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WO2019164180A1 - Composition pour dispositif électroluminescent organique, matériau de couche d'injection de trous fabriqué à partir de celle-ci, et dispositif électroluminescent organique comprenant une couche d'injection de trous - Google Patents

Composition pour dispositif électroluminescent organique, matériau de couche d'injection de trous fabriqué à partir de celle-ci, et dispositif électroluminescent organique comprenant une couche d'injection de trous Download PDF

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Publication number
WO2019164180A1
WO2019164180A1 PCT/KR2019/001805 KR2019001805W WO2019164180A1 WO 2019164180 A1 WO2019164180 A1 WO 2019164180A1 KR 2019001805 W KR2019001805 W KR 2019001805W WO 2019164180 A1 WO2019164180 A1 WO 2019164180A1
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Prior art keywords
light emitting
composition
organic light
formula
compound
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English (en)
Korean (ko)
Inventor
류승윤
김동현
이종찬
이원호
최대근
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Korea University Research and Business Foundation
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Korea University Research and Business Foundation
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Priority claimed from KR1020190016567A external-priority patent/KR102174374B1/ko
Application filed by Korea University Research and Business Foundation filed Critical Korea University Research and Business Foundation
Priority to US16/755,649 priority Critical patent/US20200274071A1/en
Priority to CN201980005324.5A priority patent/CN111373560B/zh
Priority to JP2020517536A priority patent/JP6868749B2/ja
Publication of WO2019164180A1 publication Critical patent/WO2019164180A1/fr
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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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances

Definitions

  • the present invention relates to an organic electroluminescent device comprising a composition for an organic electroluminescent device, a hole injection layer material and a hole injection layer prepared therefrom.
  • the organic light emitting display device refers to an active light emitting display device using a phenomenon in which light is generated while electrons and holes are combined when a current flows through a fluorescent or phosphorescent organic compound thin film (hereinafter, referred to as an organic film).
  • an organic light emitting display device is capable of low voltage driving, relatively low power consumption, and high color purity.
  • a general organic electroluminescent device has a structure in which an anode is formed on an upper portion of a substrate, and a hole transport layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially formed on the anode.
  • the hole transport layer, the hole transport layer, the light emitting layer and the electron transport layer and the like are organic films made of an organic compound or an organic-inorganic mixed compound.
  • the driving principle of the organic light emitting display device having the structure as described above is as follows.
  • a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole transport layer.
  • electrons are injected into the light emitting layer through the electron transport layer from the cathode and carriers are recombined in the light emitting layer to generate excitons.
  • the excitons are radiated decay, light of a wavelength corresponding to the band gap of the material is emitted.
  • the organic electroluminescent device has a stable charge balance and a hole transport layer material, a hole transport layer material, a light emitting layer material and an electron transport layer material, which are organic materials. Backed by efficient materials should be preceded.
  • the development of a material for forming an organic film for an organic light emitting device, which is stable and efficient in charge balance, has not been sufficiently achieved.
  • An object of the present invention is to provide an organic electroluminescent device comprising a composition for an organic electroluminescent device, a hole injection layer material and a hole injection layer prepared therefrom for realizing improved light emission characteristics and lifetime characteristics.
  • composition for an organic electroluminescent device comprising a conductive polymer composite including an acid group and a compound of the formula (1).
  • R 1 is C 3 -C 30 cycloalkyl, C 3 -C 30 heterocycloalkyl, C 6 -C 30 aryl or C 6 -C 30 heteroaryl;
  • R 2 is a lactam group or a fused lactam group
  • R 1 of the cycloalkyl, heterocycloalkyl, aryl or heteroaryl group and the lactam group or a fused lactam of the R 2 groups are each independently halogen, hydroxy, cyano, carboxyl, carboxylic acid salts, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 30 aryl and C 6 may be further substituted with one or more substituents selected from -C 30 heteroaryl;
  • R 1 is C 3 -C 30 cycloalkyl or C 6 -C 30 aryl
  • R 2 may be a lactam group fused with an alicyclic ring.
  • R 11 is C 1 -C 7 alkyl or C 2 -C 7 alkenyl
  • R 12 and R 13 is hydrogen, C 1 -C 7 alkyl, C 1 -C 7 alkoxy or C 1 -C 7 thioxy, the other may be linked to R 11 to form an alicyclic ring and ;
  • R 11 alkyl or alkenyl and wherein R 12 and R 13 alicyclic ring are each independently selected from halogen, hydroxy, cyano, carboxyl, carboxylic acid salt is one that is formed by the connection of the R 11, C 1 -C Further substituted with one or more substituents selected from 7 alkyl, C 1 -C 7 alkoxy, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, C 6 -C 12 aryl, and C 6 -C 12 heteroaryl And -CH 2 -in the alicyclic ring may be replaced with a heteroatom selected from O and S and the like.
