WO2020175948A1 - 유기 발광 소자 - Google Patents

유기 발광 소자 Download PDF

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WO2020175948A1
WO2020175948A1 PCT/KR2020/002861 KR2020002861W WO2020175948A1 WO 2020175948 A1 WO2020175948 A1 WO 2020175948A1 KR 2020002861 W KR2020002861 W KR 2020002861W WO 2020175948 A1 WO2020175948 A1 WO 2020175948A1
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group
compound
formula
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unsubstituted
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PCT/KR2020/002861
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English (en)
French (fr)
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김민준
이동훈
김형석
이상우
이성재
김선민
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주식회사 엘지화학
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Priority to CN202080004761.8A priority Critical patent/CN112640143A/zh
Priority to JP2021508283A priority patent/JP7238967B2/ja
Priority to EP20763691.1A priority patent/EP3832745A4/en
Priority to US17/271,292 priority patent/US20210359223A1/en
Publication of WO2020175948A1 publication Critical patent/WO2020175948A1/ko

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    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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Definitions

  • organic luminescence is a phenomenon that uses organic substances to generate electric energy.
  • An organic light-emitting device using the organic light-emitting phenomenon has a structure including an organic material layer on a positive electrode, a negative electrode, and moving.
  • the organic material layer is often composed of a layer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device.
  • it can be formed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc.
  • a voltage when a voltage is applied between the two electrodes, holes in the positive electrode and electrons in the negative electrode are injected into the organic material layer, and the injected holes and electrons may meet. It is formed, and when this exciton falls back to the ground state, it glows.
  • the present invention is an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first electrode; and an organic material layer provided between the first electrode and the second electrode,
  • the organic material layer provides an organic light-emitting device comprising a layer including a compound of Formula 1 below and a layer including a compound of Formula 2 below.
  • [13] III to 1112 are the same as or different from each other, and each independently hydrogen; nitrile; A halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or adjacent groups are bonded to each other to form a ring,
  • [18] show to show are the same or different, each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or -1 is,
  • [19] 1 is a direct bond; a phenylene group substituted or unsubstituted with deuterium; or a biphenylylene group substituted or unsubstituted with deuterium,
  • [2] ⁇ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted heteroaryl group.
  • the organic light emitting device has a low driving voltage and high efficiency. 2020/175948 1»(:1 ⁇ 1 ⁇ 2020/002861
  • FIG. 1 and 2 illustrate an organic light emitting device according to an exemplary embodiment of the present specification.
  • the present specification is an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer is It provides an organic light-emitting device comprising a layer containing the compound of and a layer containing the compound of Formula 2 above.
  • substitution means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and 2 In case of abnormal substitution, two or more substituents may be the same or different.
  • substituted or unsubstituted is deuterium; nitrile group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted silyl group; substituted or unsubstituted alkoxy Group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl group; And substituted with 1 or 2 or more substituents selected from the group consisting of substituted or unsubstituted heterocyclic groups, or two or more of the substituents exemplified above are connected It means that it is substituted with a substituent or does not have any substituents.
  • a substituent group in which two or more substituents are connected means an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an alkyl group It may be a substituted aryl group, etc. 2020/175948 1»(:1 ⁇ 1 ⁇ 2020/002861
  • the alkyl group may be straight-chain or branched, and the number of carbons is not particularly limited, but it is preferably 1 to 30. Specifically, the number of carbons is preferably 1 to 20. More specifically, the number of carbons is 1 to ⁇ It is desirable.
  • Specific examples include methyl group; ethyl group; propyl group; II-propyl group; Isopropyl group; Butyl group; 1 1 -butyl group; isobutyl group; -Butyl group; 8% -butyl group; 1-methylbutyl group: [_ethylbutyl group; Pentyl group; II -pentyl group; isopentyl group; neopentyl group; 1631-pentyl group; nuclear sil group; II-nuclear chamber;
  • the cycloalkyl group is not particularly limited, but it is preferable that it has 3 to 30 carbon atoms, and it is more preferable that it has 3 to 20 carbon atoms.
  • the alkoxy group may be linear, branched or cyclic.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1 to 30 carbon atoms. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, it is preferably 1 to 20 carbon atoms. Specifically, a methoxy group; an ethoxy group;
  • 11-nonyloxy group; II-decyloxy group; benzyloxy group; I) -It may be a methylbenzyloxy group, but is not limited thereto.
  • the amine group is-NH 2; Alkylamine group; Alkylarylamine group;
  • Arylamine group Arylheteroarylamine group; Alkylheteroarylamine group and
  • amine group includes methylamine group; dimethylamine group; ethylamine group; diethylamine group; phenyl Amine group;
  • Naphthylamine group Biphenylamine group; Anthracenylamine group; 9-methylanthracenylamine group; Diphenylamine group; Phenylnaphthylamine group; Ditolylamine group; Phenyltolylamine group;
  • Triphenylamine group Phenylbiphenylamine group; Phenylnaphthylamine group;
  • Phenylphenanthrenylamine group Biphenylphenanthrenylamine group; 2020/175948 1 » (:1 ⁇ 1 ⁇ 2020/002861
  • Phenanthrenylfluorenylamine group There are biphenylfluorenylamine groups, but are not limited thereto.
  • the silyl group is- It can be represented by the chemical formula above, And, each independently hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.
  • the silyl group is specifically a trimethylsilyl group; a triethylsilyl group; Butyl dimethyl silyl group;
  • Vinyldimethylsilyl group propyldimethylsilyl group; triphenylsilyl group; diphenylsilyl group;
  • the aryl group is not particularly limited, but preferably has 6 to 20 carbon atoms.
  • the aryl group may be monocyclic or polycyclic. Examples of the monocyclic aryl group include a phenyl group; a biphenyl group; a terphenyl group, and the like.
  • the polycyclic aryl group may be a naphthyl group; an anthracenyl group; a phenanthryl group; It may be a triphenyl group; a pyrenyl group; a fluorenyl group, but is not limited thereto.
