WO2015174640A1 - Composé, élément optoélectronique organique comprenant ledit composé et dispositif d'affichage le comprenant - Google Patents

Composé, élément optoélectronique organique comprenant ledit composé et dispositif d'affichage le comprenant Download PDF

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WO2015174640A1
WO2015174640A1 PCT/KR2015/003678 KR2015003678W WO2015174640A1 WO 2015174640 A1 WO2015174640 A1 WO 2015174640A1 KR 2015003678 W KR2015003678 W KR 2015003678W WO 2015174640 A1 WO2015174640 A1 WO 2015174640A1
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group
substituted
unsubstituted
formula
compound
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Korean (ko)
Inventor
류동완
조영경
정성현
신창주
이한일
강의수
김창우
박민지
유은선
조평석
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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Priority claimed from KR1020150051095A external-priority patent/KR101931250B1/ko
Application filed by Samsung SDI Co Ltd filed Critical Samsung SDI Co Ltd
Priority to CN201580019167.5A priority Critical patent/CN106164061B/zh
Priority to EP15791911.9A priority patent/EP3144301B1/fr
Priority to US15/117,753 priority patent/US11563179B2/en
Priority to JP2016566263A priority patent/JP6575969B2/ja
Publication of WO2015174640A1 publication Critical patent/WO2015174640A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • a compound, an organic optoelectronic device, and a display device are provided.
  • Organic optoelectronic diodes are devices that can switch electrical energy and light energy.
  • Organic optoelectronic devices can be divided into two types according to the principle of operation.
  • One is an optoelectronic device in which excitons formed by light energy are separated into electrons and holes, and the electrons and holes are transferred to other electrodes, respectively, to generate electric energy.
  • It is a light emitting device that generates light energy from energy.
  • Examples of the organic optoelectronic device may be an organic photoelectric device, an organic light emitting device, an organic solar cell and an organic photo conductor drum.
  • organic light emitting diodes have attracted much attention recently as demand for flat panel displays increases.
  • the organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material, and has a structure in which an organic layer is inserted between an anode and a cathode.
  • the organic layer may include a light emitting layer and an auxiliary layer
  • the auxiliary layer may include, for example, a hole injection layer for increasing efficiency and stability of the organic light emitting device.
  • the performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and in particular, is affected by the organic material included in the organic layer.
  • An organic optoelectronic device including the compound and a display device including the organic optoelectronic device are provided.
  • L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted group A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C 1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or and unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynyl group, or a combination thereof, '
  • R 1 to R 7 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted A substituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 Alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
  • Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, Substituted or unsubstituted C1 to C30 alkylthi group, substituted or unsubstituted C6 to C30 arylthiol group, substituted or unsubstit
  • R 2 and R 3 are represented by the following Chemical Formula 2 or the following Chemical Formula 3:
  • X is 0 or S
  • R a to R g are each independently hydrogen, deuterium, substituted or unsubstituted C1 to
  • C30 alkyl group substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted Or an unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C30
  • Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted C1 to C30 sulfonyl group, Substituted or unsubstituted C 1 to C30 alkylthio group, substituted or unsubstituted C6 to C30 arylthi group, substituted or unsubstitute
  • the compound according to one embodiment of the present invention may be for an organic optoelectronic device.
  • a display device including the organic optoelectronic device described above is provided. .
  • FIG. 1 and 2 are cross-sectional views illustrating various embodiments of an organic light emitting diode according to an embodiment of the present invention.
  • Figure 3 is a graph showing the results of measuring the PL wavelength of the compound according to an embodiment of the present invention.
  • organic light emitting element 200 organic light emitting element
  • substituted unless otherwise defined, at least one hydrogen of the substituent or compound is deuterium, halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C10 such as C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, fluoro group, trifluoromethyl group, etc.
  • hetero means one to three hetero atoms selected from the group consisting of ⁇ , ⁇ , S, P and Si in one functional group, and the remainder is carbon unless otherwise defined. do.
  • an "alkyl group” means an aliphatic hydrocarbon group.
  • the alkyl group may be a "saturated alkyl group” that does not contain any double or triple bonds.
  • the alkyl group may be an alkyl group of C1 to C20. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group.
  • a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, and methyl, ethyl, propyl, iso-propyl, ⁇ -butyl, iso-butyl, sec -butyl and t-butyl Selected from the group consisting of:
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, nucleosil group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclonucleus It means real skill.
