WO2015099481A1 - Organic electroluminescent device - Google Patents

Organic electroluminescent device Download PDF

Info

Publication number
WO2015099481A1
WO2015099481A1 PCT/KR2014/012888 KR2014012888W WO2015099481A1 WO 2015099481 A1 WO2015099481 A1 WO 2015099481A1 KR 2014012888 W KR2014012888 W KR 2014012888W WO 2015099481 A1 WO2015099481 A1 WO 2015099481A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
aryl
alkyl
layer
Prior art date
Application number
PCT/KR2014/012888
Other languages
French (fr)
Korean (ko)
Inventor
김태형
박호철
김영배
이창준
이은정
백영미
Original Assignee
주식회사 두산
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020140158154A external-priority patent/KR101742359B1/en
Application filed by 주식회사 두산 filed Critical 주식회사 두산
Priority to CN201480071035.2A priority Critical patent/CN105849227B/en
Priority to US15/107,971 priority patent/US10573822B2/en
Priority to JP2016543059A priority patent/JP6759099B2/en
Publication of WO2015099481A1 publication Critical patent/WO2015099481A1/en
Priority to US16/742,060 priority patent/US11588109B2/en
Priority to US17/589,017 priority patent/US20220336753A1/en
Priority to US17/953,510 priority patent/US20230093216A1/en

Links

Images

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/654Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14Carrier transporting layers
    • H10K50/16Electron transporting layers
    • H10K50/166Electron transporting layers comprising a multilayered structure
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • H10K85/321Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • H10K85/341Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to an organic electroluminescent device comprising at least one organic material layer.
  • the organic electroluminescent device when current or voltage is applied to two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, an exciton is formed, and the exciton falls to the ground and shines.
  • the organic EL device may be classified into a fluorescent EL device in which singlet excitons contribute to light emission and a phosphorescent EL device in which triplet excitons contribute to light emission, depending on the electron spin type of the formed exciton.
  • the electron spin of excitons formed by the recombination of electrons and holes, produces 25% and 75% of singlet excitons and triplet excitons.
  • the internal quantum efficiency cannot theoretically exceed 25% according to the production rate, and the external quantum efficiency is accepted as a limit of 5%.
  • Phosphorescent electroluminescent devices that emit light by triplet excitons exhibit luminous efficiency up to four times higher than fluorescence when a metal complex compound containing transition metal heavy atoms such as Ir and Pt is used as the phosphorescent dopant. Can be improved.
  • the phosphorescent electroluminescent device exhibits higher efficiency than fluorescence in terms of luminous efficiency on the basis of the theoretical fact.
  • a phosphorescent dopant having a deep blue color purity and a high efficiency is satisfied. Since the development level of the host of the energy gap is insufficient, the blue phosphor is not commercialized yet, and the blue phosphor is used in the product.
  • the present invention has been made to solve the above problems, and an object thereof is to provide an organic electroluminescent device having high efficiency, low voltage, and long life.
  • the present invention is an anode; cathode; And at least one organic material layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer between the anode and the cathode, and a lifetime improvement layer (Lifetime) between the light emitting layer and the electron transport layer. It provides an organic electroluminescent device further comprising an Enhancement Layer (LEL).
  • LEL Enhancement Layer
  • the life improvement layer includes a bipolar compound having both an electron attractor (EWG) having a high electron absorption and an electron donor (EDG) having a large electron donor, wherein the bipolar compound includes the following (a) ) To (d) all of the conditions are characterized.
  • the triplet energy is at least 2.3 eV
  • FIG. 1 is a cross-sectional view illustrating an organic EL device according to an exemplary embodiment of the present invention.
  • hole injection layer 302 hole transport layer
  • the present invention is an anode; cathode; And an organic material layer interposed between the anode and the cathode, wherein the organic material layer includes at least one selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a life improvement layer, an electron transport layer, and an electron injection layer.
  • the Lifetime Enhancement Layer is an organic electroluminescent device including a bipolar compound having both an electron attractor (EWG) having high electron absorption and an electron donor (EDG) having a large electron donor. It is about.
  • the bipolar compound may be used as a material of an electron transport layer, an electron injection layer, or both, in addition to the life improvement layer.
  • the anode 100 serves to inject holes into the organic material layer 300.
  • the material constituting the positive electrode 100 is not particularly limited, and conventional materials known in the art may be used.
  • Non-limiting examples thereof include metals such as vanadium, chromium, copper, zinc and gold; Alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al and SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; And carbon black.
  • metals such as vanadium, chromium, copper, zinc and gold
  • Alloys thereof Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al and SnO 2 : Sb;
  • the method of manufacturing the positive electrode 100 is not particularly limited, and may be prepared according to conventional methods known in the art. As an example, a method of coating an anode material on a substrate made of a silicon wafer, quartz, glass plate, metal plate or plastic film may be mentioned.
  • the cathode 200 serves to inject electrons into the organic material layer 300.
  • the material constituting the cathode 200 is not particularly limited, and conventional materials known in the art may be used. Non-limiting examples thereof include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead; Alloys thereof; And multilayer structure materials such as LiF / Al and LiO 2 / Al.
  • the method of manufacturing the cathode 200 is also not particularly limited, and may be manufactured according to methods known in the art.
  • the organic material layer 300 included in the organic electroluminescent device according to the present invention can be used as an organic material layer of the existing organic electroluminescent device without limitation, for example, a hole injection layer 301, a hole transport layer 302, a light emitting layer ( 303), the life improvement layer 304, the electron transport layer 305 and the electron injection layer 306 may include one or more selected from the group.
  • a hole injection layer 301 a hole transport layer 302
  • the life improvement layer 304 the electron transport layer 305 and the electron injection layer 306 may include one or more selected from the group.
  • the hole injection layer 301 and the hole transport layer 302 included in the organic material layer 300 of the present invention serve to move the holes injected from the anode 100 to the light emitting layer 303.
  • the material forming the hole injection layer 301 and the hole transport layer 302 is not particularly limited as long as the hole injection barrier is low and the hole mobility is high, and the hole injection layer / transport layer material used in the art can be used without limitation. have. Non-limiting examples thereof include arylamine derivatives.
  • the light emitting layer 303 included in the organic material layer 300 of the present invention is a layer in which holes and electrons meet to form an exciton, and the color of light emitted from the organic EL device according to the material forming the light emitting layer 303. This may vary.
  • the light emitting layer 303 may include a host and a dopant, and the host may be included in the range of 70 to 99.9 wt%, and the dopant may be included in the range of 0.1 to 30 wt%.
  • the host when the light emitting layer 303 is blue fluorescence, green fluorescence or red fluorescence, the host may be included in the range of 80 to 99.9% by weight and the dopant in the range of 0.1 to 20% by weight. In addition, when the emission layer 303 is blue fluorescence, green fluorescence or red phosphorescence, the host may be included in the range of 70 to 99 wt% and the dopant in the range of 1 to 30 wt%.
  • the host included in the light emitting layer 303 is not particularly limited as long as it is known in the art, and non-limiting examples thereof include alkali metal complex compounds; Alkaline earth metal complexes; Or condensed aromatic ring derivatives.
  • the host material may be an aluminum complex, a beryllium complex, anthracene derivative, pyrene derivative, triphenylene derivative, carbazole derivative, dibenzofuran derivative, di Preference is given to using benzothiophene derivatives or one or more combinations thereof.
  • the dopant included in the emission layer 303 is not particularly limited as long as it is known in the art, and non-limiting examples thereof include anthracene derivative, pyrene derivative, arylamine derivative, iridium (Ir) or platinum (Pt).
  • the metal complex compound etc. which are included are mentioned.
  • the light emitting layer 303 may be a single layer or two or more layers.
  • the organic light emitting diode may emit light of various colors.
  • the present invention includes a light emitting layer made of a plurality of single materials between the hole transport layer 302 and the life improvement layer 304, or an organic electroluminescent device having a mixed color by having a light emitting layer made of different materials in series. Can be provided.
  • the driving voltage of the device is increased, but the current value in the organic light emitting device is constant, thereby providing an organic EL device having improved light emission efficiency by the number of light emitting layers.
  • the lifespan improvement layer 304 included in the organic material layer 300 of the present invention is to improve the lifespan of the organic EL device and is provided between the light emitting layer 303 and the electron transport layer 305.
  • the material constituting the life improvement layer 304 is not particularly limited, but is preferably a bipolar compound having both an electron attractor (EWG) having high electron absorption and an electron donor (EDG) having a large electron donor. .
  • the bipolar compound has an ionization potential of 5.5 eV or more, specifically, may be in the range of 5.5 to 7.0 eV, preferably in the range of 5.5 to 6.5 eV.
  • the difference between the HOMO value and the LUMO value (E HOMO -E LUMO ) of the bipolar compound may be greater than 2.9 eV, specifically, greater than 2.9 eV and less than 3.5 eV.
  • the triplet energy may be 2.3 eV or more, specifically, 2.3 to 3.5 eV, and preferably 2.3 to 3.0 eV.
  • the singlet energy and triplet energy difference ⁇ Est of the bipolar compound is less than 0.5 eV, specifically, the compound is less than 0.5 eV, 0.01 eV or more range.
  • the holes move in the organic electroluminescent device at the ionization potential level.
  • the holes diffuse or move to the electron transport layer 305 beyond the light emitting layer 303, an irreversible decomposition reaction by oxidation occurs, which causes organic electroluminescence. The lifetime of the device is reduced.
  • the life improvement layer 304 made of a bipolar compound having an ionization potential [Ip (LEL)] of 5.5 eV or more is provided, the hole is prevented from diffusing or moving to the electron transport layer 305, and thus the organic electric field.
  • the life of the light emitting device can be improved. That is, the holes are blocked by the high energy barrier of the life improvement layer 304, and thus do not diffuse or move to the electron transport layer 305, but remain in the light emitting layer 303.
  • the ionization potential of the bipolar compound included in the life improvement layer 304 may be just 5.5 eV or more, but the light emitting layer 303 may be a green phosphor or a blue phosphorescent light.
  • the ionization potential of the bipolar compound is preferably 6.0 eV or more.
  • the bipolar compound has a difference between HOMO and LUMO (E HOMO -E LUMO ) of more than 2.9 eV, triplet energy of 2.3 eV or more, singlet energy and triplet energy difference ( ⁇ Est) of less than 0.5 eV. Therefore, when it is used for the life improvement layer 304, the exciton formed in the light emitting layer 303 is prevented from diffusing into the electron transporting layer 305, and light emission occurs at the interface between the light emitting layer 303 and the electron transporting layer 305. You can also stop. As a result, it is possible to prevent spectral mixing of the organic EL device and to improve stability, thereby improving the life of the organic EL device.
  • E HOMO -E LUMO the exciton formed in the light emitting layer 303 is prevented from diffusing into the electron transporting layer 305, and light emission occurs at the interface between the light emitting layer 303 and the electron transporting layer 305. You can also stop. As a result, it is possible
  • the bipolar compound has both the electron attracting force (EWG) and the electron donor (EDG) with the high electron donor (EDG) has a characteristic that the electron cloud of HOMO and LUMO is separated.
  • EWG electron attracting force
  • EDG electron donor
  • EDG electron donor
  • T1 triplet energy
  • the triplet energy of the bipolar compound included in the lifespan improvement layer 304 may be 2.3 eV or more, but when the light emitting layer 303 is made of green phosphorescent material, In the case of 2.5 eV or more and a blue phosphor, it is preferably 2.7 eV or more.
  • the electrons or holes that do not form excitons by recombination may be light emitting layers 303. Stacked). Electrons or holes accumulated in the light emitting layer 303 may prevent oxidation and reduction from occurring smoothly in the light emitting layer 303 or may affect adjacent layers to reduce the lifespan of the organic EL device.
  • the bipolar compound has a hole mobility and an electron mobility of 1 ⁇ 10 ⁇ 6 cm 2 / V ⁇ s or more at room temperature, when used in the life improvement layer 304, holes injected from the anode 100 are used.
  • the life of the organic EL device can be improved by preventing the injection of electrons to be delayed compared to the number of.
  • the bipolar compound included in the life improvement layer 304 of the present invention exhibits hole mobility of 1 ⁇ 10 ⁇ 6 cm 2 / V ⁇ s or more at room temperature by an electron donor (EDG), EWG) results in electron mobility of 1 ⁇ 10 ⁇ 6 cm 2 / V ⁇ s or more at room temperature. Therefore, when it is used for the lifespan improvement layer 304, electrons can be effectively injected into the light emitting layer 303. As such, when the electron injection into the light emitting layer 303 is smooth, the formation efficiency of the exciton in the light emitting layer 303 may be improved, thereby improving the life of the organic EL device.
  • EDG electron donor
  • the bipolar compound included in the life improvement layer 304 of the present invention has a moiety having an electron attracting (EWG) characteristic with high electron absorption and a moiety having a large electron donor (EDG) characteristic with an electron donor. Is formed by combining.
  • EWG electron attracting
  • EWG electron donor
  • the electron drawer (EWG) is characterized in that it comprises one or more electron drawer (EWG) moiety represented by the following formula.
  • a 1 to A 11 are the same as or different from each other, each independently N or C (R), and at least one is N, wherein a plurality of R's are the same or different, respectively, even if the same are indicated, and they are condensed with adjacent groups May form a ring.
  • R plural C
  • R is hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 Cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , C 6 to C 60 Aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C 1 to C 40 alkyl boron group, C 6 to C 60 aryl boron group, C 1 to C 40 A phosphine group, a C 1 to C 40 phosphine oxide group and a C 6 to C 60 arylamine group,
  • the pin group, the phosphine oxide group and the arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, nuclear atoms, 3 to 40 heterocycloalkyl group, C 6 ⁇ C 40 aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, a C 1 ⁇ C 40 alkyl Oxy group, C 6 ⁇ C 60 ary
  • the electron attracting (EWG) moiety is a nitrogen-containing heteroaromatic hydrocarbon having 5 or 6 nuclear atoms in which 1-3 carbons are substituted with nitrogen.
  • the EWG moiety may have a form in which two or more rings are simply attached to or condensed with each other, or in the form of an aryl group.
  • the electron attracting moiety (EWG) moiety may be more embodied in a structure represented by the following formula, it is preferable when the six-membered nitrogen heteroaromatic hydrocarbon containing 1 to 3 nitrogen.
  • EWG moieties include pyridine, pyrimidine, triazine, pyrazine and the like.
  • the carbon or nitrogen atom of the moiety having the electron-extracting (EWG) property having high electron absorption forms a bond with the moiety having the electron donor (EDG) property having a large electron donating property.
  • the bipolar compound included in the lifespan improvement layer 304 of the present invention is characterized by including an electron donor (EDG) moiety represented by the following Chemical Formula 1.
  • EDG electron donor
  • moieties having large electron donor (EDG) characteristics of electron donors include condensed nitrogen heteroaromatic rings such as indole, carbazole, and azepine;
  • condensed polycyclic aromatic rings such as biphenyl, triphenylene, and fluoranthene may be used, and more specifically, may be represented by the following Chemical Formula 1.
  • X 1 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),
  • Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), wherein a plurality of R 1 are each the same or different even if represented the same, and they may form a condensed ring with an adjacent group
  • X 2 and X 3 are the same as or different from each other, and each independently N or C (R 2 ), wherein a plurality of R 2 are the same or different, even though they are the same, and they may form condensed rings with adjacent groups
  • R 1 to R 2 and Ar 1 to Ar 5 are the same as or different from each other, and each independently, hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 60 aryl group, nuclear atom 5 to 60 Heteroaryl group, C 1 ⁇ C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, is selected from the group consisting of C 6 ⁇ C group 60 arylboronic of, C 1 ⁇ C 40 of the phosphine group, C 1 ⁇ C 40 phosphine
  • Alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 Alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 hetero aryl group, C 1 ⁇ C 40 of the alkyloxy group, C 6 ⁇ C 60 of the ary
  • Chemical Formula 1 may be more embodied as any one of the following A-1 to A-24. However, it is not limited thereto.
  • R 2 , Y 1 to Y 4, and Ar 1 to Ar 5 are the same as those of Formula 1 described above.
  • the electron donor (EDG) moiety is preferably A-1 to A-6.
  • Formula 1 which is an electron donor (EDG) moiety
  • EDG electron donor
  • Y 1 to Y 4 are each independently N or C (R 1 ), and when they are a plurality of C (R 1 ), Y 1 and Y 2 , Y 2 and Y 3 or Y 3 And one of Y 4 forms a condensed ring with Formula 2 below.
  • R 1 may be the same or different, respectively.
  • both X 2 And X 3 In Formula 1 is C (R 2 )
  • a plurality of R 2 may be combined with Formula 2 or Formula 3, respectively, to form a condensed ring.
  • Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), wherein when a plurality of C (R 3 ) is a plurality of R 3 are the same or different, respectively, and are bonded to the formula (1)
  • N or C (R 3 ) is a plurality of R 3 are the same or different, respectively, and are bonded to the formula (1)
  • X 4 is the same as X 1 , wherein a plurality of Ar 1 to Ar 5 are the same or different, respectively.
  • a plurality of R 3 non-forming a condensed ring may be the same or different from each other even if they are the same, and each independently represent hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a C 1 to C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 of the alkynyl group, C 3 ⁇ C 40 cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C 6 ⁇ C 60 aryl group, a nuclear Heteroaryl group of 5 to 60 atoms, C 1 ⁇ C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ alkyl boron C 40 group, C 6 ⁇ C 60 aryl boron group, C 1 ⁇ C 40
  • the phosphine group, the phosphine oxide group and the arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 1 to C 40 Alkyloxy group, C 6 ⁇ C
  • the compound formed by condensation of Chemical Formula 1 and Chemical Formula 2 may be embodied in any one of the compounds represented by the following Chemical Formulas 1a to 1f.
  • X 1 to X 4 and Y 1 to Y 8 are as defined in the formula (1) and (2).
  • Y 1 to Y 4 which form a condensed ring are N or C (R 1 ), all of which are preferred when C (R 1 ), and Y 5 to Y 8 are N Or C (R 3 ), all of which are C (R 3 ).
  • R 1 and R 3 are the same or different, respectively.
  • Ar 1 and R 1 to R 3 are the same as defined in the formula (1) and (2).
  • Ar 1 is a substituted or unsubstituted C 6 ⁇ C 40 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms,
  • R 1 to R 3 are each independently hydrogen, a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, or a substituted or unsubstituted nuclear atom 5 to 40 It is preferable when it is a heteroaryl group of.
  • Formulas B-1 to B-30 having a condensed structure of Formulas 1 and 2 include one or more condensed indole or condensed carbazole moieties.
  • the compound formed by condensation of Formula 1 and Formula 3 may be embodied as any one of the compounds represented by the following Formulas 1g to 1n.
  • X 1 , X 3 to X 4 and Y 1 to Y 14 are the same as defined in Formula 1 and Formula 3.
  • X 1 and X 4 are the same as or different from each other, preferably each independently O, S or N (Ar 1 ), more preferably all N (Ar 1 ). At this time, a plurality of Ar 1 is the same or different.
  • Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), preferably all of C (R 1 ). In this case, a plurality of R 1 are the same or different.
  • X 3 are each independently N or C (R 2 ),
  • Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), preferably all of C (R 3 ). In this case, a plurality of R 3 are the same or different.
  • Ar 1 and R 1 to R 3 are as defined in the formula (1) and (3).
  • X 1 and X 4 are each independently N (Ar 1 ) or S. That is, it is preferable that X 1 is N (Ar 1 ) and X 4 is S, X 1 is S and X 4 is N (Ar 1 ), or both X 1 and X 4 are N (Ar 1 ).
  • Ar 1 is preferably a substituted or unsubstituted C 6 ⁇ C 60 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms
  • Ar 2 to Ar 5 is the same as or different from each other, and each independently represent a substituted or unsubstituted C 1 to C 40 alkyl group (specifically, a methyl group) or a substituted or unsubstituted C 6 to C 60 aryl group (specifically, a phenyl group) desirable.
  • the chemical formulas having the condensed structure of Chemical Formulas 1 and 3 have the characteristics of an electron donor (EDG) having a large electron donor including one or more condensed azepine moieties.
  • EDG electron donor
  • the bipolar compound included as a material for the lifespan improvement layer may include a moiety having an electron donor (EDG) characteristic of which the electron donor represented by the following Chemical Formula 4 is large.
  • EDG electron donor
  • L 1 to L 3 are the same as or different from each other, and each independently selected from the group consisting of a single bond, a C 6 to C 60 arylene group, a heteroarylene group having 5 to 60 nuclear atoms,
  • Ar 6 to Ar 8 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, an aryl group having 6 to 40 carbon atoms and a heteroaryl group having 5 to 40 nuclear atoms, provided that Ar 6 to Ar Except when 8 are all the same,
  • R 4 to R 6 are the same or different, each independently, hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, an alkenyl group of C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 of, C 2 Alkynyl group of ⁇ C 40 , cycloalkyl group of C 3 ⁇ C 40 , heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 ⁇ C 60 , heteroaryl group of 5 to 60 nuclear atoms, C 1 ⁇ C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ is selected from the group consisting of C 60 aryl boron group, C 1 ⁇ C 40 of the phosphine group, C 1 ⁇ C 40 pho
  • a to c are each independently an integer of 0 to 3
  • the time period, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ⁇ C 40 Alkyl group, C 2 ⁇ C 40 Alkenyl group, C 2 ⁇ C 40 Alkynyl group, C 3 ⁇ C 40 Cycloalkyl group, C 3 ⁇ 40 Heterocycloalkyl group, C 6 ⁇ C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 1
  • L One To L 3 It is preferably each independently a single bond, phenylene, biphenylene, or carbazolylene.
  • Ar 6 to Ar 8 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, an aryl group having 6 to 40 carbon atoms and a heteroaryl group having 5 to 40 nuclear atoms, wherein Ar 6 to At least one of Ar 8 is preferably selected from a heteroaryl group having 5 to 40 nuclear atoms including at least one element selected from the group consisting of N, O, and S. However, the case where Ar 6 to Ar 8 are all the same is excluded.
  • At least one of R 1 to R 6 and Ar 1 to Ar 8 is the moiety having an electron-withdrawing (EWG) property of high electron absorption Form a bond with.
  • EWG electron-withdrawing
  • Alkyl in the present invention is a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like. Can be mentioned.
  • Alkenyl in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include vinyl and allyl. ), Isopropenyl, 2-butenyl, and the like.
  • Alkynyl in the present invention is a monovalent substituent derived from a C2-C40 straight or branched chain unsaturated hydrocarbon having one or more carbon-carbon triple bonds. Examples thereof include ethynyl, 2- Propanyl (2-propynyl) etc. are mentioned.
  • Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms combined with a single ring or two or more rings.
  • a form in which two or more rings are attached to each other (pendant) or condensed may also be included.
  • aryls include phenyl, naphthyl, phenanthryl, anthryl and the like.
  • Heteroaryl in the present invention means a monovalent substituent derived from monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se.
  • a form in which two or more rings are pendant or condensed with each other may also be included, and may also include a form condensed with an aryl group.
  • heteroaryl examples include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like.
  • 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, 2-furany
  • Aryloxy in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
  • Alkyloxy in the present invention is a monovalent substituent represented by R'O-, wherein R 'means 1 to 40 alkyl, and includes a linear, branched or cyclic structure It is interpreted as. Examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
  • Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
  • Cycloalkyl in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms.
  • Examples of such cycloalkyl include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
  • Heterocycloalkyl in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O, S or Substituted with a hetero atom such as Se.
  • heterocycloalkyl include morpholine, piperazine and the like.
  • Alkylsilyl in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms
  • arylsilyl means silyl substituted with aryl having 6 to 40 carbon atoms.
  • Condensed ring in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.
  • the electron transport layer 305 and the electron injection layer 306 included in the organic material layer 300 serves to move the electrons injected from the cathode 200 to the light emitting layer 303. do.
  • the material constituting the electron transport layer 305 and the electron injection layer 306 is not particularly limited as long as it is easy to inject electrons and has high electron mobility, but is not limited thereto.
  • the bipolar compound, anthracene derivative, and heteroaromatic compound may be used. And alkali metal complex compounds.
  • the electron transport layer 305 and / or the electron injection layer 306 of the present invention is preferably made of the same bipolar material, that is, the bipolar compound represented by the formula (1).
  • the electron transport layer 305 and / or the electron injection layer 306 may be a co-deposited alkali metal complex compound to facilitate the injection of electrons from the cathode.
  • the alkali metal complex compound may be an alkali metal, an alkaline earth metal or a rare earth metal.
  • the organic material layer 300 of the present invention as described above may further include an organic film layer (not shown) for blocking electrons and excitons between the hole transport layer 302 and the light emitting layer 303.
  • the organic layer has a high LUMO value to prevent electrons from moving to the hole transport layer 302, and has a high triplet energy to prevent the excitons of the light emitting layer 303 from diffusing into the hole transport layer 302.
  • the material constituting such an organic film layer is not particularly limited, and examples thereof include carbazole derivatives or arylamine derivatives.
  • the method of manufacturing the organic material layer 300 of the present invention is not particularly limited, but non-limiting examples include a vacuum deposition method and a solution coating method.
  • the solution coating method may be spin coating, dip coating, doctor blading, inkjet printing, thermal transfer method and the like.
  • the organic electroluminescent device of the present invention has a structure in which the anode 100, the organic material layer 300 and the cathode 200 are sequentially stacked, between the anode 100 and the organic material layer 300 or between the cathode 200 and the organic material layer
  • the insulating layer or the adhesive layer may be further included between the 300.
  • Such an organic electroluminescent device of the present invention may have excellent lifespan characteristics since life time of initial brightness is increased while maintaining the maximum luminous efficiency when voltage, current, or both are applied.
  • the bipolar compounds LE-01 to LE-36 are shown below, respectively.
  • the glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol
  • UV OZONE cleaner Power sonic 405, Hwasin Tech
  • a device was manufactured by sequentially depositing a hole injection layer, a hole transport layer, a light emitting layer, a life improvement layer, an electron transport layer, an electron injection layer, and a cathode on an ITO transparent electrode (substrate) prepared as described above.
  • the structure of the manufactured device is shown in Table 2 below.
  • Hole injection layer DS-205 (Doosan Corporation) 80 nm Hole transport layer NPB 15 nm Light emitting layer ADN + 5% DS-405 (Doosan Corporation) 30 nm Life Improvement Layer LE-01 to LE-36 5 nm Electron transport layer Alq 3 25 nm Electron injection layer LiF 1nm cathode Al 200 nm
  • a device was manufactured in the same manner as in Example 1, except that the electron transport layer was deposited at 30 nm without using the life improving layer.
  • a device was manufactured in the same manner as in Example 1, except that BCP having the following structure instead of LE-01 was used.
  • the organic EL device of Examples 1 to 12 including the life improvement layer of the present invention is superior in current efficiency, driving voltage and life than the organic EL device of Comparative Examples 1 and 2 there was.
  • the glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol
  • UV OZONE cleaner Power sonic 405, Hwasin Tech
  • a device was manufactured by sequentially depositing a hole injection layer, a hole transport layer, a light emitting layer, a life improvement layer, an electron transport layer, an electron injection layer, and a cathode on an ITO transparent electrode (substrate) prepared as described above.
  • the structure of the manufactured device is shown in Table 4 below.
  • m-MTDATA, TCTA, Ir (ppy) 3 and the structure of the CBP is as follows.
  • a device was manufactured in the same manner as in Example 37, except that an electron transport layer was deposited at 30 nm without using a lifetime improving layer.
  • a device was manufactured in the same manner as in Example 37, except for using the BCP used in Comparative Example 2 instead of LE-02.
  • the present invention can provide an organic EL device having excellent driving voltage, luminous efficiency and lifetime by introducing a lifetime improving layer, an electron transporting layer, or an electron injection layer formed of a bipolar compound having specific physical properties into the organic EL device. have.
  • a display panel having improved performance and lifespan can be provided as the organic electroluminescent device of the present invention is applied to a display panel.