  • the compound may be at least one selected from a compound of Formula 3 and a compound of Formula 4.
  • R 1 is C 3 -C 12 cycloalkyl or C 6 -C 12 aryl
  • R 21 to R 24 are each independently selected from hydrogen, halogen, hydroxy, cyano, carboxyl, carboxylate and C 1 -C 7 alkyl;
  • the cycloalkyl or aryl of R 1 may be each independently further substituted with one or more substituents selected from halogen, hydroxy, cyano, carboxyl, C 1 -C 7 alkyl and the like.
  • the compound may be one or two or more selected from ampicillin, amocillin, cephalexin, cepradine, cefachlor, and the like.
  • the conductive polymer composite including the acidic group may be a mixture of a polythiophene polymer and an aromatic sulfonate polymer.
  • the conductive polymer composite including the acidic group may be a mixture of poly (3,4-ethylenedioxythiophene) and poly (styrenesulfonate).
  • PH of the composition may be less than 9.0.
  • the pH of the composition may be 2.0 to 8.5.
  • the composition may include less than 10 moles of primary amine groups in the compound of Formula 1 based on 1 mole of sulfonic acid ions of the poly (styrenesulfonate).
  • a hole injection layer material prepared using a conductive polymer composite including an acid group and a composition for an organic electroluminescent device comprising the compound of Formula 1.
  • an organic electroluminescent device comprising the hole injection layer material.
  • the organic light emitting device includes an anode, a hole injection layer including the hole injection layer material, a hole transport layer, a light emitting layer, an electron transport layer and a cathode.
  • the organic light emitting device includes a display device; Display elements; Or elements for monochrome or white illumination; And so on.
  • composition for an organic light emitting device when used as a hole injection layer, when carriers are recombined in the emission layer region, band gap alignment due to the formation of unique interfacial dipoles, improved balance between holes and electrons And surprisingly enhanced organics by forming excitons by J / H-aggregation, inducing intermolecular bonds of antibiotic-specific ' ⁇ -lactam' structures, inducing ordered dipoles, and excitons by strong chromophores interaction The efficiency of the electroluminescent device can be realized.
  • composition for an organic light emitting device according to the present invention when using the composition for an organic light emitting device according to the present invention as a hole injection layer, it is possible to implement a low work function.
  • composition for an organic light emitting device according to the present invention is dispersed in water to adjust the acidity to implement the efficiency according to the purpose, it can effectively suppress the abrupt shortening of the device life according to the high acidity.
  • the hole injection layer material manufactured by using the composition for an organic light emitting device according to the present invention it is possible to provide an organic light emitting device excellent in light emission characteristics (efficiency) and life characteristics at the same time.
  • FIG. 1 shows a cross-sectional structure of an organic light emitting display device according to the present invention.
  • QE max the maximum external quantum efficiency
  • PE max the maximum power efficiency of the organic light emitting display device according to the present invention.
  • alkyl other than “alkyl”, “alkoxy”, “thioxy” means a functional group derived from a straight chain or pulverized hydrocarbon.
  • the alkyl and the substituent including the alkyl according to the present invention is preferably a short chain having 1 to 7 carbon atoms, preferably may be selected from methyl, ethyl, propyl and butyl, but is not limited thereto.
  • alkoxy means * -O-alkyl and thioxy means * -S-alkyl.
  • alkenyl refers to an organic radical derived from a straight chain or pulverized hydrocarbon containing one or more double bonds
  • alkynyl refers to a straight or pulverized form containing one or more triple bonds
  • carboxyl herein also means * -COOH.
  • carboxylate in the present specification means * -COOM, wherein M may be an alkali metal (Na, K, etc.).
  • cycloalkyl also refers to organic radicals derived from fully saturated or partially unsaturated hydrocarbon rings of 3 to 9 carbon atoms
  • aryl as used herein also means an organic radical derived from an aromatic hydrocarbon ring by one hydrogen removal, each ring containing 4 to 7, preferably 5 or 6 ring atoms, as appropriate. It includes a single or fused ring system, and includes a form in which a plurality of aryl is connected by a single bond. Examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. It is not limited to this.
  • halogen herein also means fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atoms.
  • lactam group herein also means heterocycloalkyl comprising an atom group which is -CONH- in the ring, the lactam group also including an N-substituted lactam group.