  • an "aryl group” means a substituent in which all elements of a cyclic substituent have a p-orbital, and these P-orbitals form a conjugate, and are monocyclic or fused ring polishes. It includes a click (ie, a ring that divides adjacent pairs of carbon atoms) functional groups.
  • a “heterocyclic group” refers to a hetero atom selected from the group consisting of N, 0, S, P, and Si in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. Containing at least one, and the rest being carbon.
  • the heterocyclic group is a fused ring, the heterocyclic group It may contain one or more heteroatoms for all or each ring.
  • the heterocyclic group is a higher concept encompassing the heteroaryl group.
  • a substituted or unsubstituted C6 to C30 aryl group and / or a substituted or unsubstituted C2 to C30 heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthra Senyl group, substituted or unsubstituted
  • Phenanthryl groups substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted P-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted Or unsubstituted chrysenyl group, substituted or unsubstituted
  • Triphenylenyl group substituted or unsubstituted perylenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or unsubstituted Substituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazoleyl group , Substituted or unsubstituted
  • Thiadiazolyl group substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted Or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted A quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group,
  • a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.
  • a single bond refers to carbon or hetero atoms other than carbon.
  • L is a single bond means that the substituents connected to L is directly connected to the central core. That is, in the present specification, a single bond refers to methylene or the like via carbon.
  • the hole characteristic refers to a characteristic capable of forming holes by donating electrons when an electric field is applied, and injecting holes formed at the anode into the light emitting layer having conductive properties along the HOMO level, and emitting layer. It refers to a property that facilitates the movement of the hole formed in the anode and movement in the light emitting layer.
  • the electron characteristic refers to a characteristic that can receive electrons when an electric field is applied, and has a conductivity characteristic along the LUMO level, and injects electrons formed in the cathode into the light emitting layer, moves electrons formed in the light emitting layer to the cathode, and It means a property that facilitates movement.
  • a compound according to one embodiment is described.
  • a compound represented by the following Chemical Formula 1 may be provided.
  • L 1 to L 3 are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted A substituted C2 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 aryleneamine group, a substituted or unsubstituted C1 to C30 alkoxylene group, a substituted or unsubstituted C1 to C30 aryloxyylene group, a substituted or unsubstituted A substituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof,
  • R 1 to R 7 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkoxy Carbonyl group, substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
  • Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C1 to C20 acylamino group, substituted or unsubstituted A substituted C1 to C30 sulfonyl group, a substituted or unsubstituted C1 to C30 alkylthio group, a substituted or unsubstituted C6 to C30 arylthiol group, a
  • R 2 and R 3 is at least one of the following general formula 2, or is represented by the following general formula (3): formula (2);
  • X is 0 or S
  • R a to R g are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C2 to C30 alkoxy Carbonyl group, substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, substituted or unsubstituted C7 to C30
  • Aryloxycarbonylamino group substituted or unsubstituted C1 to C30 sulfamoylamino group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C40 silyl group , Substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C30 acyl group, substituted or unsubstituted C1 to C20 acyloxy group, substituted or unsubstituted C 1 to C20 acylamino group, substituted or Unsubstituted C1 to C30 sulfonyl group, substituted or unsubstituted C1 to C30 alkylthiol group, substituted or unsubstituted C6 to C30 arylthiyl group, substituted or unsubstitute
  • the compound according to the embodiment of the present invention is at least one of R 2 and R 3 is represented by the formula (2) or (3), thereby increasing the hole transport of the molecule to be applied to the hole transport layer and hole transport light emitting host of the organic optoelectronic device In this case, excellent efficiency can be obtained.
  • the thin film when the thin film is applied to the organic optoelectronic device by increasing the vitrification transition temperature while improving the hole transporting properties compared to the compound of R 2 and R 3 are both aryl group, it can exhibit long life and high efficiency characteristics,
  • the heat resistance against thermal decomposition is excellent, and thus the processability and device stability can be improved by the vacuum heating deposition method.
  • Formula 1 may be specifically represented by any one of the following Formula 4 to Formula 12. [Formula 4] [Formula 5]
  • ⁇ , ⁇ 1 and X 2 are each independently 0 or S,
  • R 1 , R 2 , R 4 to R 7 , R a to R g , and R a 'to R g ' are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylamine group, substituted or unsubstituted C1 to C30 alkoxy Groups, substituted or unsubstituted C2 to C30
  • L 1 to L 3 are as defined in Chemical Formula 1.