  • the "adjacent" group is a substituent substituted on an atom directly connected to the atom to which the corresponding substituent is substituted, a substituent which is three-dimensionally closest to the substituent, or another substituent substituted on the atom to which the corresponding substituent is substituted.
  • two substituents substituted with the ortho position in the benzene ring and two substituents substituted with the same carbon in the aliphatic ring can be interpreted as "adjacent" to each other.
  • arylamine groups include substituted or unsubstituted
  • the aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group The arylamine group containing two or more groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.
  • the aryl group in the arylamine group is selected from the examples of the aryl group described above.
  • the heteroaryl group contains at least one non-carbon atom, that is, a hetero atom, and specifically, the heteroatom may contain at least one atom selected from the group consisting of 0, 3, and so on. Is not particularly limited, preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic.
  • heteroaryl group examples include a thiophene group; a furanyl group; a pyrrole group; an imidazolyl group; a thiazolyl group; Oxazolyl group; oxadiazolyl group; pyridyl group; bipyridyl group; pyrimidyl group;
  • Triazinyl group Triazolyl group; Acridyl group; Pyridazinyl group; Pyrazinyl group;
  • Benzocarbazolyl group Benzothiophene group; Dibenzothiophene group; Benzofuranyl group;
  • Phenanthrolinyl group ( £1&11( ;1 1]'0 11116); isoxazolyl group; thiadiazolyl group;
  • phenothiazinyl groups and dibenzofuranyl groups are not limited thereto.
  • heteroaryl group is a divalent group.
  • Chemical Formula 1 may be represented by the following Chemical Formula 1- 1 or Chemical Formula 1-2.
  • Ni, Sa 1, and 115 to 1112 are as defined in Formula 1. 2020/175948 1»(:1 ⁇ 1 ⁇ 2020/002861
  • Chemical Formula 1 may be represented by any one of Chemical Formulas 1-3 to 1-6 below.
  • 1 ⁇ 1 is a direct bond.
  • the is an arylene group.
  • the silver heteroarylene group In an exemplary embodiment of the present invention, is a heteroarylene group having 3 to 30 carbon atoms including any one or more of 0 or 8.
  • the show is an aryl group having 6 to 20 carbon atoms. In one embodiment of the present invention, the show silver carbon number of 6 to 30
  • the yarn 1 is a carbazole group substituted or unsubstituted with a dibenzofuran, dibenzothiophene, or a phenyl group.
  • yarns 2 and 3 are the same as each other.
  • the yarns 2 and 3 are different from each other.
  • a dibenzothiophene group, or a carbazole group may be further substituted with deuterium.
  • 1 is a direct bond, a phenylene group substituted or unsubstituted with deuterium, or a biphenylylene group substituted or unsubstituted with deuterium.
  • ⁇ is a substituted or unsubstituted polycyclic aryl group having 6 to 20 carbon atoms.
  • a polycyclic aryl group having 6 to 20 carbon atoms substituted or unsubstituted with deuterium, an alkyl group, or an aryl group.
  • ⁇ is a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.
  • four 4 is a substituted or unsubstituted aryl group.
  • the show is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
  • the show is substituted or unsubstituted with an aryl group.
  • Formula 2 since the number of carbon atoms of the aryl group that may be included in Formula 2 is 6 to 20, Formula 2 does not include a spirobifluorene group.
  • the compound of Formula 1 is any one selected from the following compounds.
  • the compound of Formula 2 is any one selected from the following compounds.
  • the structure of the organic light-emitting device of the present invention may have the same structure as shown in Figs. 1 and 2, but it is not limited to this.
  • FIG. 1 shows a structure of an organic light-emitting device in which a first electrode 2, an organic material layer 3, and a second electrode 4 are sequentially stacked on a substrate 1.
  • FIG 1 illustrates an organic light-emitting device, but is not limited thereto.
  • the structure of an organic light-emitting device in which a hole blocking layer 10, an electron injection and transport layer 11, and a second electrode 4 are sequentially stacked is illustrated.
  • the compound of formula 1 of the present invention is preferably a light-emitting layer 9 ), and the compound of Formula 2 may preferably be included in the electron blocking layer (8).
  • an additional layer may be further included, and some layers may be excluded.
  • the organic material layer includes a light-emitting layer, and the light-emitting layer includes a compound of Formula 1 above.
  • the organic material layer includes a light-emitting layer, and the light-emitting layer includes the compound of Formula 1 as a host of the light-emitting layer.
  • the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer
  • the hole injection layer, a hole transport layer, or a hole injection and transport layer is a compound of Formula 1 May include.
  • the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron
  • the injection and transport layer may include the compound of Formula 1.
  • the organic material layer is an electron blocking layer or a hole
  • Including a blocking layer, the electron blocking layer or the hole blocking layer may include the compound of Formula 1 above.
  • the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, a hole transport layer, or a hole injection and transport layer is a compound of Formula 2 May include.
  • the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer is a compound of Formula 2 May include.
  • the organic material layer is an electron blocking layer or a hole
  • Including a blocking layer, the electron blocking layer, or the hole blocking layer may include the compound of Formula 2.
  • the organic material layer includes an electron blocking layer, and the electron blocking layer includes a compound of Formula 2 above.
  • the organic material layers may be formed of the same material or different materials.
  • This specification also includes the manufacture of organic light emitting devices formed using the above compounds.
  • the organic light-emitting device according to the present invention is sputtering or electron beam
  • an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the compound of Formula 1 is deposited on it. After forming the containing organic material layer and the organic material layer containing the compound of Formula 2 above, it can be produced by depositing a material that can be used as a negative electrode thereon. In addition to this method, a negative electrode material, an organic material layer, and a positive electrode material are in turn on the substrate. Organic light emitting devices can also be made by vapor deposition.
  • the anode material is usually used to facilitate hole injection into the organic layer.
  • the cathode material the work function is usually small to facilitate electron injection into the organic material layer. It is preferable that it is a material.
  • the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, iron, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or Li0 2 /Al, but they are not limited to these.