Landscapes

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

Abstract

The present invention provides an organic electroluminescent device comprising: an anode; a cathode; and one or more organic layers which are disposed between the anode and the cathode, and which comprise one or more selected from the group consisting of a hole injection layer, a hole transporting layer, a luminescent layer, an electron transporting layer, and an electron injection layer and further comprise a lifetime enhancement layer between the luminescent layer and the electron transporting layer.

Description

유기 전계 발광 소자Organic electroluminescent element
본 발명은 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to an organic electroluminescent device comprising at least one organic material layer.
1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 전계 발광 (electroluminescent, EL) 소자에 대한 연구가 이어져 오다가, 1987년 탕(Tang)에 의하여 정공층(NPB)과 발광층(Alq3)으로 구성된 2층 적층 구조의 유기 전계 발광 소자가 제안되었다. 이후 유기 전계 발광 소자는 상용화를 위해 필요한 고효율, 장수명 특성을 구현하기 위해 소자 내에 정공주입 및 수송을 담당하는 유기층과 전자주입 및 수송을 담당하는 유기층, 정공과 전자의 결합에 의해 전계 발광이 일어나도록 유도하는 유기층 등과 같이 각각의 특징적이고, 세분화된 기능을 부여한 다층 적층 구조의 형태가 제안되었다. 다층 적층 구조의 도입은 유기 전계 발광 소자의 성능을 상용화 특성까지 향상시켜, 1997년 차량용 라디오 디스플레이 제품을 시작으로 휴대용 정보표시기기 및 TV용 디스플레이 소자로까지 그 적용 범위를 확대시켰다. In 1965, research on organic electroluminescent (EL) devices led to blue electroluminescence using anthracene single crystals was continued.In 1987, Tang formed a hole layer (NPB) and a light emitting layer (Alq 3 ). An organic electroluminescent device having a layered structure has been proposed. Afterwards, the organic electroluminescent device generates electroluminescence by combining the organic layer, which is responsible for hole injection and transport, and the organic layer, which is responsible for electron injection and transport, and holes and electrons, in order to realize high efficiency and long life characteristics required for commercialization. Forms of multi-layered laminate structures have been proposed that impart respective distinctive and granular functions, such as inducing organic layers. The introduction of the multilayered laminate structure improves the performance of the organic electroluminescent device to commercialization characteristics, and has expanded its application range from portable radio display products in 1997 to portable information display devices and TV display devices.
디스플레이의 대형화, 고해상도화의 요구는 유기 전계 발광 소자의 고효율화, 장수명화의 과제를 부여하고 있다. 특히, 같은 면적에서 더 많은 화소 형성을 통해 구현되는 고해상도화의 경우 유기 전계 발광 화소의 발광면적을 감소시키는 결과를 초래하여 수명을 감소시킬 수 밖에 없으며, 유기 전계 발광 소자가 극복해야 할 가장 중요한 기술적 과제가 되었다. The demand for larger displays and higher resolutions has led to problems of high efficiency and long life of organic EL devices. In particular, in the case of high resolution achieved through the formation of more pixels in the same area, the result is a reduction in the emission area of the organic electroluminescent pixels, which inevitably leads to a reduction in the lifetime, and is the most important technology that the organic electroluminescent device must overcome. It became a task.
유기 전계 발광 소자는 두 전극에 전류, 또는 전압을 인가하면 양극에서는 정공이 유기물층으로 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어져 빛을 내게 된다. 이때, 유기 전계 발광 소자는 형성된 엑시톤의 전자 스핀 종류에 따라 일중항 엑시톤이 발광에 기여하는 형광 전계 발광 소자와 삼중항 엑시톤이 발광에 기여하는 인광 전계 발광 소자로 구분될 수 있다. In the organic electroluminescent device, when current or voltage is applied to two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, an exciton is formed, and the exciton falls to the ground and shines. In this case, the organic EL device may be classified into a fluorescent EL device in which singlet excitons contribute to light emission and a phosphorescent EL device in which triplet excitons contribute to light emission, depending on the electron spin type of the formed exciton.
전자와 정공의 재결합에 의해 형성되는 엑시톤의 전자 스핀은 일중항 엑시톤과 삼중항 엑시톤이 25%, 75%의 비율로 생성된다. 일중항 엑시톤에 의해 발광이 이루어지는 형광 전계 발광 소자는 생성 비율에 따라 이론적으로 내부 양자 효율이 25%를 넘을 수 없으며, 외부 양자 효율은 5%가 한계로 받아들여 지고 있다. 삼중항 엑시톤에 의해 발광이 이루어지는 인광 전계 발광 소자는 Ir, Pt와 같은 전이금속 중원자(heavy atoms)가 포함된 금속 착체 화합물을 인광 도판트로 사용했을 경우, 형광에 비해 최고 4배까지 발광 효율을 향상시킬 수 있다. The electron spin of excitons, formed by the recombination of electrons and holes, produces 25% and 75% of singlet excitons and triplet excitons. In the fluorescent electroluminescent device which emits light by singlet excitons, the internal quantum efficiency cannot theoretically exceed 25% according to the production rate, and the external quantum efficiency is accepted as a limit of 5%. Phosphorescent electroluminescent devices that emit light by triplet excitons exhibit luminous efficiency up to four times higher than fluorescence when a metal complex compound containing transition metal heavy atoms such as Ir and Pt is used as the phosphorescent dopant. Can be improved.
상기와 같이 인광 전계 발광 소자는 이론적인 사실을 근거로 발광효율 면에서 형광보다 높은 효율을 나타내지만, 녹색과 적색을 제외한 청색 인광소자에 있어서는 진청색의 색순도와 고효율의 인광 도판트 및 이를 만족시키는 넓은 에너지 갭의 호스트에 대한 개발수준이 미비하여 아직까지는 청색 인광소자가 상용화되지 못하고, 청색 형광소자가 제품에 사용되고 있다. As described above, the phosphorescent electroluminescent device exhibits higher efficiency than fluorescence in terms of luminous efficiency on the basis of the theoretical fact. However, in the blue phosphorescent device except green and red, a phosphorescent dopant having a deep blue color purity and a high efficiency is satisfied. Since the development level of the host of the energy gap is insufficient, the blue phosphor is not commercialized yet, and the blue phosphor is used in the product.
상기 유기 전계 발광 소자의 특성을 향상시키기 위해 정공이 전자 전달층으로 확산되는 것을 방지하여 소자의 안정성을 증가시키기 위한 연구 결과가 보고되어 왔다. 발광층과 전자 전달층 사이에 BCP나 BPhen 등의 재료를 사용함으로 정공이 전자 전달층으로 확산되는 것을 막고, 발광층 내부로 제한시켜 효과적으로 정공과 전자의 재결합 확률을 높이는 기술이 제안되었다. 하지만 BCP나 BPhen 등의 유도체들은 정공에 대한 산화 안정성이 떨어지고, 열에 대한 내구성이 취약하여 결과적으로 유기 전계 발광 소자의 수명을 감소시켜 상업화되지 못했다. 또한 이러한 재료들은 단순히 정공을 저지하는 기능을 수행하므로 전자의 이동을 저해시켜 유기 전계 발광 소자의 구동전압을 상승시킨다.In order to improve the characteristics of the organic EL device, research has been reported to increase the stability of the device by preventing the diffusion of holes into the electron transport layer. By using a material such as BCP or BPhen between the light emitting layer and the electron transporting layer, a technique for preventing holes from diffusing into the electron transporting layer and limiting the inside of the light emitting layer to effectively increase the probability of recombination of holes and electrons has been proposed. However, derivatives such as BCP and BPhen have poor oxidative stability to holes and poor heat resistance, and as a result, have not been commercialized by reducing the lifetime of organic EL devices. In addition, these materials simply block holes, thereby inhibiting the movement of electrons, thereby increasing the driving voltage of the organic EL device.
본 발명은 상기한 문제점을 해결하기 위한 것으로, 고효율, 저전압, 장수명을 가지는 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.The present invention has been made to solve the above problems, and an object thereof is to provide an organic electroluminescent device having high efficiency, low voltage, and long life.
본 발명은 양극; 음극; 및 상기 양극과 음극 사이에, 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군에서 선택되는 유기물층이 1층 이상 설치되어 있고, 상기 발광층과 전자수송층 사이에 수명개선층(Lifetime Enhancement Layer, LEL)을 더 포함하는 유기 전계 발광 소자를 제공한다.The present invention is an anode; cathode; And at least one organic material layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer between the anode and the cathode, and a lifetime improvement layer (Lifetime) between the light emitting layer and the electron transport layer. It provides an organic electroluminescent device further comprising an Enhancement Layer (LEL).
여기서, 상기 수명개선층(LEL)은 전자흡수성이 큰 전자끌게기(EWG)와 전자공여성이 큰 전자주게기(EDG)를 모두 가지는 양극성(bipolar) 화합물을 포함하되, 상기 양극성 화합물은 하기 (a) 내지 (d) 조건을 모두 만족하는 것을 특징으로 한다. Here, the life improvement layer (LEL) includes a bipolar compound having both an electron attractor (EWG) having a high electron absorption and an electron donor (EDG) having a large electron donor, wherein the bipolar compound includes the following (a) ) To (d) all of the conditions are characterized.
(a) 이온화포텐셜[Ip(LEL)]이 5.5 eV 이상이고, (a) ionization potential [Ip (LEL)] is at least 5.5 eV,
(b) EHOMO-ELUMO > 2.9 eV, (b) E HOMO- E LUMO > 2.9 eV,
(c) 삼중항 에너지가 2.3 eV 이상이며, (c) the triplet energy is at least 2.3 eV,
(d) ΔEst < 0.5eV (ΔEst는 상기 화합물의 일중항 에너지와 삼중항 에너지의 차이를 나타냄)(d) ΔEst <0.5 eV (ΔEst represents the difference between the singlet and triplet energies of the compound)
도 1은 본 발명의 일 실시예에 따른 유기 전계 발광 소자를 나타낸 단면도이다.1 is a cross-sectional view illustrating an organic EL device according to an exemplary embodiment of the present invention.
<부호의 간단한 설명><Short description of symbols>
100: 양극 200: 음극 100: anode 200: cathode
301: 정공주입층 302: 정공수송층 301: hole injection layer 302: hole transport layer
303: 발광층 304: 수명개선층303: light emitting layer 304: life improvement layer
305: 전자수송층 306: 전자주입층305: electron transport layer 306: electron injection layer
이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 유기물층을 포함하며, 상기 유기물층은 정공주입층, 정공수송층, 발광층, 수명개선층, 전자수송층 및 전자주입층으로 이루어진 군에서 선택된 1종 이상을 포함하고, 상기 수명 개선층(Lifetime Enhancement Layer, LEL)은 전자 흡수성이 큰 전자끌게기(EWG)와 전자 공여성이 큰 전자주게기(EDG)를 모두 가지는 양극성(bipolar) 화합물을 포함하는 유기 전계 발광 소자에 관한 것이다. The present invention is an anode; cathode; And an organic material layer interposed between the anode and the cathode, wherein the organic material layer includes at least one selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a life improvement layer, an electron transport layer, and an electron injection layer. In addition, the Lifetime Enhancement Layer (LEL) is an organic electroluminescent device including a bipolar compound having both an electron attractor (EWG) having high electron absorption and an electron donor (EDG) having a large electron donor. It is about.
여기서 상기 양극성 화합물은, 수명개선층 이외에, 전자수송층, 전자주입층 또는 이들 모두의 재료로서 사용될 수 있다. Herein, the bipolar compound may be used as a material of an electron transport layer, an electron injection layer, or both, in addition to the life improvement layer.
이하, 도 1을 참조하여 설명하면 다음과 같다. Hereinafter, description will be given with reference to FIG. 1.
본 발명에 따른 유기 전계 발광 소자에 있어서, 양극(100)은 정공을 유기물층(300)으로 주입하는 역할을 한다. In the organic electroluminescent device according to the present invention, the anode 100 serves to inject holes into the organic material layer 300.
상기 양극(100)을 이루는 물질은 특별히 한정되지 않으며, 당 업계에 알려진 통상적인 것을 사용할 수 있다. 이의 비제한적인 예로는, 바나듐, 크롬, 구리, 아연, 금 등의 금속; 이들의 합금; 아연 산화물, 인듐 산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO) 등의 금속 산화물; ZnO:Al, SnO2:Sb 등의 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤, 폴리아닐린 등의 전도성 고분자; 및 카본블랙 등이 있다. The material constituting the positive electrode 100 is not particularly limited, and conventional materials known in the art may be used. Non-limiting examples thereof include metals such as vanadium, chromium, copper, zinc and gold; Alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al and SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; And carbon black.
상기 양극(100)을 제조하는 방법도 특별히 한정되지 않으며, 당 업계에 알려진 통상적인 방법에 따라 제조될 수 있다. 일례로, 실리콘 웨이퍼, 석영, 유리판, 금속판 또는 플라스틱 필름으로 이루어진 기판 상에 양극 물질을 코팅하는 방법을 들 수 있다.The method of manufacturing the positive electrode 100 is not particularly limited, and may be prepared according to conventional methods known in the art. As an example, a method of coating an anode material on a substrate made of a silicon wafer, quartz, glass plate, metal plate or plastic film may be mentioned.
본 발명에 따른 유기 전계 발광 소자에 있어서, 음극(200)은 전자를 유기물층(300)으로 주입하는 역할을 한다. In the organic electroluminescent device according to the present invention, the cathode 200 serves to inject electrons into the organic material layer 300.
상기 음극(200)을 이루는 물질은 특별히 한정되지 않으며, 당 업계에 알려진 통상적인 것을 사용할 수 있다. 이의 비제한적인 예로, 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 납 등의 금속; 이들의 합금; 및 LiF/Al, LiO2/Al 등의 다층 구조 물질을 들 수 있다. The material constituting the cathode 200 is not particularly limited, and conventional materials known in the art may be used. Non-limiting examples thereof include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead; Alloys thereof; And multilayer structure materials such as LiF / Al and LiO 2 / Al.
또한 상기 음극(200)을 제조하는 방법 역시 특별히 한정되지 않으며, 당 업계에 공지된 방법에 따라 제조될 수 있다.In addition, the method of manufacturing the cathode 200 is also not particularly limited, and may be manufactured according to methods known in the art.
본 발명에 따른 유기 전계 발광 소자에 포함되는 유기물층(300)은 기존 유기 전계 발광 소자의 유기물층으로 사용되는 것을 제한 없이 사용할 수 있으며, 일례로 정공주입층(301), 정공수송층(302), 발광층(303), 수명개선층(304), 전자수송층(305) 및 전자주입층(306)으로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있다. 이때 유기 전계 발광 소자의 특성을 고려할 때, 전술한 유기물층들을 모두 포함하는 것이 바람직하다.The organic material layer 300 included in the organic electroluminescent device according to the present invention can be used as an organic material layer of the existing organic electroluminescent device without limitation, for example, a hole injection layer 301, a hole transport layer 302, a light emitting layer ( 303), the life improvement layer 304, the electron transport layer 305 and the electron injection layer 306 may include one or more selected from the group. At this time, in consideration of the characteristics of the organic EL device, it is preferable to include all the above-mentioned organic material layers.
본 발명의 유기물층(300)에 포함되는 정공주입층(301)과 정공수송층(302)은 양극(100)에서 주입된 정공을 발광층(303)으로 이동시키는 역할을 한다. 이러한 정공주입층(301)과 정공수송층(302)을 이루는 물질은 정공 주입 장벽이 낮고 정공 이동도가 큰 물질이라면 특별히 한정되지 않으며, 당 업계에 사용되는 정공주입층/수송층 물질을 제한없이 사용할 수 있다. 이의 비제한적인 예로는, 아릴아민 유도체를 들 수 있다.The hole injection layer 301 and the hole transport layer 302 included in the organic material layer 300 of the present invention serve to move the holes injected from the anode 100 to the light emitting layer 303. The material forming the hole injection layer 301 and the hole transport layer 302 is not particularly limited as long as the hole injection barrier is low and the hole mobility is high, and the hole injection layer / transport layer material used in the art can be used without limitation. have. Non-limiting examples thereof include arylamine derivatives.