  • fused lactam group herein also means that the ring of the lactam group forms a ring system fused with an aromatic ring or an alicyclic ring, wherein the alicyclic ring is a fully saturated or partially unsaturated ring. It also includes the case of organic radicals derived from.
  • the term "compound of formula 1" may be used to include isomers thereof or acceptable salts thereof.
  • the acceptable salts mean salts according to one aspect of the present invention which are conventionally or medically available and have the desired activity of the compound.
  • an alkali metal salt such as sodium salt or potassium salt may be mentioned, but is not limited thereto.
  • the inventors of the present invention have realized that when the carriers are recombined in the emission layer region, the density of the holes and the electrons is balanced in the implementation of the high efficiency of the organic light emitting device, and studied a method for solving the problem. Accordingly, the present invention was found to realize surprisingly improved efficiency by injecting a ⁇ -lactam compound containing both primary and secondary amines into a conductive polymer composite including an acidic group as a main material of the hole injection layer. Completed.
  • composition for an organic light emitting device can achieve the bandgap alignment by the unique interfacial dipole formation, the improved balance of holes and electrons, and the formation of excitons by J / H-aggregation. Furthermore, the intermolecular bond inducing properties of the ' ⁇ -lactam' structure induce an ordered electric dipole. These aligned dipoles produce a J-aggregated energy state and an H-aggregated energy state, which play an important role in improving the efficiency of the organic light emitting device.
  • the present specification is to expand the application of the composition for the hole injection layer and the hole injection layer material prepared using the composition for realizing the high efficiency of the organic light emitting device.
  • the present invention provides a composition for an organic electroluminescent device comprising a conductive polymer composite including an acid group and a compound of the formula (1).
  • R 1 is C 3 -C 30 cycloalkyl, C 3 -C 30 heterocycloalkyl, C 6 -C 30 aryl or C 6 -C 30 heteroaryl;
  • R 2 is a lactam group or a fused lactam group
  • R 1 of the cycloalkyl, heterocycloalkyl, aryl or heteroaryl group and the lactam group or a fused lactam of the R 2 groups are each independently halogen, hydroxy, cyano, carboxyl, carboxylic acid salts, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 30 aryl and C 6 may be further substituted with one or more substituents selected from -C 30 heteroaryl;
  • the hole injection layer material manufactured using the composition for an organic light emitting display device according to an embodiment of the present invention causes Fermi level alignment, causing strong attraction with electrons and weak hole injection. cause. That is, the hole injection layer material according to the present invention can significantly increase the efficiency of the organic light emitting device by effectively suppressing the hole injection and remarkably improving the recombination efficiency with the above-described characteristics.
  • the compound of Formula 1 is wherein R 1 is C 3 -C 30 cycloalkyl or C 6 -C 30 aryl; R 2 may be a lactam group fused with an alicyclic ring.
  • the lactam group fused with the alicyclic ring of R 2 is C 1 -C 20 alkylene or C 2 -C 20 alkenylene to the C 3 -C 6 heterocycloalkyl ring containing an atom group that is -CONH- in the ring It may be to form a fused ring system.
  • one of -CH 2 -of the alkylene or alkenylene may be replaced with a heteroatom such as -O- or -S-.
  • the lactam group fused with the alicyclic ring of R 2 may be a saturated or partially unsaturated ring.
  • the compound of Formula 1 is wherein R 1 is C 3 -C 30 cycloalkyl or C 6 -C 30 aryl; R 2 may be represented by the following Chemical Formula 2.
  • R 11 is C 1 -C 7 alkyl or C 2 -C 7 alkenyl
  • R 12 and R 13 is hydrogen, C 1 -C 7 alkyl, C 1 -C 7 alkoxy or C 1 -C 7 thioxy, the other may be linked to R 11 to form an alicyclic ring and ;
  • R 11 alkyl or alkenyl and wherein R 12 and R 13 alicyclic ring are each independently selected from halogen, hydroxy, cyano, carboxyl, carboxylic acid salt is one that is formed by the connection of the R 11, C 1 -C 7 alkyl, C 1 -C 7 alkoxy, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, C 6 -C 12 aryl and C 6 -C 12 heteroaryl, and the like.
  • -CH 2 -in the alicyclic ring may be replaced with a heteroatom selected from O and S and the like.
  • the compound of Formula 1 wherein R 1 is optionally substituted C 3 -C 12 cycloalkyl or an optionally substituted C 6 -C 12 aryl; R 2 may be represented by Chemical Formula 2.