  • the hole injection material is a material capable of well injecting holes from the anode at a low voltage. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organic substances,
  • quinacridone-based organic substances there are quinacridone-based organic substances, perylene-based organic substances, anthraquinones, and conductive polymers of polyaniline and polycompounds, but they are not limited to these.
  • the hole transport material As the hole transport material, the hole is transported from the anode or the hole injection layer.
  • a material with high mobility for holes is suitable.
  • Specific examples include arylamine-based organic substances, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but they are not limited to these.
  • the light-emitting material a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material with good quantum efficiency for fluorescence or phosphorescence is preferable.
  • Poly(P-phenylenevinylene) (PPV) series polymers ; spiro compounds; polyfluorene, rubrene, etc., but they are not limited to these.
  • Dopant materials include aromatic compounds, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and an arylamino group.
  • the styrylamine compound is a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine, aryl group, silyl group, alkyl group, One or two or more substituents selected from the group consisting of cycloalkyl groups and arylamino groups are substituted or unsubstituted.
  • substituents selected from the group consisting of cycloalkyl groups and arylamino groups are substituted or unsubstituted.
  • Specific examples include styrylamine, styryldiamine, styryltriamine, and styryltetraamine, but are not limited thereto.
  • iridium complexes and platinum complexes as metal complexes, but are not limited thereto.
  • the light-emitting layer may include a host and a dopant.
  • the organic material layer includes a light-emitting layer, and the light-emitting layer comprises a host and a dopant.
  • the host includes a compound of Formula 1 of the present invention, and the dopant may include a compound of the following structural formula.
  • the emission layer includes the compound of Formula 1 as a red host.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light-emitting layer.
  • an electron transport material a material that can transfer electrons to the light-emitting layer by injecting electrons well from the cathode.
  • Suitable include new complexes of 8-hydroxyquinoline; complexes including 13 ⁇ 4 show; Organic radical compounds; hydroxyflavone-metal complexes, etc., but not limited to these.
  • the electron transport layer can be used with any desired cathode material, as used according to the prior art.
  • suitable cathode materials Is a common material that has a low work function and is followed by an aluminum or silver layer.
  • alumina or silver layer follows.
  • the electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect on the light-emitting layer or light-emitting material, and excitons generated in the light-emitting layer It is preferable to use a compound that prevents the migration of the material to the hole injection layer and has excellent thin film formation ability.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole,
  • Perylene tetracarboxylic acid, preorenylidenemethane, anthrone, etc. and their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, etc. are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinatortium,
  • the hole blocking layer is a layer that blocks the arrival of holes to the cathode, and can generally be formed under the same conditions as the hole injection layer.
  • oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum There are, but are not limited to, an aluminum complex.
  • the organic light-emitting device may be a front-emitting type, a back-emitting type or a double-sided light-emitting type, depending on the material used.
  • the organic light-emitting device of the present invention uses the above-described compounds to
  • an organic material layer Except for forming an organic material layer, it can be manufactured by conventional organic light emitting device manufacturing methods and materials.
  • the compounds of the present invention were prepared using the Buchwald-Hartwig coupling reaction, Heck coupling reaction, and Suzuki coupling reaction as representative reactions.
  • intermediate 23 (10g, 22.5mmol), 2-(4-bromophenyl)naphthalene (6.3g, 22.5mmol), sodium tert-butoxide (4.3g, 44.9mmol) was added to 200ml of Toluene, stirred and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed by decompression.
  • intermediate 33 (10 is, 19.211111101), 2-1 ⁇ 01110 ⁇ 1 ⁇ 11) 46116 (5.9 is, 19.2mmol) and sodium tert-butoxide (3.7g, 38.4mmol) were added to 200ml of Toluene, stirred and refluxed. Afterwards, bis (tri-tert-butylphosphine) palladium(0)(().2g, 0.4mmol) was added. . After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed by decompression.
  • a glass substrate coated with a thin film of 1,000 A of ITO (indium tin oxide) was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and the distilled water was used as the distilled water. Distilled water filtered secondarily with a filter manufactured by Millipore Co. was used. After washing ITO for 30 minutes, ultrasonic washing was performed for W minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. After washing the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
  • ITO indium tin oxide
  • 195 refers to the time it takes for the luminance to decrease to 95% from the initial luminance (5,000 1 out).

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Abstract

본 명세서는 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층은 화학식 1의 화합물을 포함하는 층과, 화학식 2의 화합물을 포함하는 층을 포함하는 것인 유기 발광 소자에 관한 것이다.

Description

2020/175948 1»（：1^1{2020/002861 명세서
발명의명칭:유기발광소자
기술분야
[1] 본출원은 2019년 2월 28일에 한국특허청에 제출된한국특허출원
제 10-2019-0024130호의출원일의 이익을주장하며,그내용전부는본명세서에 포함된다.
四 본명세서는유기발광소자에관한것이다.
배경기술
[3] 일반적으로유기 발광현상이란유기물질을이용하여 전기에너지를
빛에너지로전환시켜주는현상을말한다.유기발광현상을이용하는유기발광 소자는통상양극과음극및 이사이에유기물층을포함하는구조를가진다. 여기서유기물층은유기 발광소자의 효율과안정성을높이기위하여 각기다른 물질로구성된다층의구조로이루어진경우가많으며,예컨대정공주입층, 정공수송층,발광층,전자수송층,전자주입층등으로이루어 질수있다.이러한 유기 발광소자의구조에서두전극사이에 전압을걸어주게되면양극에서는 정공이,음극에서는전자가유기물층에주입되게되고,주입된정공과전자가 만났을
Figure imgf000002_0001
형성되며,이 엑시톤이다시 바닥상태로떨어질때 빛이 나게된다.
[4] 상기와같은유기발광소자를위한새로운재료의 개발이 계속요구되고있다. 발명의상세한설명
기술적과제
[5] 본명세서는유기발광소자를제공한다.