또한, 본 발명의 유기물층(300)에 포함되는 발광층(303)은 정공과 전자가 만나 엑시톤(exciton)이 형성되는 층으로, 발광층(303)을 이루는 물질에 따라 유기 전계 발광 소자가 내는 빛의 색이 달라질 수 있다. 이러한 발광층(303)은 호스트와 도펀트를 포함할 수 있는데, 상기 호스트를 70 내지 99.9 중량% 범위로 포함하고, 상기 도펀트를 0.1 내지 30 중량% 범위로 포함하는 것이 바람직하다.In addition, the light emitting layer 303 included in the organic material layer 300 of the present invention is a layer in which holes and electrons meet to form an exciton, and the color of light emitted from the organic EL device according to the material forming the light emitting layer 303. This may vary. The light emitting layer 303 may include a host and a dopant, and the host may be included in the range of 70 to 99.9 wt%, and the dopant may be included in the range of 0.1 to 30 wt%.
보다 구체적으로, 상기 발광층(303)이 청색 형광, 녹색 형광 또는 적색 형광일 경우, 상기 호스트를 80 내지 99.9 중량% 범위로 포함하고, 상기 도펀트를 0.1 내지 20 중량% 범위로 포함할 수 있다. 또한 상기 발광층(303)이 청색 형광, 녹색 형광 또는 적색 인광일 경우 상기 호스트를 70 내지 99 중량% 범위로 포함하고 상기 도펀트를 1 내지 30 중량% 범위로 포함할 수 있다.More specifically, when the light emitting layer 303 is blue fluorescence, green fluorescence or red fluorescence, the host may be included in the range of 80 to 99.9% by weight and the dopant in the range of 0.1 to 20% by weight. In addition, when the emission layer 303 is blue fluorescence, green fluorescence or red phosphorescence, the host may be included in the range of 70 to 99 wt% and the dopant in the range of 1 to 30 wt%.
상기 발광층(303)에 포함되는 호스트는 당 업계에 공지된 것이라면 특별히 한정되지 않으며, 이의 비제한적인 예로는, 알칼리 금속 착화합물; 알칼리토금속 착화합물; 또는 축합 방향족환 유도체 등이 있다. The host included in the light emitting layer 303 is not particularly limited as long as it is known in the art, and non-limiting examples thereof include alkali metal complex compounds; Alkaline earth metal complexes; Or condensed aromatic ring derivatives.
보다 구체적으로, 상기 호스트 재료로는 유기 전계 발광 소자의 발광효율 및 수명을 높일 수 있는 알루미늄 착화합물, 베릴륨 착화합물, 안트라센 유도체, 파이렌 유도체, 트리페닐렌 유도체, 카바졸 유도체, 디벤조퓨란 유도체, 디벤조싸이오펜 유도체, 또는 이들의 1종 이상의 조합을 사용하는 것이 바람직하다.More specifically, the host material may be an aluminum complex, a beryllium complex, anthracene derivative, pyrene derivative, triphenylene derivative, carbazole derivative, dibenzofuran derivative, di Preference is given to using benzothiophene derivatives or one or more combinations thereof.
또한 상기 발광층(303)에 포함되는 도펀트는 당업계에 공지된 것이라면 특별히 한정되지 않으며, 이의 비제한적인 예로는, 안트라센 유도체, 파이렌 유도체, 아릴아민 유도체, 이리듐(Ir) 또는 백금(Pt)을 포함하는 금속 착체 화합물 등을 들 수 있다.In addition, the dopant included in the emission layer 303 is not particularly limited as long as it is known in the art, and non-limiting examples thereof include anthracene derivative, pyrene derivative, arylamine derivative, iridium (Ir) or platinum (Pt). The metal complex compound etc. which are included are mentioned.
이러한 발광층(303)은 단일층이거나, 또는 2층 이상의 복수층으로 이루어질 수 있다. 여기서 발광층(303)이 복수의 층일 경우 유기 전계 발광 소자는 다양한 색의 빛을 낼 수 있다. 구체적으로, 본 발명은 정공수송층(302)과 수명개선층(304) 사이에 복수의 단일 재료로 이루어진 발광층을 구비하거나, 또는 이종 재료로 이루어진 발광층을 직렬로 구비하여 혼합색을 띠는 유기 전계 발광 소자를 제공할 수 있다. 또한 복수의 발광층을 포함할 경우 소자의 구동전압은 커지는 반면, 유기 전계 발광 소자 내의 전류 값은 일정하게 되어 발광층의 수만큼 발광 효율이 향상된 유기 전계 발광 소자를 제공할 수 있다.The light emitting layer 303 may be a single layer or two or more layers. When the light emitting layer 303 is a plurality of layers, the organic light emitting diode may emit light of various colors. Specifically, the present invention includes a light emitting layer made of a plurality of single materials between the hole transport layer 302 and the life improvement layer 304, or an organic electroluminescent device having a mixed color by having a light emitting layer made of different materials in series. Can be provided. In addition, when the plurality of light emitting layers is included, the driving voltage of the device is increased, but the current value in the organic light emitting device is constant, thereby providing an organic EL device having improved light emission efficiency by the number of light emitting layers.
본 발명의 유기물층(300)에 포함되는 수명개선층(304)은 유기 전계 발광 소자의 수명을 향상시키기 위한 것으로, 발광층(303)과 전자수송층(305) 사이에 구비된다.The lifespan improvement layer 304 included in the organic material layer 300 of the present invention is to improve the lifespan of the organic EL device and is provided between the light emitting layer 303 and the electron transport layer 305.
이러한 수명개선층(304)을 이루는 물질은 특별히 한정되지 않으나, 전자 흡수성이 큰 전자끌게기(EWG)와 전자 공여성이 큰 전자주게기(EDG)를 모두 가지는 양극성(bipolar) 화합물인 것이 바람직하다.The material constituting the life improvement layer 304 is not particularly limited, but is preferably a bipolar compound having both an electron attractor (EWG) having high electron absorption and an electron donor (EDG) having a large electron donor. .
보다 구체적으로, 상기 양극성 화합물은 이온화 포텐셜(ionization potenitial)이 5.5eV 이상이며, 구체적으로, 5.5 내지 7.0eV 범위일 수 있으며, 바람직하게는 5.5 내지 6.5eV 범위일 수 있다. More specifically, the bipolar compound has an ionization potential of 5.5 eV or more, specifically, may be in the range of 5.5 to 7.0 eV, preferably in the range of 5.5 to 6.5 eV.
또한 상기 양극성 화합물의 HOMO값과 LUMO값의 차이(EHOMO-ELUMO)는 2.9eV를 초과하며, 구체적으로 2.9eV 초과, 3.5eV 이하 범위일 수 있다. In addition, the difference between the HOMO value and the LUMO value (E HOMO -E LUMO ) of the bipolar compound may be greater than 2.9 eV, specifically, greater than 2.9 eV and less than 3.5 eV.
이때 삼중항 에너지는 2.3eV 이상, 구체적으로, 2.3 내지 3.5eV 범위일 수 있으며, 바람직하게는 2.3 내지 3.0eV 범위이다. 아울러, 상기 양극성 화합물의 일중항 에너지와 삼중항 에너지 차이(ΔEst)가 0.5eV 미만이며, 구체적으로 0.5eV 미만, 0.01eV 이상 범위인 화합물이다. In this case, the triplet energy may be 2.3 eV or more, specifically, 2.3 to 3.5 eV, and preferably 2.3 to 3.0 eV. In addition, the singlet energy and triplet energy difference ΔEst of the bipolar compound is less than 0.5 eV, specifically, the compound is less than 0.5 eV, 0.01 eV or more range.
즉, 정공은 유기 전계 발광 소자 내에서 이온화 포텐셜 레벨을 타고 이동하게 되는데, 정공이 발광층(303)을 넘어 전자수송층(305)으로 확산하거나 또는 이동할 경우 산화에 의한 비가역적 분해반응이 일어나 유기 전계 발광 소자의 수명이 떨어지게 된다.That is, the holes move in the organic electroluminescent device at the ionization potential level. When the holes diffuse or move to the electron transport layer 305 beyond the light emitting layer 303, an irreversible decomposition reaction by oxidation occurs, which causes organic electroluminescence. The lifetime of the device is reduced.
이에 비해, 본 발명에서는 이온화 포텐셜[Ip(LEL)] 5.5eV 이상인 양극성 화합물로 이루어진 수명개선층(304)을 구비함으로써, 정공이 전자수송층(305)으로 확산하거나 또는 이동하는 것이 방지되기 때문에 유기 전계 발광 소자의 수명을 개선할 수 있다. 즉, 정공은 수명개선층(304)의 높은 에너지 장벽에 막혀 전자수송층(305)으로 확산 또는 이동하지 못하고 발광층(303)에 머무르게 된다.In contrast, in the present invention, since the life improvement layer 304 made of a bipolar compound having an ionization potential [Ip (LEL)] of 5.5 eV or more is provided, the hole is prevented from diffusing or moving to the electron transport layer 305, and thus the organic electric field. The life of the light emitting device can be improved. That is, the holes are blocked by the high energy barrier of the life improvement layer 304, and thus do not diffuse or move to the electron transport layer 305, but remain in the light emitting layer 303.
여기서, 발광층(303)이 적색 인광 물질로 이루어질 경우, 상기 수명개선층(304)에 포함되는 양극성 화합물의 이온화 포텐셜은 5.5eV 이상이기만 하면 무방하나, 상기 발광층(303)이 녹색 인광 물질 또는 청색 인광 물질로 이루어질 경우에는 양극성 화합물의 이온화 포텐셜이 6.0eV 이상인 것이 바람직하다.Here, when the light emitting layer 303 is made of a red phosphorescent material, the ionization potential of the bipolar compound included in the life improvement layer 304 may be just 5.5 eV or more, but the light emitting layer 303 may be a green phosphor or a blue phosphorescent light. In the case of the material, the ionization potential of the bipolar compound is preferably 6.0 eV or more.
한편 상기 양극성 화합물은 HOMO값과 LUMO값의 차이(EHOMO-ELUMO)가 2.9eV를 초과하고, 삼중항 에너지가 2.3eV 이상이며, 일중항 에너지와 삼중항 에너지 차이(ΔEst)가 0.5eV 미만이기 때문에, 이를 수명개선층(304)에 사용할 경우 발광층(303)에서 형성된 엑시톤이 전자수송층(305)으로 확산되는 것을 방지하고, 발광층(303)과 전자수송층(305)의 계면에서 발광이 일어나는 현상도 저지할 수 있다. 이는 결과적으로 유기 전계 발광 소자의 스펙트럼 혼색을 방지하며 안정성을 향상시켜 유기 전계 발광 소자의 수명을 향상시킬 수 있다.Meanwhile, the bipolar compound has a difference between HOMO and LUMO (E HOMO -E LUMO ) of more than 2.9 eV, triplet energy of 2.3 eV or more, singlet energy and triplet energy difference (ΔEst) of less than 0.5 eV. Therefore, when it is used for the life improvement layer 304, the exciton formed in the light emitting layer 303 is prevented from diffusing into the electron transporting layer 305, and light emission occurs at the interface between the light emitting layer 303 and the electron transporting layer 305. You can also stop. As a result, it is possible to prevent spectral mixing of the organic EL device and to improve stability, thereby improving the life of the organic EL device.
보다 구체적으로, 상기 양극성 화합물은 전자 흡수성이 큰 전자끌게기(EWG)와 전자 공여성이 큰 전자주게기(EDG)를 모두 가져 HOMO와 LUMO의 전자 구름이 분리되는 특징을 가진다. 이로 인해, 화합물의 삼중항 에너지와 일중항 에너지의 차이(ΔEst)가 적어 ΔEst < 0.5eV의 관계식을 만족하므로, HOMO값과 LUMO값의 차이(EHOMO-ELUMO)가 2.9eV를 초과하더라도 높은 삼중항 에너지(T1)를 가질 수 있다.More specifically, the bipolar compound has both the electron attracting force (EWG) and the electron donor (EDG) with the high electron donor (EDG) has a characteristic that the electron cloud of HOMO and LUMO is separated. As a result, the difference between the triplet energy and the singlet energy of the compound (ΔEst) is small, which satisfies the relationship of ΔEst <0.5 eV, and thus the difference between the HOMO value and the LUMO value (E HOMO -E LUMO ) is higher than 2.9 eV. It may have a triplet energy (T1).
여기서 발광층(303)이 적색 인광 물질로 이루어질 경우 상기 수명개선층(304)에 포함되는 양극성 화합물의 삼중항 에너지는 2.3eV 이상이기만 하면 무방하나, 상기 발광층(303)이 녹색 인광 물질로 이루어질 경우에는 2.5eV 이상, 또한 청색 인광 물질로 이루어질 경우에는 2.7eV 이상인 것이 바람직하다.When the light emitting layer 303 is made of a red phosphorescent material, the triplet energy of the bipolar compound included in the lifespan improvement layer 304 may be 2.3 eV or more, but when the light emitting layer 303 is made of green phosphorescent material, In the case of 2.5 eV or more and a blue phosphor, it is preferably 2.7 eV or more.
한편, 양극(100)에서 주입된 정공의 수와 음극(200)에서 주입된 전자의 수의 차이로 인해 전자와 정공의 균형이 맞지 않으면 재결합에 의해 엑시톤을 형성하지 못한 전자 또는 정공은 발광층(303)에 쌓이게 된다. 상기 발광층(303)에 쌓인 전자 또는 정공은 발광층(303)에서 산화와 환원이 원활히 일어나지 못하게 하거나, 또는 인접하는 층에 영향을 끼쳐 유기 전계 발광 소자의 수명을 감소시키게 된다.On the other hand, if the balance between electrons and holes is not corrected due to the difference between the number of holes injected from the anode 100 and the number of electrons injected from the cathode 200, the electrons or holes that do not form excitons by recombination may be light emitting layers 303. Stacked). Electrons or holes accumulated in the light emitting layer 303 may prevent oxidation and reduction from occurring smoothly in the light emitting layer 303 or may affect adjacent layers to reduce the lifespan of the organic EL device.
이에 비해, 상기 양극성 화합물은 정공 이동도 및 전자 이동도가 상온에서 1×10-6cm2/V·s 이상임에 따라, 이를 수명개선층(304)에 사용할 경우 양극(100)으로부터 주입된 정공의 수에 비해 전자의 주입이 늦어지는 것을 방지하여 유기 전계 발광 소자의 수명을 향상시킬 수 있다.In contrast, since the bipolar compound has a hole mobility and an electron mobility of 1 × 10 −6 cm 2 / V · s or more at room temperature, when used in the life improvement layer 304, holes injected from the anode 100 are used. The life of the organic EL device can be improved by preventing the injection of electrons to be delayed compared to the number of.
실제로 본 발명의 수명개선층(304)에 포함되는 양극성 화합물은 전자주게기(EDG)에 의해 정공의 이동도가 상온에서 1×10-6cm2/V·s 이상을 나타내고, 전자끌게기(EWG)에 의해 전자 이동도가 상온에서 1×10-6cm2/V·s 이상을 나타내게 된다. 따라서 이를 수명개선층(304)에 사용할 경우, 발광층(303)으로 전자를 효과적으로 주입시킬 수 있다. 이와 같이 발광층(303)으로의 전자 주입이 원활할 경우 발광층(303)에서 엑시톤의 형성효율이 높아져 유기 전계 발광 소자의 수명을 개선할 수 있다.In fact, the bipolar compound included in the life improvement layer 304 of the present invention exhibits hole mobility of 1 × 10 −6 cm 2 / V · s or more at room temperature by an electron donor (EDG), EWG) results in electron mobility of 1 × 10 −6 cm 2 / V · s or more at room temperature. Therefore, when it is used for the lifespan improvement layer 304, electrons can be effectively injected into the light emitting layer 303. As such, when the electron injection into the light emitting layer 303 is smooth, the formation efficiency of the exciton in the light emitting layer 303 may be improved, thereby improving the life of the organic EL device.
본 발명의 수명개선층(304)에 포함되는 양극성(bipolar) 화합물은 전자 흡수성이 큰 전자끌게기(EWG) 특성을 가지는 모이어티와 전자 공여성이 큰 전자주게기(EDG) 특성을 가지는 모이어티가 결합하여 형성된다. 이때 상기 전자끌게기(EWG)로서 하기 화학식으로 표시되는 전자끌게기(EWG) 모이어티를 1개 이상 포함하는 것을 특징으로 한다.The bipolar compound included in the life improvement layer 304 of the present invention has a moiety having an electron attracting (EWG) characteristic with high electron absorption and a moiety having a large electron donor (EDG) characteristic with an electron donor. Is formed by combining. In this case, the electron drawer (EWG) is characterized in that it comprises one or more electron drawer (EWG) moiety represented by the following formula.
Figure PCTKR2014012888-appb-I000001
Figure PCTKR2014012888-appb-I000001
상기 식에서,Where
A1 내지 A11은 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R)이고, 적어도 1개는 N이며, 이때 복수의 R은 동일하게 표시되더라도 각각 동일하거나 상이하고, 이들은 인접한 기와 축합 고리를 형성할 수 있다. 예컨대 C(R)인 복수일 경우, A1과 A2, A2와 A3, A3와 A4, A4와 A5, A5와 A6, 또는 A6와 A1은 각각 서로 결합하여 축합고리를 형성할 수 있으며, A7과 A8, A8과 A9, A9와 A10, A10과 A11, A11과 A7은 각각 서로 결합하여 축합고리를 형성할 수 있다. A 1 to A 11 are the same as or different from each other, each independently N or C (R), and at least one is N, wherein a plurality of R's are the same or different, respectively, even if the same are indicated, and they are condensed with adjacent groups May form a ring. For example, in the case of plural C (R), A 1 and A 2 , A 2 and A 3 , A 3 and A 4 , A 4 and A 5 , A 5 and A 6 , or A 6 and A 1 are bonded to each other Condensed ring can be formed, and A 7 and A 8 , A 8 and A 9 , A 9 and A 10 , A 10 and A 11 , A 11 and A 7 can be combined with each other to form a condensed ring. .