  • the compound of Formula 1 is a cycloalkyl such that R 1 is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl and cyclooctadienyl; And aryl such as phenyl, naphthyl and biphenyl; wherein the cycloalkyl or aryl of R 1 is further substituted with one or more substituents selected from halogen, hydroxy, cyano, carboxyl and C 1 -C 7 alkyl and the like. It may be, the R 2 may be represented by the formula (2).
  • the compound of Formula 1 may be at least one selected from the compound of Formula 3 and the compound of Formula 4 specifically.
  • R 1 is C 3 -C 12 cycloalkyl or C 6 -C 12 aryl
  • R 21 to R 24 are each independently selected from hydrogen, halogen, hydroxy, cyano, carboxyl, carboxylate and C 1 -C 7 alkyl;
  • the cycloalkyl or aryl of R 1 may be each independently further substituted with one or more substituents selected from halogen, hydroxy, cyano, carboxyl, C 1 -C 7 alkyl and the like.
  • R 1 is cycloalkyl such as cyclopentadienyl, cyclohexadienyl, cycloheptadienyl and cyclooctadienyl; And aryl such as phenyl, naphthyl and biphenyl; wherein the cycloalkyl or aryl of R 1 may be further substituted with one or more substituents selected from hydroxy, carboxyl, and the like, wherein R 21 to R 24 are each Independently, hydrogen, halogen, hydroxy, cyano, carboxyl, carboxylate (* -COOM, M may be selected from hydrogen or alkyl such as K, Na, etc.) and alkyl such as methyl, ethyl.
  • the compound of Formula 1 may be more specifically selected from the following structures.
  • the compound of Formula 1 may be used diluted to an appropriate concentration according to the purpose.
  • the compound of Formula 1 may be 0.01 to 0.5% by weight of the compound of Formula 1 and the balance of water.
  • the compound of Formula 1 may be 1.0 to 10.0% by weight of the compound of Formula 1 and the balance of water.
  • the conductive polymer composite comprising the acid group is a sulfonic acid anion (* -SO 3 -) may be one, or the like.
  • the conductive polymer composite including the acidic group may be a mixture of a polythiophene polymer and an aromatic sulfonate polymer.
  • the conductive polymer composite including the acidic group may include poly (styrenesulfonate), and more specifically, a mixture of poly (3,4-ethylenedioxythiophene) and poly (styrenesulfonate) ( PEDOT: PSS).
  • poly (styrenesulfonate) a mixture of poly (3,4-ethylenedioxythiophene) and poly (styrenesulfonate) (PEDOT: PSS).
  • a mixture of poly (3,4-ethylenedioxythiophene) and poly (styrenesulfonate) is a poly (styrene) as an acceptor for poly (3,4-ethylenedioxythiophene), a conductive polymer.
  • Sulfonate may have a doped structure.
  • a mixture of poly (3,4-ethylenedioxythiophene) and poly (styrenesulfonate) may be present in a dispersed form as an ionic complex.
  • the PEDOT: PSS in the water-dispersed form may be included in the concentration of the solid content of 1.3 to 1.7% by weight (residual amount of water), and may be acidic with the sulfonic acid anion having a pH of about 1 to less than 2.
  • composition for an organic light emitting display device by injecting the compound of Chemical Formula 1 into a PEDOT: PSS in a dispersed form, it effectively induces the formation of excitons by J / H-aggregation, thereby significantly improving efficiency. Can be implemented.
  • the present invention is a compound comprising a primary amine and a secondary amine simultaneously in a mixture (PEDOT: PSS) of poly (3,4-ethylenedioxythiophene) and poly (styrenesulfonate), which are main materials of the hole injection layer.
  • PEDOT PSS
  • poly (3,4-ethylenedioxythiophene) and poly (styrenesulfonate) are main materials of the hole injection layer.
  • the present invention can implement the efficiency of the organic electroluminescent device surprisingly improved by introducing one or more antibiotics selected from ampicillin, amocillin, cephalexin, cepradine and Sephachlor as a compound satisfying the above-described structural characteristics By confirming the presence, it suggests a new use of the antibiotic described above.
  • composition for an organic light emitting display device may include 10 mol or less of primary amine groups in the compound of Formula 1 based on 1 mol of sulfonic acid ions of the poly (styrenesulfonate). have.
  • the primary amine group in the compound of Formula 1 may be 0.1 to 8 moles, more specifically 0.5 to 6 moles.
  • the composition for an organic light emitting display device may include 0.1 to 80% by volume of the compound of Formula 1 based on the total volume of the composition.
  • the composition may include 2 to 75% by volume of the compound of Formula 1, more specifically may include 15 to 40% by volume, more specifically may include 25 to 40% by volume. have.