과제해결수단
[6] 본발명은제 1전극;상기제 1전극에 대향하여구비된제 2전극;및상기제 1 전극과제 2전극사이에구비된유기물층을포함하는유기발광소자로서,
[7] 상기유기물층은하기화학식 1의화합물을포함하는층과,하기 화학식 2의 화합물을포함하는층을포함하는것인유기발광소자를제공한다.
[8] [화학식 1] 2020/175948 1»（：1^1{2020/002861
2
Figure imgf000003_0001
[1이 상기화학식 1에서,
[11] 니은직접결합;치환또는비치환된아릴렌기 ;또는치환또는비치환된
이고,
[12]
Figure imgf000003_0002
는비치환된아릴기 ;또는치환또는비치환된
헤테로아릴기이며,
[13] III내지 1112는서로같거나상이하고,각각독립적으로수소;니트릴기; 할로겐기;치환또는비치환된알킬기;치환또는비치환된실릴기;치환또는 비치환된아릴기;또는치환또는비치환된헤테로아릴기이거나,인접한기끼리 결합하여고리를형성하고,
[14] III내지 114중인접한어느 2개의치환기는반드시서로결합하여,치환또는 비치환된방향족고리를형성하고,
[15] [화학식 2]
Figure imgf000003_0003
[17] 화학식 2에서,
[18] 쇼 내지쇼 는서로같거나상이하고,각각독립적으로치환또는비치환된 탄소수 6내지 20의아릴기;또는 -1그 이고,
[19] 1그는직접결합;중수소로치환또는비치환된페닐렌기 ;또는중수소로치환 또는비치환된비페닐릴렌기이며,
[2이 å는치환또는비치환된탄소수 6내지 20의아릴기;또는치환또는비치환된 헤테로아릴기이다.
발명의효과
[21] 본명세서의 일실시상태에 따른유기 발광소자는낮은구동전압,높은효율 2020/175948 1»（：1^1{2020/002861
3 및수명이 개선될수있다.
도면의간단한설명
[22] 도 1및도 2는본명세서의 일실시상태에따르는유기발광소자를도시한 것이다.
[23] [부호의 설명]
[24] 1 :기판
[25] 2:제 1전극
[26] 3:유기물층
[27] 4:제 2전극
[28] 5:정공주입층
[29] 6:정공수송층
[3이 7:정공수송보조층
[31] 8:전자저지층
[32] 9:발광층
[33] 10:정공저지층
[34] 11 :전자주입 및수송층
발명의실시를위한최선의형태
[35] 이하,본명세서에 대하여더욱상세하게설명한다.
[36] 본명세서는제 1전극;상기제 1전극에 대향하여구비된제 2전극;및상기제 1 전극과제 2전극사이에구비된유기물층을포함하는유기발광소자로서,상기 유기물층은상기화학식 1의화합물을포함하는층과,상기 화학식 2의 화합물을 포함하는층을포함하는것인유기 발광소자를제공한다.
[37] 본명세서에 있어서치환기의 예시들은아래에서 설명하나,이에 한정되는 것은아니다.
[38] 상기 "치환’’이라는용어는화합물의 탄소원자에 결합된수소원자가다른 치환기로바뀌는것을의미하며,치환되는위치는수소원자가치환되는위치, 즉치환기가치환가능한위치라면한정하지 않으며， 2이상치환되는경우, 2 이상의치환기는서로동일하거나상이할수있다.
[39] 본명세서에서 "치환또는비치환된”이라는용어는중수소;니트릴기;치환 또는비치환된알킬기;치환또는비치환된시클로알킬기;치환또는비치환된 실릴기;치환또는비치환된알콕시기;치환또는비치환된아릴아민기;치환 또는비치환된아릴기 ;및치환또는비치환된헤테로고리기로이루어진군에서 선택된 1또는 2이상의치환기로치환되었거나상기 예시된치환기중 2이상의 치환기가연결된치환기로치환되거나,또는어떠한치환기도갖지 않는것을 의미한다.예컨대, "2이상의치환기가연결된치환기”는아릴기로치환된 아릴기,헤테로아릴기로치환된아릴기,아릴기로치환된헤테로고리기, 알킬기로치환된아릴기등일수있다. 2020/175948 1»（：1^1{2020/002861
[4이 본명세서에 있어서,알킬기는직쇄또는분지쇄일수있고,탄소수는특별히 한정되지 않으나 1내지 30인것이바람직하다.구체적으로탄소수 1내지 20인 것이 바람직하다.더구체적으로는탄소수 1내지 ^인것이바람직하다.
구체적인 예로는메틸기 ;에틸기 ;프로필기 ; II -프로필기 ;이소프로필기 ;부틸기 ; 11-부틸기 ;이소부틸기 ; -부틸기 ; 8% -부틸기 ; 1 -메틸부틸기 ;：[_에틸부틸기 ; 펜틸기; II -펜틸기;이소펜틸기;네오펜틸기; 1631-펜틸기;핵실기; II -핵실기;
1 -메틸펜틸기 ; 2 -메틸펜틸기 ; 4 -메틸- 2 -펜틸기 ; 3, 3 -디메틸부틸기 ; 2 -에틸부틸기 ; 헵틸기 ; -헵틸기 ; 1 -메틸핵실기 ;시클로펜틸메틸기 ;시클로핵실메틸기 ;옥틸기 ; 11-옥틸기 ;
Figure imgf000005_0001
옥틸기 ; 1 -메틸헵틸기 ; 2 -에틸핵실기 ; 2 -프로필펜틸기 ; II -노닐기 ;
2.2 -디메틸헵틸기; 1 -에틸프로필기; 1,1 -디메틸프로필기;이소핵실기;
2 -메틸펜틸기; 4 -메틸핵실기; 5 -메틸핵실기등이 있으나,이에 한정되는것은 아니다.
[41] 본명세서에 있어서,시클로알킬기는특별히 한정되지 않으나,탄소수 3내지 30인것이바람직하며,탄소수 3내지 20인것이 더바람직하다.구체적으로 시클로프로필기 ;시클로부틸기 ;시클로펜틸기 ; 3 -메틸시클로펜틸기 ;
2.3 -디메틸시클로펜틸기 ;시클로핵실기 ; 3 -메틸시클로핵실기 ;
디메틸시클로핵실기 ; 3, 4, 5 -트리메틸시클로핵실기 ;
Figure imgf000005_0002
시클로헵틸기;시클로옥틸기등이 있으나,이에 한정되는것은아니다.