상기 R은 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R is hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 Cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , C 6 to C 60 Aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C 1 to C 40 alkyl boron group, C 6 to C 60 aryl boron group, C 1 to C 40 A phosphine group, a C 1 to C 40 phosphine oxide group and a C 6 to C 60 arylamine group,
상기 R의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.Alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, force of the above R The pin group, the phosphine oxide group and the arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear atoms, 3 to 40 heterocycloalkyl group, C 6 ~ C 40 aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, a C 1 ~ C 40 alkyl Oxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ by at least one member selected from the group consisting of an aryl amine of the C 60 substituted or unsubstituted of .
상기 전자끌게기(EWG) 모이어티는 1 내지 3개의 탄소가 질소로 치환된 핵원자수 5 또는 6의 함질소 헤테로방향족 탄화수소이다. 또한, 상기 전자끌게기(EWG)모이어티는 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태, 또는 아릴기와 축합된 형태일 수 있다. The electron attracting (EWG) moiety is a nitrogen-containing heteroaromatic hydrocarbon having 5 or 6 nuclear atoms in which 1-3 carbons are substituted with nitrogen. In addition, the EWG moiety may have a form in which two or more rings are simply attached to or condensed with each other, or in the form of an aryl group.
본 발명에서, 상기 전자끌게기(EWG) 모이어티는 하기 화학식으로 표시되는 구조로 보다 구체화될 수 있으며, 질소를 1 내지 3개를 포함하는 6원 함질소 헤테로방향족 탄화수소일 때가 바람직하다. 바람직한 전자끌게기(EWG) 모이어티의 비제한적인 예로는, 피리딘, 피리미딘, 트리아진, 피라진 등이 있다.In the present invention, the electron attracting moiety (EWG) moiety may be more embodied in a structure represented by the following formula, it is preferable when the six-membered nitrogen heteroaromatic hydrocarbon containing 1 to 3 nitrogen. Non-limiting examples of preferred EWG moieties include pyridine, pyrimidine, triazine, pyrazine and the like.
Figure PCTKR2014012888-appb-I000002
Figure PCTKR2014012888-appb-I000002
본 발명에서, 전자 흡수성이 큰 전자끌게기(EWG) 특성을 가지는 상기 모이어티의 탄소 또는 질소 원자는 전자 공여성이 큰 전자주게기(EDG) 특성을 가지는 모이어티와 결합을 형성한다.In the present invention, the carbon or nitrogen atom of the moiety having the electron-extracting (EWG) property having high electron absorption forms a bond with the moiety having the electron donor (EDG) property having a large electron donating property.
본 발명의 수명개선층(304)에 포함되는 양극성 화합물은 하기 화학식 1로 표시되는 전자주게기(EDG) 모이어티를 포함하는 것을 특징으로 한다.The bipolar compound included in the lifespan improvement layer 304 of the present invention is characterized by including an electron donor (EDG) moiety represented by the following Chemical Formula 1.
이와 같이 전자 공여성이 큰 전자주게기(EDG) 특성을 가지는 모이어티의 비제한적인 예로는 인돌, 카바졸, 아제핀 등의 축합 함질소 헤테로방향족환; 또는 비페닐, 트리페닐렌, 플루오란센 등의 축합 다환 방향족환이 사용될 수 있으며, 보다 구체적으로 하기 화학식 1로 나타낼 수 있다.As such, non-limiting examples of moieties having large electron donor (EDG) characteristics of electron donors include condensed nitrogen heteroaromatic rings such as indole, carbazole, and azepine; Alternatively, condensed polycyclic aromatic rings such as biphenyl, triphenylene, and fluoranthene may be used, and more specifically, may be represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
Figure PCTKR2014012888-appb-I000003
Figure PCTKR2014012888-appb-I000003
상기 화학식 1에서,In Chemical Formula 1,
X1은 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고,X 1 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),
Y1 내지 Y4는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R1)이고, 이때 복수의 R1은 동일하게 표시되더라도 각각 동일하거나 상이하고, 이들은 인접한 기와 축합 고리를 형성할 수 있고,Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), wherein a plurality of R 1 are each the same or different even if represented the same, and they may form a condensed ring with an adjacent group And
X2 및 X3는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R2)이고, 이때 복수의 R2는 동일하게 표시되더라도 각각 동일하거나 상이하고, 이들은 인접한 기와 축합 고리를 형성할 수 있고,X 2 and X 3 are the same as or different from each other, and each independently N or C (R 2 ), wherein a plurality of R 2 are the same or different, even though they are the same, and they may form condensed rings with adjacent groups And
상기 R1 내지 R2 및 Ar1 내지 Ar5는 서로 동일하거나 또는 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 1 to R 2 and Ar 1 to Ar 5 are the same as or different from each other, and each independently, hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 60 aryl group, nuclear atom 5 to 60 Heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, is selected from the group consisting of C 6 ~ C group 60 arylboronic of, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ with an aryl amine of the C 60 of,
상기 R1 내지 R2 및 Ar1 내지 Ar5의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group of R 1 to R 2 and Ar 1 to Ar 5 , Alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 Alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 hetero aryl group, C 1 ~ C 40 of the alkyloxy group, C 6 ~ C 60 of the aryloxy group, C 1 ~ C 40 alkyl silyl group, the group C 6 ~ C 60 aryl silyl, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl group of boron, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 of the phosphine oxide group, and a C 6 ~ at least one selected from the group consisting of C 60 arylamine Substituted or unsubstituted.
본 발명에서, 상기 화학식 1은 하기 A-1 내지 A-24 중 어느 하나로 보다 구체화될 수 있다. 그러나 이에 한정되는 것은 아니다.In the present invention, Chemical Formula 1 may be more embodied as any one of the following A-1 to A-24. However, it is not limited thereto.
Figure PCTKR2014012888-appb-I000004
Figure PCTKR2014012888-appb-I000004
상기 A-1 내지 A-24에서, In the above A-1 to A-24,
R2, Y1 내지 Y4 및 Ar1 내지 Ar5의 정의는 전술한 화학식 1과 동일하다. 이때 화합물의 물리적, 화학적 특성을 고려했을 때, 전자주게기(EDG) 모이어티는 A-1 내지 A-6인 것이 바람직하다.The definitions of R 2 , Y 1 to Y 4, and Ar 1 to Ar 5 are the same as those of Formula 1 described above. In consideration of the physical and chemical properties of the compound, the electron donor (EDG) moiety is preferably A-1 to A-6.
한편 본 발명에서 전자주게기(EDG) 모이어티인 상기 화학식 1은, 화학식 1의 구조로 단독으로 사용되거나, 또는 하기 화학식 2 또는 화학식 3과 결합하여 축합된 구조로 나타낼 수 있다. On the other hand, in the present invention, Formula 1, which is an electron donor (EDG) moiety, may be used alone or as a condensed structure in combination with Formula 2 or Formula 3 below.
보다 구체적으로, 화학식 1에서 Y1 내지 Y4는 각각 독립적으로 N 또는 C(R1)이되, 이들이 복수의 C(R1)인 경우, Y1과 Y2, Y2와 Y3 또는 Y3와 Y4 중 하나는 하기 화학식 2와 축합 고리를 형성한다. 이때 복수의 R1은 각각 동일하거나 상이할 수 있다. More specifically, in Formula 1, Y 1 to Y 4 are each independently N or C (R 1 ), and when they are a plurality of C (R 1 ), Y 1 and Y 2 , Y 2 and Y 3 or Y 3 And one of Y 4 forms a condensed ring with Formula 2 below. In this case, a plurality of R 1 may be the same or different, respectively.
또한, 상기 화학식 1에서 X2 및 X3가 모두 C(R2)인 경우, 이때 복수의 R2는 하기 화학식 2 또는 화학식 3과 각각 결합하여 축합 고리를 형성할 수 있다.In addition, when both X 2 And X 3 In Formula 1 is C (R 2 ), a plurality of R 2 may be combined with Formula 2 or Formula 3, respectively, to form a condensed ring.
[화학식 2][Formula 2]
Figure PCTKR2014012888-appb-I000005
Figure PCTKR2014012888-appb-I000005
[화학식 3][Formula 3]
Figure PCTKR2014012888-appb-I000006
Figure PCTKR2014012888-appb-I000006
상기 화학식 2 및 화학식 3에서,In Chemical Formulas 2 and 3,
Y5 내지 Y14는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R3)이고, 이때 C(R3)가 복수인 경우 복수의 R3는 각각 동일하거나 상이하고, 상기 화학식 1과 결합하여 축합 고리를 형성할 수 있고, Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), wherein when a plurality of C (R 3 ) is a plurality of R 3 are the same or different, respectively, and are bonded to the formula (1) To form a condensed ring,
X4는 X1과 동일하고, 이때 복수의 Ar1 내지 Ar5은 각각 동일하거나 상이하다. X 4 is the same as X 1 , wherein a plurality of Ar 1 to Ar 5 are the same or different, respectively.
축합 환을 비(非)형성하는 복수의 R3는 동일하게 표시되더라도 서로 동일하거나 또는 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 구성된 군에서 선택되고,A plurality of R 3 non-forming a condensed ring may be the same or different from each other even if they are the same, and each independently represent hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, a C 1 to C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 of the alkynyl group, C 3 ~ C 40 cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, a nuclear Heteroaryl group of 5 to 60 atoms, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ alkyl boron C 40 group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine configured groups oxide groups and C 6 ~ arylamine of the C 60 of the Selected from the military,
상기 R3의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.Alkyl group of the R 3, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, The phosphine group, the phosphine oxide group and the arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 1 to C 40 Alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ substituted by one or more selected from the group consisting of C 60 aryl amine, or unsubstituted of The.
본 발명에서 상기 화학식 1과 화학식 2가 축합하여 형성된 화합물은, 하기 화학식 1a 내지 1f로 표시되는 화합물 중 어느 하나로 보다 구체화될 수 있다.In the present invention, the compound formed by condensation of Chemical Formula 1 and Chemical Formula 2 may be embodied in any one of the compounds represented by the following Chemical Formulas 1a to 1f.
[화학식 1a][Formula 1a]
Figure PCTKR2014012888-appb-I000007
Figure PCTKR2014012888-appb-I000007
[화학식 1b][Formula 1b]
Figure PCTKR2014012888-appb-I000008
Figure PCTKR2014012888-appb-I000008
[화학식 1c][Formula 1c]
Figure PCTKR2014012888-appb-I000009
Figure PCTKR2014012888-appb-I000009
[화학식 1d][Formula 1d]
Figure PCTKR2014012888-appb-I000010
Figure PCTKR2014012888-appb-I000010
[화학식 1e][Formula 1e]
Figure PCTKR2014012888-appb-I000011
Figure PCTKR2014012888-appb-I000011
[화학식 1f][Formula 1f]
Figure PCTKR2014012888-appb-I000012
Figure PCTKR2014012888-appb-I000012
상기 화학식 1a 내지 1f에서, In Chemical Formulas 1a to 1f,
X1 내지 X4 및 Y1 내지 Y8 은 화학식 1 및 화학식 2에서 정의한 바와 같다.X 1 to X 4 and Y 1 to Y 8 are as defined in the formula (1) and (2).
본 발명의 바람직한 일례에 따르면, 축합 고리를 비(非)형성하는 Y1 내지 Y4는 N 또는 C(R1)이고, 모두 C(R1)일 때 바람직하며, Y5 내지 Y8은 N 또는 C(R3)이고, 모두 C(R3)일 때 바람직하다. 이때 복수의 R1 및 R3는 각각 동일하거나 상이하다.According to a preferred embodiment of the present invention, Y 1 to Y 4 which form a condensed ring are N or C (R 1 ), all of which are preferred when C (R 1 ), and Y 5 to Y 8 are N Or C (R 3 ), all of which are C (R 3 ). In this case, a plurality of R 1 and R 3 are the same or different, respectively.
상기 화학식 1과 화학식 2가 축합된 본 발명의 화합물은 하기 화학식 B-1 내지 B-30 중 어느 하나로 구체화될 수 있다. 그러나, 이에 한정되는 것은 아니다.Compounds of the present invention in which Formula 1 and Formula 2 are condensed may be embodied as any one of the following Formulas B-1 to B-30. However, it is not limited to this.
Figure PCTKR2014012888-appb-I000013
Figure PCTKR2014012888-appb-I000013
상기 화학식 B-1 내지 B-30에서, In Chemical Formulas B-1 to B-30,
Ar1 및 R1 내지 R3는 화학식 1 및 화학식 2에서 정의한 것과 동일하다. Ar 1 and R 1 to R 3 are the same as defined in the formula (1) and (2).
보다 구체적으로, Ar1은 치환 또는 비치환된 C6~C40의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기이며,More specifically, Ar 1 is a substituted or unsubstituted C 6 ~ C 40 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 40 nuclear atoms,
R1 내지 R3은 각각 독립적으로 수소, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C40의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기인 경우가 바람직하다. R 1 to R 3 are each independently hydrogen, a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, or a substituted or unsubstituted nuclear atom 5 to 40 It is preferable when it is a heteroaryl group of.
여기서, 상기 화학식 1 및 화학식 2가 축합된 구조를 가지는 상기 화학식 B-1 내지 B-30은 1개 이상의 축합된 인돌 혹은 축합된 카바졸 모이어티를 포함한다. Here, Formulas B-1 to B-30 having a condensed structure of Formulas 1 and 2 include one or more condensed indole or condensed carbazole moieties.
또한, 본 발명에서 화학식 1과 화학식 3이 축합하여 형성된 화합물은 하기 화학식 1g 내지 1n으로 표시되는 화합물 중 어느 하나로 구체화될 수 있다.In addition, in the present invention, the compound formed by condensation of Formula 1 and Formula 3 may be embodied as any one of the compounds represented by the following Formulas 1g to 1n.
[화학식 1g][Formula 1g]
Figure PCTKR2014012888-appb-I000014
Figure PCTKR2014012888-appb-I000014
[화학식 1h][Formula 1h]
Figure PCTKR2014012888-appb-I000015
Figure PCTKR2014012888-appb-I000015
[화학식 1i]Formula 1i]
Figure PCTKR2014012888-appb-I000016
Figure PCTKR2014012888-appb-I000016
[화학식 1j][Formula 1j]
Figure PCTKR2014012888-appb-I000017
Figure PCTKR2014012888-appb-I000017
[화학식 1k][Formula 1k]
Figure PCTKR2014012888-appb-I000018
Figure PCTKR2014012888-appb-I000018
[화학식 1l][Formula 1l]
Figure PCTKR2014012888-appb-I000019
Figure PCTKR2014012888-appb-I000019
[화학식 1m][Formula 1m]
Figure PCTKR2014012888-appb-I000020
Figure PCTKR2014012888-appb-I000020
[화학식 1n][Formula 1n]
Figure PCTKR2014012888-appb-I000021
Figure PCTKR2014012888-appb-I000021
상기 화학식 1g 내지 1n에서, In Formula 1g to 1n,
X1, X3 내지 X4 및 Y1 내지 Y14는 화학식 1 및 화학식 3에서 정의한 바와 같다.X 1 , X 3 to X 4 and Y 1 to Y 14 are the same as defined in Formula 1 and Formula 3.
보다 구체적으로, X1 및 X4는 서로 동일하거나 상이하며, 각각 독립적으로 O, S 또는 N(Ar1)인 것이 바람직하며, 모두 N(Ar1)인 것이 더욱 바람직하다. 이때 복수의 Ar1은 동일하거나 상이하다.More specifically, X 1 and X 4 are the same as or different from each other, preferably each independently O, S or N (Ar 1 ), more preferably all N (Ar 1 ). At this time, a plurality of Ar 1 is the same or different.
Y1 내지 Y4는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R1)이고, 모두 C(R1)인 것이 바람직하다. 이때 복수의 R1은 동일하거나 상이하다.Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), preferably all of C (R 1 ). In this case, a plurality of R 1 are the same or different.
X3는 각각 독립적으로, N 또는 C(R2)이며, X 3 are each independently N or C (R 2 ),
Y5 내지 Y14는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R3)이고, 모두 C(R3)인 것이 바람직하다. 이때 복수의 R3은 동일하거나 상이하다. Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), preferably all of C (R 3 ). In this case, a plurality of R 3 are the same or different.
여기서, Ar1 및 R1 내지 R3는 화학식 1 및 화학식 3에서 정의한 바와 같다.Here, Ar 1 and R 1 to R 3 are as defined in the formula (1) and (3).
