
  • the organic thin film layer material as a hole transport layer N, N'-diphenyl-N, N'-bis (1-naphthyl)-(1,1'-biphenyl) -4,4 '-diamine (NPB), light emitting layer material aluminum tris (8-hydroxyquinoline) (Alq 3 ), LiQ as electron injection layer, Al as cathode material, each layer is vacuum-deposited or sputtered organic light emitting device To prepare.
  • the hole injection layer material of the present invention is effective to increase the life of the organic light emitting device.
  • Examples and Comparative Examples of the present invention used a hole injection layer material mainly made of 3,4-ethylenedioxythiophene monomer.
  • the technique of the present invention is not limited to this monomer but is applicable to all monomers shown in formula (3) such as pyrrole, thiophene, or other conductive polymer monomers.
  • an organic light emitting diode was manufactured using PEDOT: PSS (Grade name: Clevios P AI4083, H. C. Starck, Germany), which was previously commercialized as a hole injection layer material.
  • the organic light emitting device was made to be ITO (150 nm) // AI4083 (50 nm) // NPB (60 nm) // Alq (50 nm) // LiQ (1 nm) // Al (100 nm).
  • Example 1 is a hole injection layer material except for using the conductive polymer solution dispersed in the content of 3% by weight (wt%) in the organic solvent propylene carbonate using the imidazolium-based polymer ionic liquid compound of the present invention Is the same as the comparative example.
  • the organic solvent dispersible conductive polymer used in Example 1 was prepared by the following method. 1.5 grams of poly (1-vinyl-3-ethylimidazolium bromide) having a weight average molecular weight of 170,000 grams / mole and 1 gram of 3,4-ethylenedioxythiophene, a monomer for synthesizing conductive polymers, were placed in 150 ml of water and used as a polymerization initiator. Ammonium persulfate was added dropwise at a molar ratio of 1.2 to the monomer to prepare an aqueous conductive polymer through a polymerization reaction at room temperature.
  • the compound of the present invention can be used in various fields such as the organic light emitting device and the liquid crystal display device field.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/KR2010/001538 2009-03-11 2010-03-11 정공주입층 및 정공수송층 재료로 사용가능한 화합물 및 이를 이용한 유기발광소자 Ceased WO2010104349A2 (ko)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2010800112168A CN102348705A (zh) 2009-03-11 2010-03-11 能够被用作空穴注入层和空穴传输层材料的化合物及使用该化合物的有机发光二极管
JP2011553958A JP2012520373A (ja) 2009-03-11 2010-03-11 正孔注入層及び正孔輸送層の材料として使用可能な化合物及びこれを用いた有機発光素子
US13/255,456 US20110315976A1 (en) 2009-03-11 2010-03-11 Compounds usable as materials for a hole injection layer or hole transport layer, and organic light-emitting diode using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090020863A KR101111435B1 (ko) 2009-03-11 2009-03-11 정공주입층 및 정공수송층 재료로 사용가능한 화합물 및 이를 이용한 유기발광소자
KR10-2009-0020863 2009-03-11

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WO2010104349A3 WO2010104349A3 (ko) 2011-02-24

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JP (1) JP2012520373A (enExample)
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WO2015190727A1 (ko) * 2014-06-13 2015-12-17 주식회사 엘지화학 전도성 고분자 잉크 조성물
US10240057B2 (en) 2014-06-13 2019-03-26 Lg Chem, Ltd. Conductive polymeric ink composition
WO2020055000A1 (ko) * 2018-09-10 2020-03-19 주식회사 디엠에스 유기재료, 유기재료 제조방법 및 유기발광소자

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US8906752B2 (en) 2011-09-16 2014-12-09 Kateeva, Inc. Polythiophene-containing ink compositions for inkjet printing
CN104272485B (zh) * 2012-05-10 2018-11-16 默克专利有限公司 用于电子传输层中的包含离子有机化合物的配制剂
WO2015023302A1 (en) 2013-08-12 2015-02-19 Kateeva, Inc. Ester-based solvent systems for printable organic light-emitting diode ink formulations
KR101594917B1 (ko) * 2014-04-22 2016-02-17 국방과학연구소 유기발광 중합체, 이의 제조방법 및 이를 포함하는 유기발광 소자
EP3133664A1 (en) * 2015-08-18 2017-02-22 Novaled GmbH Triaryl amine thick layer doped with metal amides for use as hole injection layer for an organic light-emitting diode (oled)
EP4084108B1 (en) * 2015-08-18 2025-11-12 Novaled GmbH Metal amides for use as hil for an organic light-emitting diode (oled)
CN110494514A (zh) * 2017-04-10 2019-11-22 默克专利有限公司 有机功能材料的制剂
KR102380360B1 (ko) * 2017-09-28 2022-03-29 엘지디스플레이 주식회사 발광다이오드 및 이를 포함하는 발광장치
KR102787764B1 (ko) * 2019-12-27 2025-03-31 주식회사 디엠에스 유기재료 처리방법, 이에 의하여 제조된 유기재료 혼합물 및 유기재료 혼합물을 이용한 전자소자
WO2025210722A1 (ja) * 2024-04-02 2025-10-09 シャープディスプレイテクノロジー株式会社 発光素子、表示装置、発光素子の製造方法及び表示装置の製造方法

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WO2015190727A1 (ko) * 2014-06-13 2015-12-17 주식회사 엘지화학 전도성 고분자 잉크 조성물
US10240057B2 (en) 2014-06-13 2019-03-26 Lg Chem, Ltd. Conductive polymeric ink composition
WO2020055000A1 (ko) * 2018-09-10 2020-03-19 주식회사 디엠에스 유기재료, 유기재료 제조방법 및 유기발광소자

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KR20100102464A (ko) 2010-09-24
US20110315976A1 (en) 2011-12-29
KR101111435B1 (ko) 2012-02-16
WO2010104349A3 (ko) 2011-02-24
CN102348705A (zh) 2012-02-08
JP2012520373A (ja) 2012-09-06
TW201038537A (en) 2010-11-01

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