  • the remaining amount of the composition is a PEDOT: PSS in the water dispersed form, the concentration of the solid may be 1.3 to 1.7% by weight.
  • the total amount of primary amine groups may be 1.24 vg. (2 vol% Amp-PEDOT: PSS, pH 2.10).
  • the ampicillin (Ampicillin, Amp) may be 5% by weight (remaining water).
  • One example below may also be the same.
  • the total amount of the primary amine group may be 1.24 ⁇ g (10 vol% Amp -PEDOT: PSS, pH 2.80).
  • the total amount of the primary amine group may be 1.24 ⁇ g (15 vol% Amp-PEDOT: PSS, pH 3.20).
  • the total amount of the primary amine group may be 2.48 ⁇ g (25 vol% Amp- PEDOT: PSS, pH 4.48).
  • the total amount of the primary amine group may be 4.95 ⁇ g (40 vol% Amp- PEDOT: PSS, pH 7.36).
  • the total amount of the primary amine group may be 7.43 ⁇ g (75 vol% Amp- PEDOT: PSS, pH 8.28).
  • the pH is pH meter (SX723, Portable pH / Conductivity Meter, Range: (pH: -2.00 ⁇ 19.99pH), Resolution: pH: 0.1 / 0.01 / 0.001 pH, Accuracy: pH: ⁇ 0.01, Shanghai San-Xin Instrument, China, which is measured using a glass electrode, which is commonly used when measuring acidity.
  • the pH of the composition for the organic light emitting device satisfies the conditions of 9.0 or less, and stably implements the desired effect in the present invention.
  • the compound of Formula 1 has a lactam group unstable under the condition of pH 7.5 and the ring opening reaction is performed, and it is difficult to induce exciton formation by J / H-aggregation due to such structural modification, Exciton can be formed by the increase in efficiency can be expected. However, its effect is difficult to achieve under conditions above pH 9.0.
  • the pH of the composition may be specifically 2.0 to 8.5, more specifically may be 3.0 to 7.5.
  • the hole injection layer material prepared by using the composition for an organic light emitting device that satisfies the above-described pH conditions has improved density balance between holes and electrons, exciton formation by J / H-aggregation and exciton formation by strong chromophore interaction. Can be achieved at the same time. Furthermore, the intermolecular bond-inducing properties of the antibiotic-specific ' ⁇ -lactam' structure induce an ordered electrical dipole. These aligned dipoles create J- and H-cohesive energy states and play an important role in improving the efficiency of organic light emitting diodes. Therefore, the organic light emitting diode according to the present invention including the same shows superior to the efficiency (current efficiency, external quantum efficiency, power efficiency, etc.) of any conventional organic electroluminescent device.
  • composition for an organic light emitting device that satisfies the above-described pH conditions has a lower work function. Accordingly, by suppressing hole injection, electron / hole recombination can be effectively performed.
  • the present invention provides a hole injection layer material manufactured using a conductive polymer composite including an acid group and an organic electroluminescent device composition comprising the compound of Formula 1, and an organic electroluminescent device employing the same.
  • the hole injection layer material according to an embodiment of the present invention has a low work function and realizes more improved efficiency by forming excitons by J / H-aggregation and strong chromophore interaction.
  • the hole injection layer material according to an embodiment of the present invention it is possible to effectively suppress the problem of abrupt shortening of device life due to high acidity.
  • the organic electroluminescent device according to an embodiment of the present invention will be described below, but the structure is not limited thereto.
  • An organic light emitting display device includes an anode, a hole injection layer including the hole injection layer material, a hole transport layer, a light emitting layer, an electron transport layer and a cathode.
  • the organic light emitting diode may further include an electron injection layer between the light emitting layer and the cathode.
  • the organic light emitting diode may further include an electron blocking layer between the hole transport layer and the light emitting layer, and a hole blocking layer between the light emitting layer and the electron transport layer.
  • the organic light emitting device may be deposited by an environmentally friendly solution process using an organic solvent such as a halogenated solvent and a halogen-free solvent as well as a vacuum deposition method.
  • an organic solvent such as a halogenated solvent and a halogen-free solvent as well as a vacuum deposition method.
  • a positive electrode may be formed using a material such as a conductive polymer such as a metal oxide, polyaniline, polythiophene, or the like, and according to a preferred embodiment, it is ITO.