본 발명의 일례에 따르면, 상기 화학식 1a 내지 화학식 1n에서, X1 및 X4는 각각 독립적으로, N(Ar1) 또는 S인 것이 바람직하다. 즉, X1이 N(Ar1)이고 X4가 S이거나, X1이 S이고 X4가 N (Ar1)이거나, 또는 X1 및 X4가 모두 N(Ar1)인 것이 바람직하다.According to one embodiment of the present invention, in Formulas 1a to 1n, X 1 and X 4 are each independently N (Ar 1 ) or S. That is, it is preferable that X 1 is N (Ar 1 ) and X 4 is S, X 1 is S and X 4 is N (Ar 1 ), or both X 1 and X 4 are N (Ar 1 ).
또한 상기 화학식 1a 내지 화학식 1n에서, Ar1은 치환 또는 비치환된 C6~C60의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기인 것이 바람직하며, Ar2 내지 Ar5는 서로 동일하거나 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기(구체적으로, 메틸기) 또는 치환 또는 비치환된 C6~C60의 아릴기(구체적으로 페닐기)인 것이 바람직하다. In addition, in Formula 1a to Formula 1n, Ar 1 is preferably a substituted or unsubstituted C 6 ~ C 60 aryl group, or a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, Ar 2 to Ar 5 is the same as or different from each other, and each independently represent a substituted or unsubstituted C 1 to C 40 alkyl group (specifically, a methyl group) or a substituted or unsubstituted C 6 to C 60 aryl group (specifically, a phenyl group) desirable.
여기서, 상기 화학식 1 및 화학식 3이 축합된 구조를 가지는 상기 화학식은 1개 이상의 축합된 아제핀 모이어티를 포함하여 전자 공여성이 큰 전자주게기(EDG)의 특성을 가지게 된다.Here, the chemical formulas having the condensed structure of Chemical Formulas 1 and 3 have the characteristics of an electron donor (EDG) having a large electron donor including one or more condensed azepine moieties.
한편 본 발명에서 수명개선층의 재료로 포함되는 양극성 화합물은, 하기 화학식 4로 표시되는 전자 공여성이 큰 전자주게기(EDG) 특성을 가지는 모이어티를 포함할 수 있다. Meanwhile, in the present invention, the bipolar compound included as a material for the lifespan improvement layer may include a moiety having an electron donor (EDG) characteristic of which the electron donor represented by the following Chemical Formula 4 is large.
[화학식 4][Formula 4]
Figure PCTKR2014012888-appb-I000022
Figure PCTKR2014012888-appb-I000022
상기 화학식 4에서,In Chemical Formula 4,
L1 내지 L3는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, C6~C60의 아릴렌기, 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고,L 1 to L 3 are the same as or different from each other, and each independently selected from the group consisting of a single bond, a C 6 to C 60 arylene group, a heteroarylene group having 5 to 60 nuclear atoms,
Ar6 내지 Ar8은 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 중수소, C6~C40의 아릴기 및 핵원자수 5 내지 40의 헤테로아릴기로 이루어진 군에서 선택되고, 단 Ar6 내지 Ar8가 모두 동일한 경우는 제외하고,Ar 6 to Ar 8 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, an aryl group having 6 to 40 carbon atoms and a heteroaryl group having 5 to 40 nuclear atoms, provided that Ar 6 to Ar Except when 8 are all the same,
R4 내지 R6은 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 4 to R 6 are the same or different, each independently, hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, an alkenyl group of C 1 ~ C 40 alkyl group, C 2 ~ C 40 of, C 2 Alkynyl group of ˜C 40 , cycloalkyl group of C 3 ˜C 40 , heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C 6 ˜C 60 , heteroaryl group of 5 to 60 nuclear atoms, C 1 ˜ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ is selected from the group consisting of C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ C 60 aryl group of an amine of,
a 내지 c는 각각 독립적으로 0 내지 3의 정수이고,a to c are each independently an integer of 0 to 3,
상기 L1 내지 L3, R4 내지 R6 및 Ar6 내지 Ar8의 아릴렌기, 헤테로아릴렌기, 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.The arylene group, heteroarylene group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyl jade of L 1 to L 3 , R 4 to R 6 and Ar 6 to Ar 8 The time period, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 Alkyl group, C 2 ~ C 40 Alkenyl group, C 2 ~ C 40 Alkynyl group, C 3 ~ C 40 Cycloalkyl group, C 3 ~ 40 Heterocycloalkyl group, C 6 ~ C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, a alkyl boronic of C 1 ~ C 40, C 6 ~ C group 60 arylboronic of, C 1 ~ C 40 of the phosphine group, C 1 ~ phosphine oxide of a C 40 group, and a C 6 ~ C 60 of Arya Substituted or unsubstituted with one or more selected from the group consisting of min groups.
보다 구체적으로, 상기 화학식 4에서, L1 내지 L3는 각각 독립적으로 단일결합, 페닐렌, 비페닐렌, 또는 카바졸릴렌인 것이 바람직하다.More specifically, in Formula 4, L One To L 3 It is preferably each independently a single bond, phenylene, biphenylene, or carbazolylene.
상기 Ar6 내지 Ar8은 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 중수소, C6~C40의 아릴기 및 핵원자수 5 내지 40의 헤테로아릴기로 이루어진 군에서 선택되고, 이때 Ar6 내지 Ar8중 적어도 하나는 N, O, S 로 이루어진 군에서 선택되는 1 이상의 원소를 포함하는 핵원자수 5 내지 40의 헤테로아릴기에서 선택되는 것이 바람직하다. 단, Ar6 내지 Ar8가 모두 동일한 경우는 제외된다.Ar 6 to Ar 8 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, an aryl group having 6 to 40 carbon atoms and a heteroaryl group having 5 to 40 nuclear atoms, wherein Ar 6 to At least one of Ar 8 is preferably selected from a heteroaryl group having 5 to 40 nuclear atoms including at least one element selected from the group consisting of N, O, and S. However, the case where Ar 6 to Ar 8 are all the same is excluded.
본 발명에서, 상기 화학식 1a 내지 화학식 1n 및 화학식 4로 표시되는 화합물에서, R1 내지 R6 및 Ar1 내지 Ar8 중 적어도 하나는 전자 흡수성이 큰 전자끌게기(EWG) 특성을 가지는 상기 모이어티와 결합을 형성한다.In the present invention, in the compounds represented by Formula 1a to Formula 1n and Formula 4, at least one of R 1 to R 6 and Ar 1 to Ar 8 is the moiety having an electron-withdrawing (EWG) property of high electron absorption Form a bond with.
본 발명에서의 알킬은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있다.Alkyl in the present invention is a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like. Can be mentioned.
본 발명에서의 알케닐(alkenyl)은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있다.Alkenyl in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include vinyl and allyl. ), Isopropenyl, 2-butenyl, and the like.
본 발명에서의 알키닐(alkynyl)은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등을 들 수 있다.Alkynyl in the present invention is a monovalent substituent derived from a C2-C40 straight or branched chain unsaturated hydrocarbon having one or more carbon-carbon triple bonds. Examples thereof include ethynyl, 2- Propanyl (2-propynyl) etc. are mentioned.
본 발명에서의 아릴은 단독 고리 또는 2이상의 고리가 조합된 탄소수 6 내지 60의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴 등을 들 수 있다.Aryl in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms combined with a single ring or two or more rings. In addition, a form in which two or more rings are attached to each other (pendant) or condensed may also be included. Examples of such aryls include phenyl, naphthyl, phenanthryl, anthryl and the like.
본 발명에서의 헤테로아릴은 핵원자수 5 내지 60의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 아릴기와 축합된 형태도 포함할 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리, 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있다.Heteroaryl in the present invention means a monovalent substituent derived from monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are pendant or condensed with each other may also be included, and may also include a form condensed with an aryl group. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolinzinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like.
본 발명에서의 아릴옥시는 RO-로 표시되는 1가의 치환기로 상기 R은 탄소수 6 내지 60의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있다.Aryloxy in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
본 발명에서의 알킬옥시는 R'O-로 표시되는 1가의 치환기로 상기 R'는 1 내지 40개의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함하는 것으로 해석한다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있다.Alkyloxy in the present invention is a monovalent substituent represented by R'O-, wherein R 'means 1 to 40 alkyl, and includes a linear, branched or cyclic structure It is interpreted as. Examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서의 아릴아민은 탄소수 6 내지 60의 아릴로 치환된 아민을 의미한다.Arylamine in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.
본 발명에서의 시클로알킬은 탄소수 3 내지 40의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 놀보닐(norbornyl), 아다만틴(adamantine) 등을 들 수 있다.Cycloalkyl in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
본 발명에서의 헤테로시클로알킬은 핵원자수 3 내지 40의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등을 들 수 있다.Heterocycloalkyl in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, O, S or Substituted with a hetero atom such as Se. Examples of such heterocycloalkyl include morpholine, piperazine and the like.
본 발명에서의 알킬실릴은 탄소수 1 내지 40의 알킬로 치환된 실릴이고, 아릴실릴은 탄소수 6 내지 40의 아릴로 치환된 실릴을 의미한다.Alkylsilyl in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 6 to 40 carbon atoms.
본 발명에서의 축합 고리는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.Condensed ring in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.
본 발명에 따른 유기 전계 발광 소자에 있어서, 상기 유기물층(300)에 포함되는 전자수송층(305)과 전자주입층(306)은 음극(200)에서 주입된 전자를 발광층(303)으로 이동시키는 역할을 한다. In the organic electroluminescent device according to the present invention, the electron transport layer 305 and the electron injection layer 306 included in the organic material layer 300 serves to move the electrons injected from the cathode 200 to the light emitting layer 303. do.
이러한 전자수송층(305)과 전자주입층(306)을 이루는 물질은 전자 주입이 용이하고 전자 이동도가 큰 물질이라면 특별히 한정되지 않으나, 이의 비제한적인 예로, 상기 양극성 화합물, 안트라센 유도체, 헤테로방향족 화합물, 알칼리 금속 착화합물 등을 들 수 있다.The material constituting the electron transport layer 305 and the electron injection layer 306 is not particularly limited as long as it is easy to inject electrons and has high electron mobility, but is not limited thereto. The bipolar compound, anthracene derivative, and heteroaromatic compound may be used. And alkali metal complex compounds.
보다 구체적으로, 본 발명의 전자수송층(305) 및/또는 전자주입층(306)은 상기 수명개선층(304)과 동일한 양극성 물질, 즉 상기 화학식 1로 표시되는 양극성 화합물로 이루어지는 것이 바람직하다. 또한 상기 전자수송층(305) 및/또는 전자주입층(306)은 음극으로부터 전자의 주입이 용이하도록 알칼리 금속 착화합물이 공증착된 것을 사용할 수도 있다. 이때, 상기 알칼리 금속 착화합물로는 알칼리 금속, 알칼리 토금속 또는 희토류 금속 등을 들 수 있다.More specifically, the electron transport layer 305 and / or the electron injection layer 306 of the present invention is preferably made of the same bipolar material, that is, the bipolar compound represented by the formula (1). In addition, the electron transport layer 305 and / or the electron injection layer 306 may be a co-deposited alkali metal complex compound to facilitate the injection of electrons from the cathode. In this case, the alkali metal complex compound may be an alkali metal, an alkaline earth metal or a rare earth metal.
상기와 같은 본 발명의 유기물층(300)은 정공수송층(302)과 발광층(303) 사이에 전자와 엑시톤을 블로킹하는 유기막층(미도시)을 더 포함할 수 있다. The organic material layer 300 of the present invention as described above may further include an organic film layer (not shown) for blocking electrons and excitons between the hole transport layer 302 and the light emitting layer 303.
이러한 유기막층은 높은 LUMO 값을 가져 전자가 정공수송층(302)으로 이동하는 것을 막고, 높은 삼중항 에너지를 가져 발광층(303)의 엑시톤이 정공수송층(302)으로 확산되는 것을 방지한다. 이와 같은 유기막층을 이루는 물질은 특별히 한정되지 않으며, 이의 비제한적인 예로 카바졸 유도체 또는 아릴아민 유도체 등을 들 수 있다.The organic layer has a high LUMO value to prevent electrons from moving to the hole transport layer 302, and has a high triplet energy to prevent the excitons of the light emitting layer 303 from diffusing into the hole transport layer 302. The material constituting such an organic film layer is not particularly limited, and examples thereof include carbazole derivatives or arylamine derivatives.
이러한 본 발명의 유기물층(300)을 제조하는 방법은 특별히 한정되지 않으나, 비제한적인 예로, 진공 증착법, 용액 도포법을 들 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 열 전사법 등을 들 수 있다.The method of manufacturing the organic material layer 300 of the present invention is not particularly limited, but non-limiting examples include a vacuum deposition method and a solution coating method. Examples of the solution coating method may be spin coating, dip coating, doctor blading, inkjet printing, thermal transfer method and the like.
이상의 본 발명의 유기 전계 발광 소자는 양극(100), 유기물층(300) 및 음극(200)이 순차적으로 적층된 구조를 가지되, 양극(100)과 유기물층(300) 사이 또는 음극(200)과 유기물층(300) 사이에 절연층 또는 접착층을 더 포함할 수도 있다. 이러한 본 발명의 유기 전계 발광 소자는 전압, 전류, 또는 이들 모두를 인가하는 경우 최대 발광효율을 유지하면서 초기 밝기의 반감시간(Life time)이 증가되기 때문에 수명 특성이 우수할 수 있다.The organic electroluminescent device of the present invention has a structure in which the anode 100, the organic material layer 300 and the cathode 200 are sequentially stacked, between the anode 100 and the organic material layer 300 or between the cathode 200 and the organic material layer The insulating layer or the adhesive layer may be further included between the 300. Such an organic electroluminescent device of the present invention may have excellent lifespan characteristics since life time of initial brightness is increased while maintaining the maximum luminous efficiency when voltage, current, or both are applied.
이하 본 발명을 실시예를 통하여 상세히 설명하나, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples are merely illustrative of the present invention, and the present invention is not limited by the following Examples.
[준비예 1 내지 36] 화합물 LE-01 내지 LE-36 준비Preparation Examples 1 to 36 Preparation of Compounds LE-01 to LE-36
본 발명의 양극성 화합물로 하기 LE-01 내지 LE-36으로 표시되는 화합물을 준비하였으며, 이들의 ΔEst, 삼중항 에너지, 이온화포텐셜, EHOMO-ELUMO, 전자이동도 및 정공이동도를 당 업계에 공지된 방법으로 각각 측정하여 하기 표 1에 나타내었다.Compounds represented by the following LE-01 to LE-36 were prepared as the bipolar compound of the present invention, and ΔEst, triplet energy, ionization potential, E HOMO- E LUMO , electron mobility, and hole mobility were prepared in the art. Each measured by a known method is shown in Table 1 below.
양극성 화합물인 LE-01 내지 LE-36을 하기에 각각 나타내었다.The bipolar compounds LE-01 to LE-36 are shown below, respectively.
Figure PCTKR2014012888-appb-I000023
Figure PCTKR2014012888-appb-I000023
Figure PCTKR2014012888-appb-I000024
Figure PCTKR2014012888-appb-I000024
표 1
계산값(B3LYP/6-31G*) 실측값
양극성 화합물 ΔEst(S1-T1) 삼중항 에너지 이온화포텐셜 EHOMO-ELUMO 전자이동도 정공이동도
LE-01 0.058 2.39 5.54 3.55 8.9X10-5 5.5X10-5
LE-02 0.168 2.45 5.50 3.47 5.8X10-5 3.3X10-5
LE-03 0.355 2.54 5.71 3.3 8.8X10-4 1.1X10-5
LE-04 0.059 2.53 5.6 3.37 7.6X10-4 1.2X10-5
LE-05 0.138 2.65 5.58 3.43 7.5X10-4 9.0X10-5
LE-06 0.177 2.50 5.64 3.07 9.6X10-4 9.9X10-5
LE-07 0.121 2.48 5.65 3.42 9.2X10-4 9.6X10-5
LE-08 0.298 2.74 6.01 3.33 5.1X10-5 5.5X10-5
LE-09 0.291 2.38 5.71 3.32 9.9X10-4 2.5X10-5
LE-10 0.321 2.35 5.69 3.31 1.0X10-5 6.5X10-5