[42] 본명세서에 있어서,알콕시기는직쇄,분지쇄또는고리쇄일수있다.
알콕시기의 탄소수는특별히 한정되지 않으나,탄소수 1내지 30인것이 바람직하다.구체적으로탄소수 1내지 20인것이바람직하다.더구체적으로 탄소수 1내지 인것이 바람직하다.구체적으로,메톡시기;에톡시기;
11-프로폭시기 ;이소프로폭시기 ; 프로필옥시기 ; II -부톡시기 ;이소부톡시기 ;
1631-부톡시기 ; 8 -부톡시기 ; II -펜틸옥시기 ;네오펜틸옥시기 ;이소펜틸옥시기 ;
!!-핵실옥시기 ; 3, 3 -디메틸부틸옥시기 ; 2 -에틸부틸옥시기 ; II -옥틸옥시기 ;
11-노닐옥시기 ; II -데실옥시기 ;벤질옥시기 ; I) -메틸벤질옥시기등이될수있으나, 이에 한정되는것은아니다.
[43] 본명세서에 있어서,아민기는 - NH2;알킬아민기; 알킬아릴아민기;
아릴아민기 ; 아릴헤테로아릴아민기 ; 알킬헤테로아릴아민기 및
헤테로아릴아민기로이루어진군으로부터선택될수있으며,탄소수는특별히 한정되지 않으나, 1내지 30인것이 바람직하다.아민기의구체적인 예로는 메틸아민기;디메틸아민기;에틸아민기;디에틸아민기;페닐아민기;
나프틸아민기 ;바이페닐아민기 ;안트라세닐아민기 ; 9 -메틸안트라세닐아민기 ; 디페닐아민기 ; 페닐나프틸아민기 ;디톨릴아민기 ; 페닐톨릴아민기 ;
트리페닐아민기 ; 페닐바이페닐아민기 ; 페닐나프틸아민기 ;
바이페닐나프틸아민기 ; 나프틸플루오레닐아민기 ;
페닐페난트레닐아민기 ; 바이페닐페난트레닐아민기 ; 2020/175948 1»（：1^1{2020/002861
5 페닐플루오레닐아민기 ; 페닐터페닐아민기；
페난트레닐플루오레닐아민기 ; 바이페닐플루오레닐아민기등이 있으나, 이에 한정되는것은아니다.
[44] 본명세서에 있어서,실릴기는 -
Figure imgf000006_0001
의화학식으로표시될수있고,상기
Figure imgf000006_0002
하고,각각독립적으로수소;치환또는 비치환된알킬기 ;또는치환또는비치환된아릴기일수있다.상기실릴기는 구체적으로트리메틸실릴기 ;트리에틸실릴기 ; 부틸디메틸실릴기 ;
비닐디메틸실릴기;프로필디메틸실릴기;트리페닐실릴기;디페닐실릴기;
페닐실릴기등이 있으나,이에 한정되는것은아니다.
[45] 본명세서에 있어서 ,아릴기는특별히 한정되지 않으나,탄소수 6내지 20인 것이 바람직하다.상기아릴기는단환식또는다환식일수있다.상기단환식 아릴기로는페닐기;바이페닐기;터페닐기등이 될수있으나,이에 한정되는 것은아니다.상기다환식 아릴기로는나프틸기;안트라세닐기;페난트릴기; 트리페닐기;파이레닐기;플루오레닐기등이될수있으나,이에 한정되는것은 아니다.
[46] 본명세서에 있어서,”인접한”기는해당치환기가치환된원자와직접 연결된 원자에치환된치환기，해당치환기와입체구조적으로가장가깝게위치한 치환기 ,또는해당치환기가치환된원자에치환된다른치환기를의미할수 있다.예컨대,벤젠고리에서오르토 (031110)위치로치환된 2개의치환기 및 지방족고리에서동일탄소에치환된 2개의치환기는서로”인접한”기로해석될 수있다.
[47] 본명세서에 있어서 ,아릴아민기의 예로는치환또는비치환된
모노아릴아민기,치환또는비치환된디아릴아민기,또는치환또는비치환된 트리아릴아민기가있다.상기아릴아민기중의아릴기는단환식아릴기일수 있고,다환식 아릴기일수있다.상기아릴기가 2이상을포함하는아릴아민기는 단환식 아릴기,다환식아릴기,또는단환식아릴기와다환식아릴기를동시에 포함할수있다.예컨대,상기 아릴아민기중의 아릴기는전술한아릴기의 예시 중에서선택될수있다.
[48] 본명세서에 있어서,헤테로아릴기는탄소가아닌원자,즉이종원자를 1이상 포함하는것으로서，구체적으로상기 이종원자는 0, 및 3등으로이루어진 군에서선택되는원자를 1이상포함할수있다.탄소수는특별히 한정되지 않으나,탄소수 2내지 30인것이 바람직하며,탄소수 2내지 20인것이더 바람직하고,상기 헤테로아릴기는단환식또는다환식일수있다.
헤테로아릴기의 예로는티오펜기 ;퓨라닐기 ;피롤기 ;이미다졸릴기 ;티아졸릴기 ; 옥사졸릴기 ;옥사디아졸릴기 ;피리딜기 ;바이피리딜기 ;피리미딜기 ;
트리아지닐기 ;트리아졸릴기 ;아크리딜기 ;피리다지닐기 ;피라지닐기 ;
퀴놀리닐기 ;퀴나졸리닐기 ;퀴녹살리닐기 ;프탈라지닐기 ;피리도피리미딜기 ; 피리도피라지닐기 ;피라지노피라지닐기 ;이소퀴놀리닐기 ;인돌릴기 ; 2020/175948 1»（：1^1{2020/002861
6 카바졸릴기 ;벤즈옥사졸릴기 ;벤즈이미다졸릴기 ;벤조티아졸릴기 ;
벤조카바졸릴기 ;벤조티오펜기 ;디벤조티오펜기 ;벤조퓨라닐기 ;
페난쓰롤리닐기 ( £11&11(；11]'011116);이소옥사졸릴기 ;티아디아졸릴기 ;
페노티아지닐기 및디벤조퓨라닐기등이 있으나,이에 한정되는것은아니다.