  • R 2 and R 3 may each independently be selected from a substituted or unsubstituted C2 to C30 heterocyclic group or a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted phenyl group, substituted or Unsubstituted naphthalene group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted pyrenyl group, substituted or Unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothio 3 ⁇ 4yl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted
  • Benzothiophenyl group substituted or unsubstituted benzofuranyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted benzoquinolinyl group, substituted or unsubstituted benzoisoquinolineyl group, It may be selected from a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazineyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, and the like.
  • R 2 and R 3 are each independently selected from a substituted or unsubstituted group listed in Group I, and at least one of R 2 and R 3 is selected from a substituted or unsubstituted group listed in Group 1-1 below. Can be selected. '
  • X and W are each independently 0 or S, and R and R 'are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof, and * is a point of attachment.
  • R 1 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 aryl group, or these It can be a combination of.
  • R 1 is a methyl group, an ethyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclonuclear group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naph A methyl group, a substituted or unsubstituted pyridyl group, Substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted quinolinyl group, or a combination thereof,
  • a methyl group for example, a methyl group, an ethyl group, or one selected from the groups listed in the following group ⁇ .
  • Formula 1, and R 4 to R 7 , R a to R g , and R a 'to R g of Formulas 4 to 12 are each independently hydrogen, deuterium, substituted or unsubstituted Or a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C12 cycloalkyl group, a substituted or unsubstituted C2 to C12 heterocyclic group, or a substituted or unsubstituted C6 to C12 aryl group.
  • R 4 to R 7 , R a to R g , and R a ′ to R 8 ′ in Formula 1, and Formulas 4 to 12 are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group. Or a substituted or unsubstituted C6 to C12 aryl group.
  • Formula 1, and L 1 to L 3 of Formulas 4 to 12 are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroaryl It may be a Rengi ⁇
  • L 1 to L 3 are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substitution Or an unsubstituted pyrimidylene group, a substituted or unsubstituted benzofuranylene group, or a combination thereof,
  • the above-mentioned compounds may be for organic optoelectronic devices.
  • an organic optoelectronic device to which the above-described compound is applied will be described.
  • the auxiliary caterpillar provides an organic optoelectronic device comprising the compound described above.
  • the auxiliary layer may be a hole transport layer.
  • the organic optoelectronic device is not particularly limited as long as the device can switch electrical energy and light energy. Examples thereof include an organic photoelectric device, an organic light emitting device, an organic solar cell, and an organic photosensitive drum.
  • an organic optoelectronic device 100 includes an anode 120 and a cathode 1 10 facing each other, and an organic layer 105 positioned between the anode 120 and the cathode 1 10. ).
  • the anode 120 may be made of, for example, a conductor having a high hole function, for example, to facilitate hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer.
  • the anode 120 may be, for example, a metal such as nickel, platinum, vanadium, cream, copper, zinc, gold or an alloy thereof; Zinc oxide, indium oxide, indium tin oxide ( ⁇ ),
  • Metal oxides such as indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO and A1 or Sn0 2 and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDT), polypyrrole and polyaniline, and the like. It is not limited.
  • the cathode 1 10 may be made of a low work function conductor, for example, to facilitate electron injection, and may be made of metal, metal oxide and / or conductive polymer, for example.
  • the negative electrode 1 10 is made of, for example, metals such as magnesium, kale, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or the like. alloy; Multilayer structure materials such as LiF / AI, Li0 2 / Al, LiF / Ca, LiF / Al, and BaF 2 / Ca, but are not limited thereto.
  • the organic layer 105 includes the light emitting layer 130.
  • the light emitting layer 130 may include, for example, a compound alone, or may include two kinds in combination. Including two kinds in combination, for example
  • the host can be, for example, a phosphorescent host or a fluorescent host.
  • the dopant may be an inorganic, organic, organic or inorganic compound and may be selected from known dopants.
  • the organic light emitting diode 200 further includes a hole auxiliary layer 140 in addition to the light emitting layer 230.
  • the hole auxiliary layer 140 may further increase hole injection and / or hole mobility between the anode 120 and the emission layer 230 and block electrons.
  • the hole auxiliary layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer. The aforementioned compound may be included in the hole auxiliary layer 140.
  • the organic layer 105 of FIG. 1 or 2 may further include an electron injection layer, an electron transport layer, an auxiliary electron transport layer, a hole transport layer, an auxiliary hole transport layer, a hole injection layer, or a combination thereof.