LE-11 0.261 2.81 6.01 3.36 9.9X10-5 4.1X10-5
LE-12 0.340 2.78 6.05 3.23 1.1X10-6 5.4X10-5
LE-13 0.235 2.59 5.50 3.51 1.3X10-6 1.1X10-5
LE-14 0.265 2.51 5.51 3.41 2.1X10-6 1.6X10-5
LE-15 0.049 2.59 5.56 3.50 7.5X10-5 5.5X10-5
LE-16 0.051 2.54 5.51 3.49 8.5X10-6 4.5X10-5
LE-17 0.058 2.43 5.64 3.15 7.8X10-5 5.0X10-5
LE-18 0.074 2.50 5.68 3.24 6.5X10-4 4.2X10-5
LE-19 0.082 2.45 5.73 3.20 7.5X10-4 8.5X10-5
LE-20 0.168 2.56 5.70 3.17 5.8X10-5 3.3X10-5
LE-21 0.235 2.48 5.60 3.14 6.4X10-4 6.1X10-5
LE-22 0.129 2.57 5.70 2.93 7.0X10-4 4.2X10-5
LE-23 0.090 2.53 5.83 3.54 7.0X10-5 5.5X10-5
LE-24 0.044 2.47 5.69 3.06 6.6X10-3 9.1X10-5
LE-25 0.157 2.43 5.99 3.10 8.1X10-4 7.9X10-5
LE-26 0.054 2.39 5.82 3.23 9.5X10-3 9.4X10-5
LE-27 0.121 2.41 5.75 3.12 3.7X10-4 4.8X10-5
LE-28 0.057 2.50 6.01 3.33 5.1X10-5 5.5X10-5
LE-29 0.045 2.37 6.19 3.36 3.9X10-4 8.1X10-5
LE-30 0.244 2.45 6.09 3.35 5.6X10-4 7.5X10-5
LE-31 0.235 2.40 5.70 3.14 6.4X10-4 6.1X10-5
LE-32 0.129 2.34 5.68 2.93 7.0X10-4 4.2X10-5
LE-33 0.342 2.55 6.21 3.23 7.5X10-4 5.9X10-5
LE-34 0.295 2.47 6.15 3.06 6.6X10-3 9.1X10-5
LE-35 0.310 2.43 6.09 3.10 8.1X10-4 7.9X10-5
LE-36 0.265 2.39 6.18 3.23 9.5X10-3 9.4X10-5
정공이동도 및 전자이동도는 양극성 화합물을 1㎛ 두께로 성막하여 캐리어의 이동시간(Transit time)을 측정함
Table 1
Calculated Value (B3LYP / 6-31G *) Actual value
Bipolar compound ΔEst (S1-T1) Triplet energy Ionization potential E HOMO -E LUMO Electron mobility Hole mobility
LE-01 0.058 2.39 5.54 3.55 8.9X10 -5 5.5X10 -5
LE-02 0.168 2.45 5.50 3.47 5.8X10 -5 3.3X10 -5
LE-03 0.355 2.54 5.71 3.3 8.8X10 -4 1.1X10 -5
LE-04 0.059 2.53 5.6 3.37 7.6X10 -4 1.2X10 -5
LE-05 0.138 2.65 5.58 3.43 7.5X10 -4 9.0X10 -5
LE-06 0.177 2.50 5.64 3.07 9.6X10 -4 9.9X10 -5
LE-07 0.121 2.48 5.65 3.42 9.2X10 -4 9.6X10 -5
LE-08 0.298 2.74 6.01 3.33 5.1X10 -5 5.5X10 -5
LE-09 0.291 2.38 5.71 3.32 9.9X10 -4 2.5X10 -5
LE-10 0.321 2.35 5.69 3.31 1.0X10 -5 6.5X10 -5
LE-11 0.261 2.81 6.01 3.36 9.9X10 -5 4.1X10 -5
LE-12 0.340 2.78 6.05 3.23 1.1X10 -6 5.4X10 -5
LE-13 0.235 2.59 5.50 3.51 1.3X10 -6 1.1X10 -5
LE-14 0.265 2.51 5.51 3.41 2.1X10 -6 1.6X10 -5
LE-15 0.049 2.59 5.56 3.50 7.5X10 -5 5.5X10 -5
LE-16 0.051 2.54 5.51 3.49 8.5X10 -6 4.5X10 -5
LE-17 0.058 2.43 5.64 3.15 7.8X10 -5 5.0X10 -5
LE-18 0.074 2.50 5.68 3.24 6.5X10 -4 4.2X10 -5
LE-19 0.082 2.45 5.73 3.20 7.5X10 -4 8.5X10 -5
LE-20 0.168 2.56 5.70 3.17 5.8X10 -5 3.3X10 -5
LE-21 0.235 2.48 5.60 3.14 6.4X10 -4 6.1X10 -5
LE-22 0.129 2.57 5.70 2.93 7.0X10 -4 4.2X10 -5
LE-23 0.090 2.53 5.83 3.54 7.0X10 -5 5.5X10 -5
LE-24 0.044 2.47 5.69 3.06 6.6X10 -3 9.1X10 -5
LE-25 0.157 2.43 5.99 3.10 8.1X10 -4 7.9X10 -5
LE-26 0.054 2.39 5.82 3.23 9.5X10 -3 9.4X10 -5
LE-27 0.121 2.41 5.75 3.12 3.7X10 -4 4.8X10 -5
LE-28 0.057 2.50 6.01 3.33 5.1X10 -5 5.5X10 -5
LE-29 0.045 2.37 6.19 3.36 3.9X10 -4 8.1X10 -5
LE-30 0.244 2.45 6.09 3.35 5.6X10 -4 7.5X10 -5
LE-31 0.235 2.40 5.70 3.14 6.4X10 -4 6.1X10 -5
LE-32 0.129 2.34 5.68 2.93 7.0X10 -4 4.2X10 -5
LE-33 0.342 2.55 6.21 3.23 7.5X10 -4 5.9X10 -5
LE-34 0.295 2.47 6.15 3.06 6.6X10 -3 9.1X10 -5
LE-35 0.310 2.43 6.09 3.10 8.1X10 -4 7.9X10 -5
LE-36 0.265 2.39 6.18 3.23 9.5X10 -3 9.4X10 -5
Hole mobility and electron mobility measure the transit time of carrier by depositing bipolar compound into 1㎛ thickness.
[실시예 1 내지 36] 청색 형광 유기 전계 발광 소자의 제조Examples 1 to 36 Fabrication of Blue Fluorescent Organic Electroluminescent Devices
ITO(Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척하고 건조시킨 후, UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.The glass substrate coated with ITO (Indium tin oxide) with a thickness of 1500Å was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried, transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV The substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극(기판) 상에 정공 주입층, 정공 수송층, 발광층, 수명 개선층, 전자 수송층, 전자 주입층 및 음극을 순차적으로 증착하여 소자를 제조하였다. 제조된 소자의 구조는 하기 표 2와 같다.A device was manufactured by sequentially depositing a hole injection layer, a hole transport layer, a light emitting layer, a life improvement layer, an electron transport layer, an electron injection layer, and a cathode on an ITO transparent electrode (substrate) prepared as described above. The structure of the manufactured device is shown in Table 2 below.
표 2
화합물 두께
정공주입층 DS-205(두산社) 80nm
정공수송층 NPB 15nm
발광층 ADN + 5% DS-405 (두산社) 30nm
수명개선층 LE-01 내지 LE-36 5nm
전자수송층 Alq3 25nm
전자주입층 LiF 1nm
음극 Al 200nm
TABLE 2
compound thickness
Hole injection layer DS-205 (Doosan Corporation) 80 nm
Hole transport layer NPB 15 nm
Light emitting layer ADN + 5% DS-405 (Doosan Corporation) 30 nm
Life Improvement Layer LE-01 to LE-36 5 nm
Electron transport layer Alq 3 25 nm
Electron injection layer LiF 1nm
cathode Al
200 nm
상기 표 2에서 사용된, NPB, ADN 및 Alq3의 구조는 하기와 같다.As used in Table 2, the structure of NPB, ADN and Alq 3 is as follows.
Figure PCTKR2014012888-appb-I000025
Figure PCTKR2014012888-appb-I000025
[비교예 1] 청색 형광 유기 전계 발광 소자의 제조Comparative Example 1 Fabrication of Blue Fluorescent Organic Electroluminescent Device
수명 개선층을 사용하지 않고 전자수송층을 30㎚로 증착한 것을 제외하고는, 상기 실시예 1과 동일한 과정으로 소자를 제조하였다.A device was manufactured in the same manner as in Example 1, except that the electron transport layer was deposited at 30 nm without using the life improving layer.
[비교예 2] 청색 형광 유기 전계 발광 소자의 제조Comparative Example 2 Fabrication of Blue Fluorescent Organic Electroluminescent Device
LE-01 대신 하기 구조의 BCP를 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 과정으로 소자를 제조하였다.A device was manufactured in the same manner as in Example 1, except that BCP having the following structure instead of LE-01 was used.
Figure PCTKR2014012888-appb-I000026
Figure PCTKR2014012888-appb-I000026
[실험예 1]Experimental Example 1
상기 실시예 1 내지 36 및 비교예 1, 2에서 제조된 각각의 소자에 대하여 전류밀도 10mA/cm2에서의 구동전압, 전류효율, 발광파장 및 수명(T97)을 측정하였고, 그 결과를 하기 표 3에 나타내었다.For each device manufactured in Examples 1 to 36 and Comparative Examples 1 and 2, the driving voltage, current efficiency, light emission wavelength, and lifetime (T 97 ) at a current density of 10 mA / cm 2 were measured. Table 3 shows.
표 3
화합물 구동전압(V) 전류효율(cd/A) 발광 피크(nm) 수명(hr)
실시예 1 LE-01 4.5 5.9 458 45
실시예 2 LE-02 4.7 5.6 458 50
실시예 3 LE-03 4.5 5.9 458 75
실시예 4 LE-04 4.2 6.0 458 54
실시예 5 LE-05 4.1 5.7 458 42
실시예 6 LE-06 4.3 6.1 458 78
실시예 7 LE-07 4.2 6.0 458 75
실시예 8 LE-08 4.7 5.7 457 82
실시예 9 LE-09 4.4 6.1 458 51
실시예 10 LE-10 4.1 5.7 458 39
실시예 11 LE-11 4.9 5.4 458 103
실시예 12 LE-12 5.0 5.3 457 88
실시예 13 LE-13 5.0  5.5 458 39 
실시예 14 LE-14 4.9 5.6 458 40 
실시예 15 LE-15 4.2  6.1 458 59 
실시예 16 LE-16 4.6 5.7 458 45 
실시예 17 LE-17 4.5 6.1 458 55
실시예 18 LE-18 4.3 6.5 458 59
실시예 19 LE-19 4.4 6.4 457 60
실시예 20 LE-20 4.7 6.0 458 50
실시예 21 LE-21 4.5 6.2 458 75
실시예 22 LE-22 4.2 6.6 458 55
실시예 23 LE-23 4.1 6.6 458 92
실시예 24 LE-24 4.4 6.2 457 45
실시예 25 LE-25 4.3 6.1 458 78
실시예 26 LE-26 4.1 6.2 458 64
실시예 27 LE-27 4.2 6.0 458 75
실시예 28 LE-28 4.7 6.4 457 85
실시예 29 LE-29 4.3 6.0 458 62
실시예 30 LE-30 4.5 6.3 458 60
실시예 31 LE-31 4.6 6.2 458 55
실시예 32 LE-32 4.5 6.4 457 59
실시예 33 LE-33 4.4 6.3 458 81
실시예 34 LE-34 4.5 6.3 458 70
실시예 35 LE-35 4.5 6.3 458 83
실시예 36 LE-36 4.5 6.2 457 92
비교예 1 - 4.7 5.6 458 32
비교예 2 BCP 5.3 5.9 458 28
수명은 수명측정기를 통해 발광휘도가 97% 되는 시간을 측정함
TABLE 3
compound Driving voltage (V) Current efficiency (cd / A) Emission Peak (nm) Life (hr)
Example 1 LE-01 4.5 5.9 458 45
Example 2 LE-02 4.7 5.6 458 50
Example 3 LE-03 4.5 5.9 458 75
Example 4 LE-04 4.2 6.0 458 54
Example 5 LE-05 4.1 5.7 458 42
Example 6 LE-06 4.3 6.1 458 78
Example 7 LE-07 4.2 6.0 458 75
Example 8 LE-08 4.7 5.7 457 82
Example 9 LE-09 4.4 6.1 458 51
Example 10 LE-10 4.1 5.7 458 39
Example 11 LE-11 4.9 5.4 458 103
Example 12 LE-12 5.0 5.3 457 88
Example 13 LE-13 5.0 5.5 458 39
Example 14 LE-14 4.9 5.6 458 40
Example 15 LE-15 4.2 6.1 458 59
Example 16 LE-16 4.6 5.7 458 45
Example 17 LE-17 4.5 6.1 458 55
Example 18 LE-18 4.3 6.5 458 59
Example 19 LE-19 4.4 6.4 457 60
Example 20 LE-20 4.7 6.0 458 50
Example 21 LE-21 4.5 6.2 458 75
Example 22 LE-22 4.2 6.6 458 55
Example 23 LE-23 4.1 6.6 458 92
Example 24 LE-24 4.4 6.2 457 45
Example 25 LE-25 4.3 6.1 458 78
Example 26 LE-26 4.1 6.2 458 64
Example 27 LE-27 4.2 6.0 458 75
Example 28 LE-28 4.7 6.4 457 85
Example 29 LE-29 4.3 6.0 458 62
Example 30 LE-30 4.5 6.3 458 60
Example 31 LE-31 4.6 6.2 458 55
Example 32 LE-32 4.5 6.4 457 59
Example 33 LE-33 4.4 6.3 458 81
Example 34 LE-34 4.5 6.3 458 70
Example 35 LE-35 4.5 6.3 458 83
Example 36 LE-36 4.5 6.2 457 92
Comparative Example 1 - 4.7 5.6 458 32
Comparative Example 2 BCP 5.3 5.9 458 28
Life time measures the time when the luminance is 97%
상기 표 3을 살펴보면, 본 발명의 수명개선층을 포함하는 실시예 1 내지 12의 유기 전계 발광 소자는 비교예 1 및 2의 유기 전계 발광 소자보다 전류효율, 구동전압 및 수명이 우수하다는 것을 확인할 수 있었다.Looking at the Table 3, it can be seen that the organic EL device of Examples 1 to 12 including the life improvement layer of the present invention is superior in current efficiency, driving voltage and life than the organic EL device of Comparative Examples 1 and 2 there was.
[실시예 37 내지 51] 녹색 인광 유기 전계 발광 소자의 제조Examples 37 to 51 Fabrication of Green Phosphorescent Organic Electroluminescent Device
ITO(Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척하고 건조시킨 후 UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.The glass substrate coated with ITO (Indium tin oxide) with a thickness of 1500Å was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate for 5 minutes by UV and vacuum The substrate was transferred to the evaporator.
상기와 같이 준비된 ITO 투명 전극(기판) 상에 정공 주입층, 정공 수송층, 발광층, 수명 개선층, 전자 수송층, 전자 주입층 및 음극을 순차적으로 증착하여 소자를 제조하였다. 제조된 소자의 구조는 하기 표 4와 같다.A device was manufactured by sequentially depositing a hole injection layer, a hole transport layer, a light emitting layer, a life improvement layer, an electron transport layer, an electron injection layer, and a cathode on an ITO transparent electrode (substrate) prepared as described above. The structure of the manufactured device is shown in Table 4 below.
표 4
화합물 두께
정공주입층 m-MTDATA 60nm
정공수송층 TCTA 80nm
발광층 CBP + 10% Ir(ppy)3 30nm
수명개선층 하기 표 5 참조 5nm
전자수송층 Alq3 25nm
전자주입층 LiF 1nm
음극 Al 200nm
Table 4
compound thickness
Hole injection layer m-MTDATA 60 nm
Hole transport layer TCTA 80 nm
Light emitting layer CBP + 10% Ir (ppy) 3 30 nm
Life Improvement Layer See Table 5 below 5 nm
Electron transport layer Alq 3 25 nm
Electron injection layer LiF 1nm
cathode Al
200 nm
상기 표 4에서 사용된, m-MTDATA, TCTA, Ir(ppy)3 및 CBP의 구조는 하기와 같다.As used in Table 4, m-MTDATA, TCTA, Ir (ppy) 3 and the structure of the CBP is as follows.
Figure PCTKR2014012888-appb-I000027
Figure PCTKR2014012888-appb-I000027
[비교예 3] 녹색 인광 유기 전계 발광 소자의 제조Comparative Example 3 Fabrication of Green Phosphorescent Organic Electroluminescent Device
수명개선층을 사용하지 않고 전자수송층을 30㎚로 증착한 것을 제외하고는, 상기 실시예 37과 동일한 과정으로 소자를 제조하였다.A device was manufactured in the same manner as in Example 37, except that an electron transport layer was deposited at 30 nm without using a lifetime improving layer.
[비교예 4] 녹색 인광 유기 전계 발광 소자의 제조Comparative Example 4 Fabrication of Green Phosphorescent Organic Electroluminescent Device
LE-02 대신 상기 비교예 2에서 사용된 BCP를 사용하는 것을 제외하고는, 상기 실시예 37과 동일한 과정으로 소자를 제조하였다.A device was manufactured in the same manner as in Example 37, except for using the BCP used in Comparative Example 2 instead of LE-02.
[실험예 2]Experimental Example 2
상기 실시예 37 내지 51 및 비교예 3, 4에서 제조된 각각의 소자에 대하여 전류밀도 10mA/cm2에서의 구동전압, 전류효율, 발광파장 및 수명(T97)을 측정하였고, 그 결과를 하기 표 5에 나타내었다.For each device manufactured in Examples 37 to 51 and Comparative Examples 3 and 4, the driving voltage, current efficiency, light emission wavelength, and lifetime (T 97 ) at a current density of 10 mA / cm 2 were measured. Table 5 shows.
표 5
화합물 구동전압(V) 전류효율(cd/A) 발광피크(nm) 수명(hr, T97)
실시예 37 LE-02 7.3 37.0 516 49
실시예 38 LE-07 7.2 36.9 516 65
실시예 39 LE-08 7.4 37.0 517 85
실시예 40 LE-09 7.1 37.8 516 55
실시예 41 LE-10 7.0 35.3 515 54
실시예 42 LE-11 7.4 36.9 516 98
실시예 43 LE-12 7.3 37.1 516 103
실시예 44 LE-17 7.3 37.0 516 51
실시예 45 LE-18 7.1 38.2 516 49
실시예 46 LE-19 7.2 36.9 516 68
실시예 47 LE-22 7.4 37.0 517 59
실시예 48 LE-23 7.1 40.1 516 95
실시예 49 LE-25 7.0 35.3 515 66
실시예 50 LE-26 7.4 36.9 516 74
실시예 51 LE-28 6.8 39.8 516 103
비교예 3 - 7.2 36.8 516 45
비교예 4 BCP 7.9 40.2 516 40
수명은 수명측정기를 통해 발광 휘도가 97% 되는 시간을 측정함
Table 5
compound Driving voltage (V) Current efficiency (cd / A) Light emitting peak (nm) Life (hr, T 97 )
Example 37 LE-02 7.3 37.0 516 49
Example 38 LE-07 7.2 36.9 516 65
Example 39 LE-08 7.4 37.0 517 85
Example 40 LE-09 7.1 37.8 516 55
Example 41 LE-10 7.0 35.3 515 54
Example 42 LE-11 7.4 36.9 516 98
Example 43 LE-12 7.3 37.1 516 103
Example 44 LE-17 7.3 37.0 516 51
Example 45 LE-18 7.1 38.2 516 49
Example 46 LE-19 7.2 36.9 516 68
Example 47 LE-22 7.4 37.0 517 59
Example 48 LE-23 7.1 40.1 516 95
Example 49 LE-25 7.0 35.3 515 66
Example 50 LE-26 7.4 36.9 516 74
Example 51 LE-28 6.8 39.8 516 103
Comparative Example 3 - 7.2 36.8 516 45
Comparative Example 4 BCP 7.9 40.2 516 40
Life span measures the time when the luminance is 97%
상기 표 5를 살펴보면, 본 발명의 수명개선층을 포함하는 실시예 37 내지 51의 유기 전계 발광 소자는 비교예 3 및 4의 유기 전계 발광 소자보다 전류효율, 구동전압 및 수명이 우수하다는 것을 확인할 수 있었다.Looking at Table 5, it can be seen that the organic electroluminescent devices of Examples 37 to 51 including the life improvement layer of the present invention are superior in current efficiency, driving voltage and lifetime than the organic electroluminescent devices of Comparative Examples 3 and 4. there was.
본 발명은 특정 물성을 가지는 양극성(bipolar) 화합물로 이루어진 수명 개선층, 전자 수송층 또는 전자 주입층을 유기 전계 발광 소자에 도입함에 따라 구동전압, 발광효율 및 수명이 우수한 유기 전계 발광 소자를 제공할 수 있다. 또한 본 발명의 유기 전계 발광 소자를 디스플레이 패널에 적용함에 따라 성능 및 수명이 향상된 디스플레이 패널을 제공할 수 있다.The present invention can provide an organic EL device having excellent driving voltage, luminous efficiency and lifetime by introducing a lifetime improving layer, an electron transporting layer, or an electron injection layer formed of a bipolar compound having specific physical properties into the organic EL device. have. In addition, as the organic electroluminescent device of the present invention is applied to a display panel, a display panel having improved performance and lifespan can be provided.