[49] 본명세서에 있어서,아릴렌기는 2가기인것을제외하고는전술한아릴기에 관한설명이 적용될수있다.
[5이 본명세서에 있어서,헤테로아릴렌기는 2가기인것을제외하고는전술한 헤테로아릴기에 관한설명이 적용될수있다.
[51] 본명세서의 일실시상태에 있어서,상기화학식 1은하기 화학식 1- 1또는 화학식 1-2로표시될수있다.
[52] [화학식 1- 1]
[53]
Figure imgf000007_0001
[54] [화학식 1-2]
[55]
Figure imgf000007_0002
[56] 상기화학식 1-1및 1-2에서,
[57] 니,사1,및 115내지 1112는화학식 1에서 정의한바와같다. 2020/175948 1»（：1^1{2020/002861
7
[58] 본명세서의 일실시상태에 있어서,상기화학식 1은하기 화학식 1-3내지 화학식 1-6중어느하나로표시될수있다.
[59] [화학식 1-3]
[6이
Figure imgf000008_0001
Figure imgf000008_0002
[63] [화학식 1-5] 2020/175948 1»（：1^1{2020/002861
8
[64]
Figure imgf000009_0001
Figure imgf000009_0003
[67] 상기화학식 1-3내지화학식 1-6에서 ,
[68] 사1,및 115내지 1112는화학식 1에서정의한바와같다.
[69] 본발명의 일실시상태에 있어서
Figure imgf000009_0002
결합,치환또는비치환된 2020/175948 1»（：1/10公020/002861
9 탄소수 6내지 20의아릴렌기,또는치환또는비치환된탄소수 3내지 30의 헤테로아릴렌기이다.
본발명의 일실시상태에 있어서,상기 1^1은직접결합이다.
본발명의 일실시상태에 있어서,상기 은아릴렌기이다.
본발명의 일실시상태에 있어서,상기 은헤테로아릴렌기이다. 본발명의 일실시상태에 있어서,상기 은 0,또는 8중어느하나이상을 포함하는탄소수 3내지 30의 헤테로아릴렌기이다.
[74] 본발명의 일실시상태에 있어서,상기쇼 은치환또는비치환된탄소수 6 내지 20의아릴기,또는치환또는비치환된탄소수 3내지 30의
헤테로아릴기이다.
본발명의 일실시상태에 있어서,상기쇼 은탄소수 6내지 20의 아릴기이다. 본발명의 일실시상태에 있어서,상기쇼 은탄소수 6내지 30의
헤테로아릴기이다.
[77] 본발명의 일실시상태에 있어서,상기쇼 은페닐기;비페닐기;터페닐기; 디메틸플루오렌기;쿼터페닐기;나프틸기;안트라센기;페난트렌기;파이렌기; 또는트리페닐렌기이다.
본발명의 일실시상태에 있어서,상기사1은디벤조퓨란,디벤조티오펜,또는 페닐기로치환또는비치환된카바졸기이다.
[79] 본발명의 일실시상태에 있어서 ,상기사2및사3은서로같다.
[80] 본발명의 일실시상태에 있어서 ,상기사2및사3은서로상이하다.
[81] 본발명의 일실시상태에 있어서 ,상기쇼 및 은각각독립적으로페닐기 , 비페닐기,터페닐기,나프틸기,페난트릴기,트리페닐렌기,알킬기로치환된 플루오렌기,디벤조퓨란기,디벤조티오펜기,또는카바졸기이다.또한,이들은 중수소로추가로치환될수있다.
02247935635681
77777788888888 78 본발명의 일실시상태에 있어서 ,상기 1그는직접결합,중수소로치환또는 비치환된페닐렌기,또는중수소로치환또는비치환된비페닐릴렌기이다. 본발명의 일실시상태에 있어서,상기 å는치환또는비치환된탄소수 6내지 20의다환의아릴기이다.
본발명의 일실시상태에 있어서,상기 는중수소,알킬기,또는아릴기로치환 또는비치환된탄소수 6내지 20의다환의 아릴기이다.
본발명의 일실시상태에 있어서,상기 å는치환또는비치환된탄소수 3내지 30의 헤테로아릴기이다.
본발명의 일실시상태에 있어서,상기 는중수소,알킬기,또는아릴기로치환 또는비치환된탄소수 3내지 30의헤테로아릴기이다.
본발명의 일실시상태에 있어서 ,상기사4는치환또는비치환된아릴기이다. 본발명의 일실시상태에 있어서 ,상기쇼 는치환또는비치환된탄소수 6 내지 20의아릴기이다.
본발명의 일실시상태에 있어서 ,상기쇼 는아릴기로치환또는비치환된 2020/175948 1»（：1^1{2020/002861
10 탄소수 6내지 20의아릴기이다.
[9이 본발명의일실시상태에 있어서,상기화학식 2에서포함될수있는아릴기의 탄소수는 6내지 20이므로,상기화학식 2는스피로비플루오렌기등은포함하지 않는다.
[91] 본명세서의일실시상태에 있어서,상기화학식 1의화합물은하기화합물 중에서선택되는어느하나이다.
[92]
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
() 2020/175948 1»(：1/10公020/002861
20
[106]
Figure imgf000021_0001
[107] 본명세서의일실시상태에 있어서,상기화학식 2의화합물은하기화합물 중에서선택되는어느하나이다.
[108]
[109]
[110]
[111]
[112]
Figure imgf000026_0001
[113]
[114]
[115]
Figure imgf000029_0001
[116]
[117]
[118]
[119]
[120]
[121]
2020/175948 1»（：1^1{2020/002861
35
[122]
Figure imgf000036_0001
[123] 본발명의유기발광소자의구조는도 1및도 2에나타낸것과같은구조를 가질수있으나,이에만한정되는것은아니다.