  • the compound described above may be included in the auxiliary hole transport layer.
  • the emission layer 230 and the auxiliary hole transport layer may be adjacent to each other.
  • the compounds of the present invention can be included in these organic layers.
  • the organic light emitting diodes 100 and 200 form an anode or a cathode on a substrate, and then evaporation,
  • Dry film formation methods such as sputtering, plasma plating and ion plating; or
  • the organic layer may be formed by a wet film method such as spin coating, dipping, flow coating, or the like, followed by forming a cathode or an anode thereon.
  • the aforementioned compounds can be included as fluorescent materials.
  • the fluorescent material may have a maximum emission wavelength of 550 nm or less, and specifically, a maximum emission wavelength may appear in a range of 420 nm to 550 nm.
  • HOMO level of the compound represented by Formula 1 may be more than 5.4eV 5.8eV.
  • the triplet excitation energy (T1) of the compound represented by Formula 1 may be 2.4 eV or more and 2.7 eV or less.
  • the organic light emitting diode described above may be applied to an organic light emitting diode display.
  • Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After the completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure.
  • the product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 27 g (89% yield) of the target compound intermediate M-1 as a white solid.
  • the product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 19.2 g (yield 74%) of the target compound intermediate M-12 as a white solid.
  • Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure.
  • the product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give 17.9 g (yield 69%) of the target compound intermediate M-13 as a white solid. It was.
  • each compound was dissolved in THF, and then PL (photoluminescence) wavelength was measured using HITACHI F-4500.
  • the PL wavelength measurement results of the A-137 of Example 2 are shown in FIG. 3.
  • the energy level of each material was calculated by the Gaussian 09 method using a supercomputer GAIA (IBM power 6), and the results are shown in Table 1 below.
  • HOMO energy levels differ by more than 0.1 eV, which can affect device efficiency when used as a hole transport layer for organic optoelectronic devices.
  • a glass substrate coated with a thin film of indium tin oxide (1500 ⁇ ) of 1500 A was washed with distilled water ultrasonically. After washing the distilled water, ultrasonic washing with isopropyl alcohol, acetone, methane and the like, and then dried and transferred to a plasma cleaner, and then washed the substrate using oxygen plasma for 5 minutes and then transferred to a vacuum depositor.
  • 4,4'-bisP ⁇ -[4- ⁇ N, N-bis (3-methylphenyl) amino ⁇ -phenyl] -N-phenylamino] biphenyl (DNTPD) was formed on the ⁇ substrate using the prepared ⁇ transparent electrode as an anode. Was vacuum deposited to form a hole injection layer having a thickness of 600A.
  • HT-1 was then vacuum deposited to form a 250 A thick hole transport layer.
  • a secondary hole transport layer having a thickness of 50A was formed by vacuum deposition using the compound prepared in Example 1 on the hole transport layer.
  • 9,10-di- (2-naphthyl) anthracene (ADN) is used as a host on the auxiliary hole transport layer, and 3,2,5,8,1 l-tetra (tert-butyl) perylene (TBPe) is used as a dopant.
  • ADN 9,10-di- (2-naphthyl) anthracene
  • TBPe 3,2,5,8,1 l-tetra (tert-butyl) perylene
  • Alq3 was vacuum deposited on the emission layer to form an electron transport layer having a thickness of 250 A.
  • An organic light emitting device was manufactured by sequentially depositing LiF lOA and A1 1000A on the electron transport layer to form a cathode.
  • the organic light emitting device has a structure having five organic thin layers, specifically
  • Example 7 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 2 instead of Example 1.
  • Example 7
  • Example 8 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 3 instead of Example 1.
  • Example 8
  • Example ad-9 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 4 instead of Example 1.
  • Example ad-9 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example 4 instead of Example 1.
  • An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example ad-3 instead of Example 1. Due Diligence ad-10
  • Example 5 An organic light emitting diode was manufactured according to the same method as Example 5 except for using Example ad-6 instead of Example 1. Comparative Example 1
  • An organic light emitting diode was manufactured according to the same method as Example 5 except for using HT-2 instead of compound A-5 of Example 1.
  • the current value flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while increasing the voltage from 0V to 10V, and the measured current value was divided by the area to obtain a result.