  • the cathode is an effective material for injecting electrons, which are negative-charge carriers, including gold, aluminum, copper, silver, or alloys thereof; Aluminum, indium, calcium, barium, magnesium and alloys thereof, such as calcium / aluminum alloys, magnesium / silver alloys, aluminum / lithium alloys, and the like; Or in some cases, metals belonging to rare earths, lanthanides, actinides; And the like, preferably aluminum, or an aluminum / calcium alloy.
  • the hole injection layer is formed using the composition for organic electroluminescent devices according to the present invention. That is, the hole injection layer formed by using the composition for an organic light emitting device according to the present invention has a low work function, improved density balance of holes and electrons, formation of excitons by J / H-aggregation, and antibiotic-specific ' ⁇ . It exhibits surprisingly improved efficiency by simultaneously inducing intermolecular bonds of the -lactam 'structure, inducing aligned dipoles, and exciton formation by strong chromophore interactions. In particular, it realizes a markedly improved efficiency at low driving low pressures.
  • the hole injection layer can effectively improve the interfacial properties with the anode material such as ITO, and its surface is applied on the top of the uneven ITO can serve to smooth the surface of the ITO .
  • the hole injection layer may appropriately control the difference between the work function level of ITO and the HOMO level of the hole transport layer, which can be used as the anode.
  • the hole injection layer may be used a material commonly used, for example, copper phthlalocyanine (CuPc), N, N'-dinaphthyl-N, N'-phenyl- (1,1'-biphenyl)- 4,4'-diamine, NPD), 4,4 ', 4' '-tris [methylphenyl (phenyl) amino] triphenyl amine (m-MTDATA), 4,4', 4 ''-tris [1-naphthyl ( phenyl) amino] triphenyl amine (1-TNATA), 4,4 ', 4' '-tris [2-naphthyl (phenyl) amino] triphenyl amine (2-TNATA), 1,3,5-tris [N- ( 4-diphenylaminophenyl) phenylamino] aromatic amines such as benzene (p-DPA-TDAB) and the like, but are not limited thereto.
  • CuPc
  • the hole transport layer may be a material having a HOMO level higher than the HOMO level of the light emitting layer for smooth hole transport.
  • TCTA Tris (4-carbazoyl-9-ylphenyl) amine
  • TAPC 4,4'-Cyclohexylidenebis [N, N-bis (4-methylphenyl) benzenamine]
  • TPD N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1'-diphenyl-4,4'-diamine
  • TPB N, N'-bis (1-naphthyl) -N , N'-biphenyl- [1,1'-biphenyl] -4,4'-diamine
  • NPB N, N'-di (naphthalene-1-yl) -N, N'-diphenyl-benzidene
  • TPA Tree Phenylamine
  • MPMP MPMP
  • the light emitting layer is a material capable of emitting red (R), green (G), or blue (B), and may include a fluorescent or phosphorescent material. Preferably, it may be a green light emitting layer emitting green light.
  • the green light emitting layer may be one of a yellowish red light emitting layer, a yellowish green light emitting layer, and a dark green light green.
  • the wavelength range of the light to be emitted may be in the range of 490nm to 580nm.
  • the light emitting layer may include a dopant compound and a host compound, and a known material capable of emitting light as described above may be used.
  • the dopant compound may be a metal complex including at least one metal selected from Ir, Ru, Pd, Pt, Os, and Re.
  • ligands forming the metal complex include 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2- (2-thienyl) pyridine derivatives, 2- (1-naphthyl) pyridine derivatives, 2- Phenylquinoline derivatives, and the like, and may further have additional substituents.
  • the dopant compound examples include bisthienylpyridine acetylacetonate iridium, bis (benzothienylpyridine) acetylacetonate iridium, and bis (2-phenylbenzo Thiazole) acetylacetonate iridium ⁇ Bis (2-phenylbenzothiazole) acetylacetonate Iridium ⁇ ⁇ tris (1-phenylisoquinoline) Iridium ⁇ , tris (phenylpyridine) Iridium ⁇ , tris (2-biphenylpyridine) iridium ⁇ tris (2-phenylpyridine) Iridium ⁇ , tris (3-biphenylpyridine ) Iridium ⁇ tris (3-biphenylpyridine) Iridium ⁇ , tris (4-biphenylpyridine) Iridium ⁇ and the like can be used, but is not limited thereto.