[124] 도 1에는기판 (1)위에제 1전극 (2),유기물층 (3),및제 2전극 (4)이순차적으로 적층된유기발광소자의구조가예시되어 있다.
[125] 상기도 1은유기 발광소자를예시한것이며 이에 한정되지 않는다.
[126] 도 2에는기판 (1)위에제 1전극 (2),정공주입층 (5),정공수송층 (6),정공수송 보조층 (7),전자저지층 (8),발광층 (9),정공저지층 (10),전자주입 및수송층 (11) 및제 2전극 (4)이순차적으로적층된유기 발광소자의구조가예시되어 있다.본 발명의 화학식 1의 화합물은바람직하게는발광층 (9)에포함될수있고,화학식 2의 화합물은바람직하게는전자저지층 (8)에포함될수있다.
[127] 상기도 1및도 2에서사용된적층구조외에추가의층을더포함할수도있고, 일부층을제외하여사용할수도있다.
[128] 본발명의 일실시상태에 있어서,상기유기물층은발광층을포함하고,상기 발광층은상기화학식 1의화합물을포함한다.
[129] 본발명의 일실시상태에 있어서,상기유기물층은발광층을포함하고,상기 발광층은상기화학식 1의화합물을상기발광층의호스트로포함한다.
[130] 본발명의 일실시상태에 있어서,상기유기물층은정공주입층,정공수송층, 또는정공주입 및수송층을포함하고,상기정공주입층,정공수송층,또는정공 주입 및수송층은상기화학식 1의화합물을포함할수있다.
[131] 본발명의 일실시상태에 있어서,상기유기물층은전자주입층,전자수송층, 또는전자주입 및수송층을포함하고,상기 전자주입층,전자수송층,또는전자 주입및수송층은상기화학식 1의화합물을포함할수있다.
[132] 본발명의일실시상태에 있어서,상기유기물층은전자저지층,또는정공
저지층을포함하고,상기전자저지층,또는정공저지층은상기화학식 1의 화합물을포함할수있다.
[133] 본발명의일실시상태에 있어서,상기유기물층은정공주입층,정공수송층, 또는정공주입및수송층을포함하고,상기정공주입층,정공수송층,또는정공 주입및수송층은상기화학식 2의화합물을포함할수있다.
[134] 본발명의일실시상태에 있어서,상기유기물층은전자주입층,전자수송층, 또는전자주입및수송층을포함하고,상기전자주입층,전자수송층,또는전자 주입및수송층은상기화학식 2의화합물을포함할수있다.
[135] 본발명의일실시상태에 있어서,상기유기물층은전자저지층,또는정공
저지층을포함하고,상기전자저지층,또는정공저지층은상기화학식 2의 화합물을포함할수있다.
[136] 본발명의일실시상태에 있어서,상기유기물층은전자저지층을포함하고, 상기전자저지층은상기화학식 2의화합물을포함한다.
[137] 상기유기발광소자가복수개의유기물층을포함하는경우,상기유기물층은 동일한물질또는다른물질로형성될수있다.
[138] 본명세서의유기발광소자는유기물층중 1층이상이상기화학식 1또는
화학식 2의화합물을이용하여형성되는것을제외하고는당기술분야에알려져 있는재료와방법으로제조될수있다.
[139] 본명세서는또한,상기화합물을이용하여형성된유기발광소자의제조
방법을제공한다.
[14이 예컨대,본발명에따른유기발광소자는스퍼터링 (sputtering)이나전자빔
증발 (e-beam evaporation)과같은 PVD(physical vapor deposition)방법을이용하여 , 기판상에금속또는전도성을가지는금속산화물또는이들의합금을증착시켜 양극을형성하고,그위에상기화학식 1의화합물을포함하는유기물층과상기 화학식 2의화합물을포함하는유기물층을형성한후,그위에음극으로사용할 수있는물질을증착시킴으로써제조될수있다.이와같은방법외에도,기판 상에음극물질부터유기물층,양극물질을차례로증착시켜유기발광소자를 만들수도있다.
[141] 상기양극물질로는통상유기물층으로정공주입이원활할수있도록
일함수가큰물질이바람직하다.본발명에서사용될수있는양극물질의 구체적인예로는바나둠,크롬,구리,아연,금과같은금속또는이들의합금; 아연산화물,인듐산화물,인듐주석산화물 (ITO),인듐아연산화물 (EO)과같은 금속산화물; ZnO:Al또는 Sn02 : 와같은금속과산화물의조합;
폴리 (3 -메틸티오펜),폴리 [3,4-(에틸렌 -1,2 -디옥시 )티오펜] (PEDT),폴리피롤및 폴리아닐린과같은전도성고분자등이 있으나,이들에만한정되는것은아니다.
[142] 상기음극물질로는통상유기물층으로전자주입이용이하도록일함수가작은 물질인것이바람직하다.음극물질의구체적인예로는마그네슘,칼슘,나트륨, 칼륨,티타늄,인둠,이트륨,리튬,가돌리늄,알루미늄,은,주석및납과같은 금속또는이들의합금; LiF/Al또는 Li02/Al과같은다층구조물질등이 있으나, 이들에만한정되는것은아니다.
[143] 상기정공주입물질로는낮은전압에서양극으로부터정공을잘주입받을수 있는물질로서 ,정공주입물질의 HOMO(highest occupied molecular orbital)가 양극물질의일함수와주변유기물층의 HOMO사이인것이바람직하다.정공 주입물질의구체적인예로는금속포피린 (porphyrine),올리고티오펜,아릴아민 계열의유기물,핵사니트릴핵사아자트리페닐렌계열의유기물,
퀴나크리돈 (quinacridone)계열의유기물,페릴렌 (perylene)계열의유기물, 안트라퀴논및폴리아닐린과폴리화합물의계열의전도성고분자등이있으나, 이들에만한정되는것은아니다.