  • the luminance was measured using a luminance meter (Minolta Cs-I OOOA) while increasing the voltage from 0V to 10V to obtain a result. (3) Measurement of luminous efficiency
  • the current efficiency (cd / A) of the same current density (10 mA / cm 2 ) was calculated using the luminance, current density and voltage measured from (1) and (2). (4) life measurement
  • Examples 5 to 8 Examples ad-9 and ad-10 are significantly improved luminous efficiency compared to Comparative Examples 1 and 2, the lifetime is also equal or It can be seen that the improved characteristics are shown above.
  • Examples 5-8, Examples ad-9 and ad-10 are at least 13% more efficient than Comparative Example 1, which does not use auxiliary HTL. Increased, with minimal compared to Comparative Example 2 using HT-2 as the secondary HTL.
  • biphenyl-bis (8-hydroxyquinoline) aluminum [Balq] was vacuum deposited on the emission layer to form a hole blocking layer having a thickness of 50 A.
  • Tris (8-hydroxyquinoline) aluminum [Alq 3 ] was vacuum deposited on the hole blocking layer to obtain a 250 A thickness.
  • An organic light emitting device was manufactured by forming an electron transport layer and sequentially depositing LiF lOA and AP000A on the electron transport layer to form a cathode.
  • the organic light emitting device has a structure having five organic thin layers, specifically
  • Example ad-11 An organic light emitting diode was manufactured according to the same method as Example 2 instead of Example 1.
  • Example ad-13 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example 3 instead of Example 1.
  • Example ad-14 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example 3 instead of Example 1.
  • Example ad-15 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-1 instead of Example 1.
  • Example ad-15 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-1 instead of Example 1.
  • Example ad-15 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-1 instead of Example 1.
  • Example ad-17 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example ad-3 instead of Example 1.
  • Example ad-17 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example ad-3 instead of Example 1.
  • Example ad-17 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using Example ad-3 instead of Example 1.
  • Example ad-17 Example ad-17
  • Example ad-1 1 An organic light emitting diode was manufactured according to the same method as Example ad-1 1 except for using Example ad-4 instead of Example 1. Comparative Example 3
  • Example ad-1 instead of HT-1, ⁇ , ⁇ '-di (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine
  • Example ad-1 N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine is substituted for HT-1.
  • An organic light emitting diode was manufactured according to the same method except that [TCTA] was used. Comparative Example 5 An organic light emitting diode was manufactured according to the same method as Example ad-11 except for using HT-1 instead of Example 1.
  • HT-1 and Alq3 used in the organic light emitting device fabrication are as described above, and the structure of NPB TCTA, CBP, Balq, Ir (ppy) 3 is as follows.
  • the method of measuring the current density change, the brightness change, and the luminous efficiency according to the voltage is the same as the method of the blue organic light emitting device, and the life time measuring method is as follows, and the results are shown in Table 3. Life measurement
  • Examples ad-1 1 to ad-17 can be seen to exhibit improved characteristics in terms of luminous efficiency, driving voltage, life compared to Comparative Examples 3 to 5.
  • Examples ad-1 1 to ad-17 showed an efficiency increase of at least 70% compared to Comparative Example 3 without the use of auxiliary HTL, the minimum compared to Comparative Example 5
  • HT-1 was then vacuum deposited to form a 200 A thick hole transport layer.
  • An auxiliary hole transport layer having a thickness of 100A was formed by vacuum deposition using the compound prepared in Example 1 on the hole transport layer.
  • (4,4'- ⁇ , ⁇ '-dicarbazole) biphenyl [CBP] was used as a host on the auxiliary hole transport layer, and dopant bis (2-phenylquinoline) (acetylacetonate) iridium ( ⁇ ) [Ir (pq) 2 acac] to 5 wt% to form a 300 A thick light emitting layer by vacuum deposition.
  • biphenyl-bis (8-hydroxyquinoline) aluminum [Balq] was vacuum deposited on the emission layer to form a hole blocking layer having a thickness of 50A.
  • Tris (8-hydroxyquinoline) aluminum [Alq 3 ] was vacuum deposited on the hole blocking layer to obtain a thickness of 250 A.
  • An organic light emitting device was manufactured by forming an electron transport layer and sequentially depositing UF 10A and A 000 000 A on the electron transport layer to form a cathode.
  • the organic light emitting device has a structure having six organic thin layers, specifically
  • Example ad-20 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 2 instead of Example 1.
  • Example ad-20 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 2 instead of Example 1.