  • the host compound examples include PAmTPI (9,9-dimethyl-10-phenyl-2- (3- (1,4,5-triphenyl-1H-imidazol-2-yl) phenyl) -9,10-dihydroacridine ), Diphenyl-4-triphenylsilylphenylphosphine oxide (TSPO1), 4,4-N, N-dicarbazole-biphenyl (4,4-N, N-dicarbazole-biphenyl , CBP), N, N-dicarbazoyl-3,5-benzene (N, N-dicarbazoyl-3,5-benzene, mCP), polyvinylcarbazole (PVK), polyfluorene, 4,4'-bis [9- (3,6biphenylcarbazolyl)]-1-1,1'-biphenyl4,4'-bis [9- (3,6-biphenylcarbazolyl)]- 1-1,1
  • the electron transport layer is mainly composed of a material containing a chemical component that attracts electrons, which requires high electron mobility and stably supplies electrons to the light emitting layer through smooth electron transport.
  • TSPO1 diphenyl-4-triphenylsilylphenylphosphine oxide
  • TPBi 1,3,5-tris (N-phenylbenzimiazole-2-yl) benzene
  • Alq 3 Tris (8-hydroxyquinolinato) aluminum
  • DDPA 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • PBD (2- (4-biphenyl) -5- (4-tert-butyl) -1,3,4-oxadizole
  • TAZ 3- (4-biphenyl) -4-phenyl-5- (4-tert- azole compounds such as butyl) -1,2,4-triazole
  • phenylquinozaline TmPyPB (3,3 '-[5'--
  • the electron injection layer is used to induce smooth electron injection.
  • an alkali metal or alkaline earth metal ion form is used, such as LiF, BaF 2 , CsF, Liq, and the like. It may be configured to induce doping.
  • an electron blocking layer may be further included between the hole transport layer and the light emitting layer, and a hole blocking layer may be further provided between the light emitting layer and the electron transport layer, and a known electron blocking material and a hole blocking material may be used.
  • An organic light emitting display device includes a display device; Display elements; Or a device for monochrome or white illumination.
  • ITO Indium Tin Oxide
  • a hole injection layer (40nm) consisting of 2vol% Amp-PEDOT: PSS (ampicillin 2 vol% and residual PEDOT: PSS; PEDOT: PSS is CLEVIOS P VP AL 4083, Heraeus , pH 2.10) on the ITO glass substrate
  • the light emission characteristics of the green phosphorescent organic light emitting diode were evaluated.
  • the emission area was 4 mm2 and the driving voltage was a direct bias voltage.
  • the green phosphorescent organic light emitting device showed an external quantum efficiency (EQE) of up to 35.0%, a current efficiency of up to 120.0 cd / A, and a power efficiency of up to 68.0 Im / W or more (Table 1 and FIGS. 2 to 2). 5).
  • EQE external quantum efficiency
  • the green phosphorescent organic light emitting device showed an external quantum efficiency (QE) of up to 34.1%, a current efficiency (CE) of up to 118.9 cd / A, and a power efficiency (PE) of up to 63.3 Im / W (following). Table 1 and FIGS. 2-5).
  • Example 1 2 vol% Amp-PEDOT: PSS (2 vol% ampicillin and residual PEDOT: PSS; PEDOT: PSS was 75 vol% Amp-PEDOT: PSS (pH 8.28) instead of CLEVIOS P VP AL 4083, Heraeus).
  • the green phosphorescent organic light emitting diode having the same cross-sectional structure was completed, and the light emission characteristics were evaluated by the method of Example 1.
  • the green phosphorescent organic light emitting device showed an external quantum efficiency of up to 24.9%, a current efficiency of up to 83.7 cd / A, and a power efficiency of up to 37.7 Im / W (see Table 1 and FIGS. 2 to 5 below). .
  • Example 1 using only PEDOT: PSS (0 vol% Amp-PEDOT: PSS, pH 1.48) without using ampicillin, a green phosphorescent organic light emitting device having the same cross-sectional structure as Example 1 was completed, and The luminescence properties were evaluated by the method of Example 1.
  • the green phosphorescent organic light emitting device showed an external quantum efficiency of up to 21.3%, a current efficiency of up to 72.9 cd / A, and a power efficiency of up to 37.7 Im / W (see Table 1 and FIGS. 2 to 5 below). .
  • the performance of the organic light emitting diode according to the present invention that is, the driving voltage (V on ), the maximum external quantum efficiency (QE), the maximum current efficiency (CE), the maximum power efficiency (PE) and the color coordinates (CIE) by measuring 1 and FIGS. 2 to 5.
  • the performance of the organic light emitting diode according to the voltage change was measured.
  • the measurement was performed using a current-voltmeter (Keithley 2400A Source Meter) and a luminance meter (Minolta CS-2000) while increasing the voltage at regular intervals (0.5V) from -5 V to 15 V.
  • the external quantum efficiency, current efficiency, and power efficiency were calculated using the density, luminance, and color coordinate values, which are shown in FIGS. 2 to 5, and the maximum values of the respective efficiency are shown in Table 1 below.