Claims (20)

  1. 양극; anode;
    음극; 및 cathode; And
    상기 양극과 음극 사이에, 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군에서 선택되는 유기물층이 1층 이상 설치되어 있고, At least one organic material layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is provided between the anode and the cathode,
    상기 발광층과 전자수송층 사이에 수명개선층(Lifetime Enhancement Layer, LEL)을 더 포함하는 유기 전계 발광소자로서, An organic electroluminescent device further comprising a Lifetime Enhancement Layer (LEL) between the light emitting layer and the electron transport layer.
    상기 수명개선층은 전자흡수성이 큰 전자끌게기(EWG)와 전자공여성이 큰 전자주게기(EDG)를 가지는 양극성(bipolar) 화합물을 포함하되,The lifespan improvement layer includes a bipolar compound having an electron attractor (EWG) having a high electron absorption and an electron donor (EDG) having a large electron donor,
    상기 양극성 화합물은 하기 (a) 내지 (d) 조건을 만족하는 것을 특징으로 하는 유기 전계 발광 소자:The bipolar compound is an organic electroluminescent device, characterized in that to satisfy the following conditions (a) to (d):
    (a) 이온화포텐셜[Ip(LEL)]이 5.5eV 이상이고, (a) ionization potential [Ip (LEL)] is 5.5 eV or more,
    (b) EHOMO-ELUMO > 2.9 eV,(b) E HOMO- E LUMO > 2.9 eV,
    (c) 삼중항 에너지가 2.3eV 이상이며, (c) triplet energy is 2.3 eV or greater,
    (d) ΔEst < 0.5eV (ΔEst는 상기 화합물의 일중항 에너지와 삼중항 에너지의 차이를 나타냄)(d) ΔEst <0.5 eV (ΔEst represents the difference between the singlet and triplet energies of the compound)
  2. 제1항에 있어서,The method of claim 1,
    상기 발광층이 청색 형광, 녹색 형광, 또는 적색 인광인 경우, 수명개선층에 포함되는 양극성 화합물의 삼중항 에너지는 2.3eV 이상인 것을 특징으로 하는 유기 전계 발광 소자.When the light emitting layer is blue fluorescence, green fluorescence, or red phosphorescence, the triplet energy of the bipolar compound included in the lifespan improvement layer is 2.3 eV or more.
  3. 제1항에 있어서,The method of claim 1,
    상기 발광층이 녹색 인광인 경우, 수명개선층에 포함되는 양극성 화합물의 삼중항 에너지는 2.5eV 이상이고, 이온화 포텐셜이 6.0eV 이상인 것을 특징으로 하는 유기 전계 발광 소자.When the light emitting layer is green phosphorescence, the triplet energy of the bipolar compound included in the life improvement layer is 2.5 eV or more, the ionization potential is 6.0 eV or more, characterized in that the organic electroluminescent device.
  4. 제1항에 있어서,The method of claim 1,
    상기 발광층이 청색 인광인 경우, 수명개선층에 포함되는 양극성 화합물의 삼중항 에너지는 2.7eV 이상이고, 이온화 포텐셜이 6.0eV 이상인 것을 특징으로 하는 유기 전계 발광 소자.When the light emitting layer is blue phosphorescence, the triplet energy of the bipolar compound included in the life improvement layer is 2.7 eV or more, the ionization potential is 6.0 eV or more, characterized in that the organic electroluminescent device.
  5. 제1항에 있어서,The method of claim 1,
    상기 수명개선층에 포함되는 양극성 화합물의 전자 이동도 및 정공 이동도는 각각 상온에서 1×10-6 cm2/V·s 이상인 것을 특징으로 하는 유기 전계 발광 소자.The electron mobility and the hole mobility of the bipolar compound included in the life improvement layer are at least 1 × 10 −6 cm 2 / V · s at room temperature, respectively.
  6. 제1항에 있어서,The method of claim 1,
    상기 양극성 화합물은 하기 화학식으로 표시되는 전자끌게기(EWG) 모이어티를 1개 이상 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The bipolar compound is an organic electroluminescent device, characterized in that it comprises one or more electron attracting (EWG) moiety represented by the following formula.
    Figure PCTKR2014012888-appb-I000028
    Figure PCTKR2014012888-appb-I000028
    상기 식에서, Where
    A1 내지 A11은 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R)이되, 적어도 1개는 N이며, C(R)이 복수인 경우 이들은 서로 동일하거나 상이하고,A 1 to A 11 are the same as or different from each other, and each independently N or C (R), at least one is N, and when there are a plurality of C (R), they are the same or different from each other,
    상기 R은 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 인접한 기와 축합 고리를 형성하고, R is each independently hydrogen, deuterium, halogen, cyano, nitro, amino, C 1 -C 40 alkyl, C 2 -C 40 alkenyl, C 2 -C 40 alkynyl, C 3 ~ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ~ alkyloxy group of C 40, C 6 Aryloxy group of ~ C 60 , C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~, or selected from the group consisting of an aryl amine of the C 60 of the adjacent group to form a condensed ring,
    상기 R의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.Alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, force of the above R The pin group, the phosphine oxide group and the arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear atoms, 3 to 40 heterocycloalkyl group, C 6 ~ C 40 aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, a C 1 ~ C 40 alkyl Oxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ by at least one member selected from the group consisting of an aryl amine of the C 60 substituted or unsubstituted of .
  7. 제6항에 있어서,The method of claim 6,
    상기 양극성 화합물은 하기 화학식으로 표시되는 전자끌게기(EWG) 모이어티를 1개 이상 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The bipolar compound is an organic electroluminescent device, characterized in that it comprises one or more electron attracting (EWG) moiety represented by the following formula.
    Figure PCTKR2014012888-appb-I000029
    Figure PCTKR2014012888-appb-I000029
  8. 제1항에 있어서,The method of claim 1,
    상기 양극성(bipolar) 화합물은 하기 화학식 1로 표시되는 전자주게기(EDG) 모이어티를 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The bipolar compound is an organic electroluminescent device comprising an electron donor (EDG) moiety represented by the formula (1).
    [화학식 1][Formula 1]
    Figure PCTKR2014012888-appb-I000030
    Figure PCTKR2014012888-appb-I000030
    상기 화학식 1에서,In Chemical Formula 1,
    X1은 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고,X 1 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),
    Y1 내지 Y4는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R1)이고, 이때 복수의 R1은 서로 동일하거나 상이하고, 이들은 인접한 기와 축합 고리를 형성할 수 있고,Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), wherein a plurality of R 1 are the same or different from each other, and they may form a condensed ring with an adjacent group,
    X2 및 X3는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R2)이고, 이때 복수의 R2는 서로 동일하거나 상이하고, 이들은 인접한 기와 축합 고리를 형성할 수 있고,X 2 and X 3 are the same as or different from each other, and each independently N or C (R 2 ), wherein a plurality of R 2 are the same or different from each other, and they may form a condensed ring with an adjacent group,
    상기 R1 내지 R2 및 Ar1 내지 Ar5는 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 1 to R 2 and Ar 1 to Ar 5 are the same as or different from each other, and each independently, hydrogen, deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 60 aryl group, nuclear atom 5 to 60 Heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 is selected from the group consisting of alkyl boron group, C 6 ~ C 60 aryl group of boron, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ C 60 aryl group of an amine of,
    상기 R1 내지 R2 및 Ar1 내지 Ar5의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group of R 1 to R 2 and Ar 1 to Ar 5 , Alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 Alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 hetero aryl group, C 1 ~ C 40 of the alkyloxy group, C 6 ~ C 60 of the aryloxy group, C 1 ~ C 40 alkyl silyl group, the group C 6 ~ C 60 aryl silyl, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl group of boron, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 of the phosphine oxide group, and a C 6 ~ at least one selected from the group consisting of C 60 arylamine Substituted or unsubstituted.
  9. 제8항에 있어서,The method of claim 8,
    상기 화학식 1로 표시되는 화합물은 하기 A-1 내지 A-24 중 어느 하나로 표시되는 것을 특징으로 하는 유기 전계 발광 소자.The compound represented by Chemical Formula 1 is represented by any one of the following A-1 to A-24.
    Figure PCTKR2014012888-appb-I000031
    Figure PCTKR2014012888-appb-I000031
    상기 식에서, R2, Y1 내지 Y4 및 Ar1 내지 Ar5는 제8항에서 정의된 바와 동일하다.Wherein R 2 , Y 1 to Y 4 and Ar 1 to Ar 5 are the same as defined in claim 8.
  10. 제1항에 있어서,The method of claim 1,
    상기 양극성(bipolar) 화합물은 하기 화학식 1과 하기 화학식 2, 또는 하기 화학식 1과 하기 화학식 3이 서로 결합하여 축합 고리를 형성하는 모이어티를 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The bipolar compound includes an organic electroluminescent device comprising a moiety in which Formula 1 and Formula 2, or Formula 1 and Formula 3 combine with each other to form a condensed ring.
    [화학식 1][Formula 1]
    Figure PCTKR2014012888-appb-I000032
    Figure PCTKR2014012888-appb-I000032
    상기 화학식 1에서,In Chemical Formula 1,
    X1은 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고,X 1 is selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ),
    Y1 내지 Y4는 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R1)이고, 이때 Y1과 Y2, Y2와 Y3 또는 Y3와 Y4 중 하나는 하기 화학식 2 또는 화학식 3과 축합 고리를 형성하며(이때 복수의 R1은 서로 동일하거나 상이함),Y 1 to Y 4 are the same as or different from each other, and each independently N or C (R 1 ), wherein one of Y 1 and Y 2 , Y 2 and Y 3 or Y 3 and Y 4 is represented by the following Formula 2 or Formula Form a condensed ring with 3 (wherein a plurality of R 1 are the same or different from each other),
    X2 및 X3는 서로 동일하거나 또는 상이하며, 각각 독립적으로 N 또는 C(R2)이고(이때 복수의 R2는 서로 동일하거나 상이함),X 2 and X 3 are the same as or different from each other, and each independently N or C (R 2 ), wherein a plurality of R 2 are the same or different from each other,
    [화학식 2][Formula 2]
    Figure PCTKR2014012888-appb-I000033
    Figure PCTKR2014012888-appb-I000033
    [화학식 3][Formula 3]
    Figure PCTKR2014012888-appb-I000034
    Figure PCTKR2014012888-appb-I000034
    상기 화학식 2 및 화학식 3에서,In Chemical Formulas 2 and 3,
    Y5 내지 Y14은 서로 동일하거나 상이하며, 각각 독립적으로 N 또는 C(R3)이고, 이때 복수의 R3는 서로 동일하거나 상이하고, 상기 화학식 1과 축합 고리를 형성할 수 있고, Y 5 to Y 14 are the same as or different from each other, and each independently N or C (R 3 ), wherein a plurality of R 3 are the same as or different from each other, and may form a condensed ring with Formula 1,
    X4는 X1과 동일하고, 이때 복수의 Ar1 내지 Ar5은 서로 동일하거나 상이하며, X 4 is the same as X 1 , wherein a plurality of Ar 1 to Ar 5 are the same as or different from each other,
    축합 환을 비(非)형성하는 복수의 R3는 서로 동일하거나 상이하며, 각각 독립적으로, 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기, 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,The plurality of R 3 non-forming condensed rings are the same or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a nitro group, an amino group, an alkyl group of C 1 to C 40 , and a C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 60 aryl group, nuclear atom 5 to 60 Heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 of the phosphine oxide group, and a C 6 ~ C 60 of is selected from the group consisting of an aryl amine ,
    상기 R3의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.Alkyl group of the R 3, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, The phosphine group, the phosphine oxide group and the arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 Alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 1 to C 40 Alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ substituted by one or more selected from the group consisting of C 60 aryl amine, or unsubstituted of The.
  11. 제10항에 있어서,The method of claim 10,
    상기 양극성(bipolar) 화합물은 하기 화학식 1a 내지 화학식 1n로 표시되는 전자주게기(EDG) 모이어티 중 어느 하나를 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The bipolar compound is an organic electroluminescent device, characterized in that it comprises any one of the electron donor (EDG) moiety represented by the formula (1a) to formula (1n).
    [화학식 1a][Formula 1a]
    Figure PCTKR2014012888-appb-I000035
    Figure PCTKR2014012888-appb-I000035
    [화학식 1b][Formula 1b]
    Figure PCTKR2014012888-appb-I000036
    Figure PCTKR2014012888-appb-I000036
    [화학식 1c][Formula 1c]
    Figure PCTKR2014012888-appb-I000037
    Figure PCTKR2014012888-appb-I000037
    [화학식 1d][Formula 1d]
    Figure PCTKR2014012888-appb-I000038
    Figure PCTKR2014012888-appb-I000038
    [화학식 1e][Formula 1e]
    Figure PCTKR2014012888-appb-I000039
    Figure PCTKR2014012888-appb-I000039
    [화학식 1f][Formula 1f]
    Figure PCTKR2014012888-appb-I000040
    Figure PCTKR2014012888-appb-I000040
    [화학식 1g][Formula 1g]
    Figure PCTKR2014012888-appb-I000041
    Figure PCTKR2014012888-appb-I000041
    [화학식 1h][Formula 1h]
    Figure PCTKR2014012888-appb-I000042
    Figure PCTKR2014012888-appb-I000042
    [화학식 1i]Formula 1i]
    Figure PCTKR2014012888-appb-I000043
    Figure PCTKR2014012888-appb-I000043
    [화학식 1j][Formula 1j]
    Figure PCTKR2014012888-appb-I000044
    Figure PCTKR2014012888-appb-I000044
    [화학식 1k][Formula 1k]
    Figure PCTKR2014012888-appb-I000045
    Figure PCTKR2014012888-appb-I000045
    [화학식 1l][Formula 1l]
    Figure PCTKR2014012888-appb-I000046
    Figure PCTKR2014012888-appb-I000046
    [화학식 1m][Formula 1m]
    Figure PCTKR2014012888-appb-I000047
    Figure PCTKR2014012888-appb-I000047
    [화학식 1n][Formula 1n]
    Figure PCTKR2014012888-appb-I000048
    Figure PCTKR2014012888-appb-I000048
    상기 화학식 1a 내지 1n에서, In Chemical Formulas 1a to 1n,
    X1 내지 X4 및 Y1 내지 Y14는 제10항에서 정의한 바와 같다.X 1 to X 4 and Y 1 to Y 14 are as defined in claim 10.
  12. 제1항에 있어서,The method of claim 1,
    상기 양극성(bipolar) 화합물은 하기 화학식 4로 표시되는 전자주게기(EDG) 모이어티를 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The bipolar compound is an organic electroluminescent device comprising an electron donor (EDG) moiety represented by the formula (4).
    [화학식 4][Formula 4]
    Figure PCTKR2014012888-appb-I000049
    Figure PCTKR2014012888-appb-I000049
    상기 화학식 4에서,In Chemical Formula 4,
    L1 내지 L3는 서로 동일하거나 상이하며, 각각 독립적으로 단일결합, C6~C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고,L 1 to L 3 are the same as or different from each other, and each independently selected from the group consisting of a single bond, a C 6 to C 60 arylene group, and a heteroarylene group having 5 to 60 nuclear atoms,
    Ar6 내지 Ar8은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, C6~C40의 아릴기 및 핵원자수 5 내지 40의 헤테로아릴기에서 선택되고, 단 Ar6 내지 Ar8가 모두 동일한 경우는 제외하고,Ar 6 to Ar 8 are the same as or different from each other, and are each independently selected from hydrogen, deuterium, an aryl group having 6 to 40 carbon atoms and a heteroaryl group having 5 to 40 nuclear atoms, provided that Ar 6 to Ar 8 are all Except in the same case,
    R4 내지 R6은 서로 동일하거나 상이하며, 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,R 4 to R 6 are the same or different and are each independently hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 60 aryl group, nuclear atom 5 to 60 heteroaryl group, C 1 to C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C a group of the arylboronic 60, is selected from the group consisting of C 1 ~ C 40 of the phosphine group, C 1 ~ C 40 phosphine oxide group, and a C 6 ~ C 60 aryl group of an amine of,
    a 내지 c는 각각 독립적으로 0 내지 3의 정수이고,a to c are each independently an integer of 0 to 3,
    상기 L1 내지 L3, R4 내지 R6 및 Ar6 내지 Ar8의 아릴렌기, 헤테로아릴렌기, 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 포스핀기, 포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, 중수소, 할로겐기, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C1~C40의 포스핀기, C1~C40의 포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환 또는 비치환된다.The arylene group, heteroarylene group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyl jade of L 1 to L 3 , R 4 to R 6 and Ar 6 to Ar 8 The time period, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl boron group, phosphine group, phosphine oxide group and arylamine group are each independently deuterium, halogen group, cyano group, nitro group, amino group, C 1 ~ C 40 Alkyl group, C 2 ~ C 40 Alkenyl group, C 2 ~ C 40 Alkynyl group, C 3 ~ C 40 Cycloalkyl group, C 3 ~ 40 Heterocycloalkyl group, C 6 ~ C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, a alkyl boronic of C 1 ~ C 40, C 6 ~ C group 60 arylboronic of, C 1 ~ C 40 of the phosphine group, C 1 ~ phosphine oxide of a C 40 group, and a C 6 ~ C 60 of Arya Substituted or unsubstituted with one or more selected from the group consisting of min groups.
  13. 제1항에 있어서,The method of claim 1,
    상기 전자수송층의 재료와 상기 수명개선층의 재료가 동일한 것을 특징으로 하는 유기 전계 발광 소자.The material of the electron transport layer and the material of the life improvement layer is the same.
  14. 제1항에 있어서,The method of claim 1,
    상기 전자주입층의 재료와 상기 수명개선층의 재료가 동일한 것을 특징으로 하는 유기 전계 발광 소자.The material of the electron injection layer and the material of the life improvement layer is the same.
  15. 제1항에 있어서,The method of claim 1,
    상기 전자주입층 또는 상기 전자수송층은 알칼리 금속 착물이 공증착되어 구비되는 것을 특징으로 하는 유기 전계 발광 소자.The electron injection layer or the electron transport layer is an organic electroluminescent device, characterized in that the alkali metal complex is provided by co-deposition.
  16. 제1항에 있어서,The method of claim 1,
    상기 정공수송층과 상기 발광층 사이에 전자와 엑시톤을 블로킹하는 유기막층이 더 구비하는 것을 특징으로 하는 유기 전계 발광 소자.And an organic film layer blocking electrons and excitons between the hole transport layer and the light emitting layer.
  17. 제1항에 있어서,The method of claim 1,
    상기 발광층은 호스트 재료와 도펀트 재료를 포함하고, 상기 도펀트를 0.1중량% 내지 30중량% 범위로 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The light emitting layer comprises a host material and a dopant material, the organic electroluminescent device, characterized in that it comprises the dopant in the range of 0.1% to 30% by weight.
  18. 제1항에 있어서,The method of claim 1,
    상기 정공수송층과 상기 전자수송층 사이에 복수의 발광층을 순차적으로 적층시켜 전압, 전류 인가시 혼합색을 구현하는 것을 특징으로 하는 유기 전계 발광 소자.Organic light emitting device, characterized in that to achieve a mixed color when a voltage, current is applied by sequentially stacking a plurality of light emitting layer between the hole transport layer and the electron transport layer.
  19. 제1항에 있어서,The method of claim 1,
    상기 정공수송층과 상기 전자수송층 사이에 단일 재료의 발광층을 복수로 적층하거나, 이종 재료의 복수의 발광층을 직렬로 구비하여 전압, 전류 인가시 혼합색을 구현하거나 효율을 증가시키는 것을 특징으로 하는 유기 전계 발광 소자.Organic electroluminescence characterized in that a plurality of light emitting layers of a single material is laminated between the hole transport layer and the electron transport layer, or a plurality of light emitting layers of different materials are provided in series to implement mixed colors or increase efficiency when voltage and current are applied. device.
  20. 제1항에 있어서,The method of claim 1,
    전압, 전류 또는 이들 모두를 인가하는 경우, 최대 발광효율은 유지하면서 초기 밝기의 반감시간(Lifetime)이 증가하는 것을 특징으로 하는 유기 전계 발광 소자.When applying voltage, current, or both, the organic EL device characterized in that the half-life (Lifetime) of the initial brightness increases while maintaining the maximum luminous efficiency.
PCT/KR2014/012888 2013-12-27 2014-12-26 Organic electroluminescent device WO2015099481A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201480071035.2A CN105849227B (en) 2013-12-27 2014-12-26 Organic electroluminescent device
US15/107,971 US10573822B2 (en) 2013-12-27 2014-12-26 Organic electroluminescent device
JP2016543059A JP6759099B2 (en) 2013-12-27 2014-12-26 Organic electroluminescent device
US16/742,060 US11588109B2 (en) 2013-12-27 2020-01-14 Organic electroluminescent device
US17/589,017 US20220336753A1 (en) 2013-12-27 2022-01-31 Organic electroluminescent device
US17/953,510 US20230093216A1 (en) 2013-12-27 2022-09-27 Organic electroluminescent device