  • Example ad-18 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example 4 instead of Example 1.
  • Example ad-21 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-1 instead of Example 1.
  • Example ad-22 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-1 instead of Example 1.
  • Example ad-23 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-3 instead of Example 1.
  • Example ad-23 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-3 instead of Example 1.
  • Example ad-23 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-3 instead of Example 1.
  • Example ad-18 An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using Example ad-5 instead of Example 1. Comparative Example 6
  • Example ad-18 ⁇ , ⁇ '-di (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine [ ⁇ ] is used instead of HT-1, and ⁇ , ⁇ '-di is used instead of Example 1.
  • An organic light emitting diode was manufactured according to the same method except that (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine [ ⁇ ] was used. Comparative Example 7
  • Example ad-18 ⁇ , ⁇ '-di (1-naphthyl) - ⁇ , ⁇ '-diphenylbenzidine [ ⁇ ] was used instead of HT-1, and Tris (4,4 ') was used instead of Example 1. , 4 "-(9-carbazolyl))-triphenylamine
  • An organic light emitting diode was manufactured according to the same method as Example ad-18 except for using HT-1 instead of Example 1.
  • the structures of DNTPD, NPB, HT-1, TCTA, CBP, Balq, and Alq3 used in fabricating the organic light emitting diode are as described above, and the structure of Ir (pq) 2 acac is as follows.
  • the method of measuring the current density change, the luminance change, and the luminous efficiency according to the voltage is the same as the method of the blue organic light emitting device, and the life time measuring method is as follows, and the results are shown in Table 4 below. Life measurement
  • the light was emitted at an initial luminance of 1,000 nit and over time.
  • the decrease in luminance was measured as the T80 lifetime when the luminance was reduced to 80% of the initial luminance.
  • Examples a d-18 to ad-23 showed at least an efficiency increase of at least 19% compared to Comparative Example 6 without the use of auxiliary HTL, and at least 8% increase in efficiency compared to Comparative Example 8. Compared with Comparative Example 4 using TCTA as the auxiliary HTL, the efficiency was higher and the T80 life was increased by at least 28%.
  • the present invention is not limited to the above embodiments, but may be manufactured in various forms. Those skilled in the art will appreciate that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un composé représenté par la formule 1, un élément optoélectronique organique le comprenant, ainsi qu'un dispositif d'affichage comprenant cet élément optoélectronique organique. La Formule 1 et la description associée sont tels que définies dans la spécification.
PCT/KR2015/003678 2014-05-13 2015-04-13 Composé, élément optoélectronique organique comprenant ledit composé et dispositif d'affichage le comprenant Ceased WO2015174640A1 (fr)

Priority Applications (4)

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CN201580019167.5A CN106164061B (zh) 2014-05-13 2015-04-13 用于有机光电装置的化合物、有机光电装置及显示装置
EP15791911.9A EP3144301B1 (fr) 2014-05-13 2015-04-13 Composé, élément optoélectronique organique comprenant ledit composé et dispositif d'affichage le comprenant
US15/117,753 US11563179B2 (en) 2014-05-13 2015-04-13 Compound, organic optoelectronic element comprising same and display device thereof
JP2016566263A JP6575969B2 (ja) 2014-05-13 2015-04-13 化合物、これを含む有機光電子素子および表示装置

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KR20140057324 2014-05-13
KR10-2014-0057324 2014-05-13
KR10-2015-0051095 2015-04-10
KR1020150051095A KR101931250B1 (ko) 2014-05-13 2015-04-10 화합물, 이를 포함하는 유기 광전자 소자 및 표시장치

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EP3029023A4 (fr) * 2014-07-11 2017-01-18 Idemitsu Kosan Co., Ltd Composé, matériau pour élément électroluminescent organique, élément électroluminescent organique et dispositif électronique
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JP2019501527A (ja) * 2015-12-15 2019-01-17 クンシャン ニュー フラット パネル ディスプレイ テクノロジー センター カンパニー リミテッド 有機発光表示デバイス及び表示装置
JP2019016788A (ja) * 2017-07-03 2019-01-31 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 有機発光素子
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JP2019501527A (ja) * 2015-12-15 2019-01-17 クンシャン ニュー フラット パネル ディスプレイ テクノロジー センター カンパニー リミテッド 有機発光表示デバイス及び表示装置
JP2019016788A (ja) * 2017-07-03 2019-01-31 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 有機発光素子
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