  • the organic EL device employing the hole injection layer manufactured using the composition for an organic EL device according to the present invention can realize high color purity with improved efficiency even at a low driving voltage. It was.
  • the organic light emitting display device according to the present invention has excellent power efficiency compared to Comparative Example 1, and emits high luminance light even at a low driving voltage, thereby showing high color purity and remarkable quantum efficiency.
  • the organic light emitting display device according to the present invention can significantly reduce the power consumption can implement excellent power efficiency.
  • the organic light emitting device according to the present invention can effectively suppress the problem of abrupt shortening of device life due to high acidity of the hole injection layer material.
  • the organic light emitting device according to the present invention realizes an external quantum efficiency of up to 35.0%, a current efficiency of up to 120.0 cd / A, and a power efficiency of up to 68.0 m / W.
  • the performance of the organic light emitting device according to the present invention exceeds the performance of any single unit green phosphorescent organic light emitting device reported so far, and is useful for a high performance display device, a display device, or a monochrome or white lighting device. It is expected to be used.
  • the organic light emitting device according to the present invention follows the Lambertian curve, and proved that the measured value is not fictional through the integrating sphere measurement. Therefore, according to the present invention, it is expected to be substantially applied to the present organic light emitting device technology and to implement an improved effect.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne une composition pour un dispositif électroluminescent organique, un matériau de couche d'injection de trous fabriqué à partir de celle-ci, et un dispositif électroluminescent organique comprenant la couche d'injection de trous. En particulier, le dispositif électroluminescent organique utilisant le matériau de couche d'injection de trous produit en utilisant une composition pour un dispositif électroluminescent organique selon la présente invention peut réaliser une efficacité remarquablement améliorée et supprimer efficacement le problème de raccourcissement de la durée de vie du dispositif en raison d'une acidité élevée.
PCT/KR2019/001805 2018-02-21 2019-02-14 Composition pour dispositif électroluminescent organique, matériau de couche d'injection de trous fabriqué à partir de celle-ci, et dispositif électroluminescent organique comprenant une couche d'injection de trous Ceased WO2019164180A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/755,649 US20200274071A1 (en) 2018-02-21 2019-02-14 Composition for Organic Electroluminescent Device, Hole Injection Layer Material Manufactured Therefrom, and Organic Electroluminescent Device Comprising Hole Injection Layer
CN201980005324.5A CN111373560B (zh) 2018-02-21 2019-02-14 有机场致发光器件用组合物、由其制备的空穴注入层材料
JP2020517536A JP6868749B2 (ja) 2018-02-21 2019-02-14 有機エレクトロルミネッセンス素子用の組成物、これより製造された正孔注入層材料および正孔注入層を含む有機エレクトロルミネッセンス素子

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KR20180020531 2018-02-21
KR10-2018-0020531 2018-02-21
KR10-2019-0016567 2019-02-13
KR1020190016567A KR102174374B1 (ko) 2018-02-21 2019-02-13 유기전계발광소자용 조성물, 이로부터 제조된 정공주입층 재료 및 정공주입층을 포함하는 유기전계발광소자

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6165708A (en) * 1995-06-07 2000-12-26 Igen International, Inc. Electrochemiluminescent monitoring of compounds
KR101346437B1 (ko) * 2005-12-14 2014-01-02 하.체. 스타르크 게엠베하 운트 코. 카게 전기-광학 구조체용 투명 중합체 전극
US20140093902A1 (en) * 2009-08-31 2014-04-03 Tufts University Silk transistor devices
KR20160148675A (ko) * 2014-04-30 2016-12-26 캠브리지 엔터프라이즈 리미티드 전계 발광 소자
KR101771581B1 (ko) * 2011-05-23 2017-08-28 삼성디스플레이 주식회사 유기 전계 발광 소자

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6165708A (en) * 1995-06-07 2000-12-26 Igen International, Inc. Electrochemiluminescent monitoring of compounds
KR101346437B1 (ko) * 2005-12-14 2014-01-02 하.체. 스타르크 게엠베하 운트 코. 카게 전기-광학 구조체용 투명 중합체 전극
US20140093902A1 (en) * 2009-08-31 2014-04-03 Tufts University Silk transistor devices
KR101771581B1 (ko) * 2011-05-23 2017-08-28 삼성디스플레이 주식회사 유기 전계 발광 소자
KR20160148675A (ko) * 2014-04-30 2016-12-26 캠브리지 엔터프라이즈 리미티드 전계 발광 소자

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