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2013-0166103 2013-12-27
KR20130166103 2013-12-27
KR1020140158154A KR101742359B1 (en) 2013-12-27 2014-11-13 Organic electro luminescence device
KR10-2014-0158154 2014-11-13

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US15/107,971 A-371-Of-International US10573822B2 (en) 2013-12-27 2014-12-26 Organic electroluminescent device
US16/742,060 Continuation US11588109B2 (en) 2013-12-27 2020-01-14 Organic electroluminescent device

Publications (1)

Publication Number Publication Date
WO2015099481A1 true WO2015099481A1 (en) 2015-07-02

Family

ID=53479242

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/012888 WO2015099481A1 (en) 2013-12-27 2014-12-26 Organic electroluminescent device

Country Status (1)

Country Link
WO (1) WO2015099481A1 (en)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150194610A1 (en) * 2014-01-06 2015-07-09 Samsung Electronics Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
KR20160012409A (en) * 2014-07-24 2016-02-03 주식회사 두산 Organic compounds and organic electro luminescence device comprising the same
WO2017026643A1 (en) * 2015-08-13 2017-02-16 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2017095086A1 (en) * 2015-12-03 2017-06-08 주식회사 두산 Organic light-emitting compound and organic electroluminescent device using same
US20170179395A1 (en) * 2015-12-22 2017-06-22 Samsung Display Co., Ltd. Organic light-emitting device
US20170179396A1 (en) * 2015-12-22 2017-06-22 Samsung Display Co., Ltd. Organic light-emitting device
US20170179401A1 (en) * 2015-12-22 2017-06-22 Samsung Display Co., Ltd. Organic light-emitting device
EP3185332A1 (en) * 2015-12-22 2017-06-28 Samsung Display Co., Ltd. Organic light-emitting device
EP3185331A1 (en) * 2015-12-22 2017-06-28 Samsung Display Co., Ltd. Organic light-emitting device
CN106910834A (en) * 2015-12-22 2017-06-30 三星显示有限公司 Organic luminescent device
CN106910833A (en) * 2015-12-22 2017-06-30 三星显示有限公司 Organic light emitting apparatus
CN107226818A (en) * 2016-03-24 2017-10-03 上海和辉光电有限公司 A kind of luminous organic material and its application in OLED
CN107226819A (en) * 2016-03-24 2017-10-03 上海和辉光电有限公司 A kind of luminous organic material and its application in OLED
US20170294613A1 (en) * 2016-04-07 2017-10-12 Samsung Display Co., Ltd. Organic light-emitting device
US10230053B2 (en) * 2015-01-30 2019-03-12 Samsung Display Co., Ltd. Organic light-emitting device
US10280171B2 (en) 2016-05-31 2019-05-07 Board Of Regents, The University Of Texas System Heterocyclic inhibitors of PTPN11
USRE47654E1 (en) 2010-01-15 2019-10-22 Idemitsu Koasn Co., Ltd. Organic electroluminescence device
US10954243B2 (en) 2018-05-02 2021-03-23 Navire Pharma, Inc. Substituted heterocyclic inhibitors of PTPN11
US11104675B2 (en) 2018-08-10 2021-08-31 Navire Pharma, Inc. PTPN11 inhibitors
US11466017B2 (en) 2011-03-10 2022-10-11 Board Of Regents, The University Of Texas System Heterocyclic inhibitors of PTPN11

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060040830A (en) * 2004-11-05 2006-05-11 삼성에스디아이 주식회사 Organic electroluminescence display
WO2006115232A1 (en) * 2005-04-21 2006-11-02 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device, and electronic device
WO2008074847A1 (en) * 2006-12-20 2008-06-26 Thomson Licensing Organic light-emitting diode having a barrier layer made of bipolar material
WO2010137733A1 (en) * 2009-05-29 2010-12-02 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and method for manufacturing the same
KR20130039298A (en) * 2011-10-11 2013-04-19 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Light-emitting element, light-emitting device, electronic device, lighting device, and pyrene-based compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060040830A (en) * 2004-11-05 2006-05-11 삼성에스디아이 주식회사 Organic electroluminescence display
WO2006115232A1 (en) * 2005-04-21 2006-11-02 Semiconductor Energy Laboratory Co., Ltd. Light emitting element, light emitting device, and electronic device
WO2008074847A1 (en) * 2006-12-20 2008-06-26 Thomson Licensing Organic light-emitting diode having a barrier layer made of bipolar material
WO2010137733A1 (en) * 2009-05-29 2010-12-02 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and method for manufacturing the same
KR20130039298A (en) * 2011-10-11 2013-04-19 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Light-emitting element, light-emitting device, electronic device, lighting device, and pyrene-based compound

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE47654E1 (en) 2010-01-15 2019-10-22 Idemitsu Koasn Co., Ltd. Organic electroluminescence device
US11466017B2 (en) 2011-03-10 2022-10-11 Board Of Regents, The University Of Texas System Heterocyclic inhibitors of PTPN11
US20150194610A1 (en) * 2014-01-06 2015-07-09 Samsung Electronics Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
US10622568B2 (en) * 2014-01-06 2020-04-14 Samsung Electronics Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
KR102238282B1 (en) 2014-07-24 2021-04-08 솔루스첨단소재 주식회사 Organic compounds and organic electro luminescence device comprising the same
KR20160012409A (en) * 2014-07-24 2016-02-03 주식회사 두산 Organic compounds and organic electro luminescence device comprising the same
WO2016013894A3 (en) * 2014-07-24 2016-08-04 주식회사 두산 Organic compound and organic electroluminescent device comprising same
US10230053B2 (en) * 2015-01-30 2019-03-12 Samsung Display Co., Ltd. Organic light-emitting device
TWI707857B (en) * 2015-08-13 2020-10-21 南韓商羅門哈斯電子材料韓國公司 Organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2017026643A1 (en) * 2015-08-13 2017-02-16 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent device comprising the same
KR102530095B1 (en) 2015-12-03 2023-05-09 솔루스첨단소재 주식회사 Organic light-emitting compound and organic electroluminescent device using the same
KR20170065291A (en) * 2015-12-03 2017-06-13 주식회사 두산 Organic light-emitting compound and organic electroluminescent device using the same
WO2017095086A1 (en) * 2015-12-03 2017-06-08 주식회사 두산 Organic light-emitting compound and organic electroluminescent device using same
CN106910831A (en) * 2015-12-22 2017-06-30 三星显示有限公司 Organic light emitting apparatus
EP3185332A1 (en) * 2015-12-22 2017-06-28 Samsung Display Co., Ltd. Organic light-emitting device
CN106910833A (en) * 2015-12-22 2017-06-30 三星显示有限公司 Organic light emitting apparatus
CN106981576A (en) * 2015-12-22 2017-07-25 三星显示有限公司 Organic light emitting apparatus
US11937500B2 (en) * 2015-12-22 2024-03-19 Samsung Display Co., Ltd. Organic light-emitting device
CN111740024B (en) * 2015-12-22 2023-08-25 三星显示有限公司 organic light emitting device
US11696496B2 (en) 2015-12-22 2023-07-04 Samsung Display Co., Ltd. Organic light-emitting device
CN106910835A (en) * 2015-12-22 2017-06-30 三星显示有限公司 Organic light emitting apparatus
US20170179395A1 (en) * 2015-12-22 2017-06-22 Samsung Display Co., Ltd. Organic light-emitting device
CN111653677B (en) * 2015-12-22 2023-04-14 三星显示有限公司 Organic light emitting device
CN106910834A (en) * 2015-12-22 2017-06-30 三星显示有限公司 Organic luminescent device
CN106981576B (en) * 2015-12-22 2020-01-03 三星显示有限公司 Organic light emitting device
EP3185331A1 (en) * 2015-12-22 2017-06-28 Samsung Display Co., Ltd. Organic light-emitting device
CN111048677A (en) * 2015-12-22 2020-04-21 三星显示有限公司 Organic light emitting device
CN106910831B (en) * 2015-12-22 2020-05-05 三星显示有限公司 Organic light emitting device
CN106910834B (en) * 2015-12-22 2020-07-07 三星显示有限公司 Organic light emitting device
CN106910833B (en) * 2015-12-22 2020-08-07 三星显示有限公司 Organic light emitting device
CN111653677A (en) * 2015-12-22 2020-09-11 三星显示有限公司 Organic light emitting device
CN111740024A (en) * 2015-12-22 2020-10-02 三星显示有限公司 Organic light emitting device
CN106910832A (en) * 2015-12-22 2017-06-30 三星显示有限公司 Organic light emitting apparatus
CN106910835B (en) * 2015-12-22 2020-10-27 三星显示有限公司 Organic light emitting device
US11617290B2 (en) 2015-12-22 2023-03-28 Samsung Display Co., Ltd. Organic light-emitting device
US20170179396A1 (en) * 2015-12-22 2017-06-22 Samsung Display Co., Ltd. Organic light-emitting device
US20170179401A1 (en) * 2015-12-22 2017-06-22 Samsung Display Co., Ltd. Organic light-emitting device
CN106910832B (en) * 2015-12-22 2021-06-25 三星显示有限公司 Organic light emitting device
CN111048677B (en) * 2015-12-22 2022-09-23 三星显示有限公司 Organic light emitting device
CN107226819B (en) * 2016-03-24 2019-08-23 上海和辉光电有限公司 A kind of luminous organic material and its application in OLED device
CN107226819A (en) * 2016-03-24 2017-10-03 上海和辉光电有限公司 A kind of luminous organic material and its application in OLED
CN107226818A (en) * 2016-03-24 2017-10-03 上海和辉光电有限公司 A kind of luminous organic material and its application in OLED
US11678498B2 (en) * 2016-04-07 2023-06-13 Samsung Display Co., Ltd. Organic light-emitting device
US20170294613A1 (en) * 2016-04-07 2017-10-12 Samsung Display Co., Ltd. Organic light-emitting device
US10851110B2 (en) 2016-05-31 2020-12-01 Board Of Regents, The University Of Texas System Heterocyclic inhibitors of PTPN11
US10280171B2 (en) 2016-05-31 2019-05-07 Board Of Regents, The University Of Texas System Heterocyclic inhibitors of PTPN11
US11840536B2 (en) 2016-05-31 2023-12-12 Board Of Regents, The University Of Texas System Heterocyclic inhibitors of PTPN11
US10954243B2 (en) 2018-05-02 2021-03-23 Navire Pharma, Inc. Substituted heterocyclic inhibitors of PTPN11
US11932643B2 (en) 2018-05-02 2024-03-19 Navire Pharma, Inc. Substituted heterocyclic inhibitors of PTPN11
US11104675B2 (en) 2018-08-10 2021-08-31 Navire Pharma, Inc. PTPN11 inhibitors
US11945815B2 (en) 2018-08-10 2024-04-02 Navire Pharma, Inc. PTPN11 inhibitors

Similar Documents

Publication Publication Date Title
WO2015099481A1 (en) Organic electroluminescent device
WO2016064102A1 (en) Organic electroluminescent device
WO2016068585A1 (en) Organic electroluminescence device
WO2011081286A2 (en) Novel compound for an organic photoelectric device, and organic photoelectric device including same
WO2013036044A2 (en) Material for organic light-emitting device, and organic light-emitting device using same
WO2019045252A1 (en) Organic electroluminescent device
WO2017052225A1 (en) Organic light emitting diode
WO2014129869A1 (en) Organic field effect light-emitting device
WO2018009009A1 (en) Heterocyclic compound, and organic light-emitting device using same
WO2016195406A2 (en) Heterocyclic compound and organic light emitting device including same
WO2017142310A1 (en) Heterocyclic compound and organic electroluminescent device comprising same
WO2019172649A1 (en) Polycyclic compound and organic light emitting element comprising same
WO2021230451A1 (en) Organic electroluminescent device
WO2020040514A1 (en) Organic light emitting diode
WO2017142304A1 (en) Heterocyclic compound and organic electroluminescent device comprising same
WO2020130511A1 (en) Compound and organic light-emitting device including same
WO2014084612A1 (en) Novel compound and organic electronic element using same
WO2016148382A1 (en) Organic light emitting device
WO2017138755A1 (en) Heterocyclic compound and organic electroluminescent device containing same
WO2020060283A1 (en) Organic light emitting diode
WO2015008940A1 (en) Organic electroluminescent device
WO2017142308A1 (en) Heterocyclic compound and organic electroluminescent device comprising same
WO2019088751A1 (en) Compound and organic light emitting device comprising same
WO2015088249A1 (en) Organic light emitting compound and organic electroluminescent device using same
WO2018194278A2 (en) Organic electroluminescent device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14873131

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016543059

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15107971

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 18/10/2016)

122 Ep: pct application non-entry in european phase

Ref document number: 14873131

Country of ref document: EP

Kind code of ref document: A1