[144] 상기정공수송물질로는양극이나정공주입층으로부터정공을수송받아
발광층으로옮겨줄수있는물질로정공에대한이동성이큰물질이적합하다. 구체적인예로는아릴아민계열의유기물,전도성고분자,및공액부분과 비공액부분이함께있는블록공중합체등이 있으나,이들에만한정되는것은 아니다.
[145] 상기발광물질로는정공수송층과전자수송층으로부터정공과전자를각각 수송받아결합시킴으로써가시광선영역의빛을낼수있는물질로서,형광이나 인광에대한양자효율이좋은물질이바람직하다.구체적인예로는
8 -히드록시-퀴놀린알루미늄착물 (Alq3);카르바졸계열화합물;이량체화 스티릴 (dimerized styryl)화합물; BAlq; 10-히드록시벤조퀴놀린-금속화합물; 벤족사졸,벤즈티아졸및벤즈이미다졸계열의화합물;
폴리 (P-페닐렌비닐렌 )(PPV)계열의고분자;스피로 (spiro)화합물;폴리플루오렌, 루브렌등이 있으나,이들에만한정되는것은아니다.
[146] 도펀트재료로는방향족화합물,스트릴아민화합물,붕소착체,플루오란텐 화합물,금속착체등이 있다.구체적으로방향족화합물로는치환또는 비치환된아릴아미노기를갖는축합방향족환유도체로서,아릴아미노기를 갖는피렌,안트라센,크리센,페리플란텐등이 있으며,스티릴아민화합물로는 치환또는비치환된아릴아민에적어도 1개의아릴비닐기가치환되어있는 화합물로,아릴기,실릴기,알킬기,시클로알킬기및아릴아미노기로이루어진 군에서 1또는 2이상선택되는치환기가치환또는비치환된다.구체적으로 스티릴아민,스티릴디아민,스티릴트리아민,스티릴테트라아민등이있으나, 이에한정되지않는다.또한,금속착체로는이리듐착체,백금착체등이있으나, 이에한정되지않는다.
[147] 본발명의일실시상태에 있어서,상기발광층은호스트와도펀트를포함할수 있다.본발명의일실시상태에있어서,상기유기물층은발광층을포함하고, 상기발광층은호스트와도펀트를 99:1내지 70:30의질량비로포함한다.상기 2020/175948 1»(：1/10公020/002861
38 호스트는본발명의화학식 1의화합물을포함하고,상기도펀트는하기 구조식의화합물을포함할수있다.본발명의일실시상태에있어서,상기 발광층은상기화학식 1의화합물을적색호스트로포함한다.
[148]
Figure imgf000039_0001
¾)_10 베 ¾)_12 [149]
Dp-19 Dp-20 Dp-21 2020/175948 1»（：1^1{2020/002861
41
[151]
Figure imgf000042_0001
Figure imgf000042_0002
[152] 상기 전자수송층은전자주입층으로부터 전자를수취하여발광층까지 전자를 수송하는층으로전자수송물질로는캐소드로부터 전자를잘주입 받아 발광층으로옮겨줄수있는물질로서,전자에 대한이동성이큰물질이
적합하다.구체적인 예로는 8 -히드록시퀴놀린의신착물;쇼1¾을포함한착물; 유기 라디칼화합물;히드록시플라본-금속착물등이 있으나,이들에만한정되는 것은아니다.전자수송층은종래기술에따라사용된바와같이 임의의 원하는 캐소드물질과함께사용할수있다.특히,적절한캐소드물질의 예는낮은 일함수를가지고알루미늄층또는실버층이 뒤따르는통상적인물질이다.
구체적으로세슘,바륨,칼슘,이테르븀및사마륨이고,각경우알루미늄증또는 실버층이 뒤따른다.
[153] 상기 전자주입층은전극으로부터 전자를주입하는층으로,전자를수송하는 능력을갖고,캐소드로부터의 전자주입 효과,발광층또는발광재료에 대하여 우수한전자주입 효과를가지며 ,발광층에서 생성된여기자의 정공주입층에의 이동을방지하고,또한,박막형성능력이우수한화합물이바람직하다.
구체적으로는플루오레논,안트라퀴노다이메탄,다이페노퀴논,티오피란 다이옥사이드,옥사졸,옥사다이아졸,트리아졸,이미다졸,
페릴렌테트라카복실산,프레오레닐리덴메탄,안트론등과그들의유도체,금속 착체화합물및함질소 5원환유도체등이 있으나,이에 한정되지 않는다.
[154] 상기금속착체화합물로서는 8 -하이드록시퀴놀리나토리튬,
비스（8 -하이드록시퀴놀리나토）아연,비스（8 -하이드록시퀴놀리나토）구리 , 비스（8 -하이드록시퀴놀리나토）망간,트리스（8 -하이드록시퀴놀리나토）알루미늄, 트리스（2 -메틸- 8 -하이드록시퀴놀리나토）알루미늄,
트리스（8 -하이드록시퀴놀리나토）갈륨,
비스（10 -하이드록시벤조 ]퀴놀리나토）베릴륨,
비스（10 -하이드록시벤조 ]퀴놀리나토）아연,
비스（2 -메틸- 8 -퀴놀리나토）클로로갈륨,
비스（2 -메틸- 8 -퀴놀리나토）（0 -크레졸라토）갈륨,
비스（2 -메틸- 8 -퀴놀리나토）（1 -나프톨라토）알루미늄,
비스（2 -메틸- 8 -퀴놀리나토）（2 -나프톨라토）갈륨등이 있으나,이에 한정되지 않는다.
[155] 상기정공저지층은정공의캐소드도달을차단하는층으로,일반적으로정공 주입층과동일한조건으로형성될수있다.구체적으로옥사디아졸유도체나 트리아졸유도체,페난트롤린유도체, BCP,알루미늄착물 (aluminum complex) 등이 있으나,이에한정되지않는다.
[156] 본명세서에따른유기발광소자는사용되는재료에따라전면발광형,후면 발광형또는양면발광형일수있다.
[157] 본발명의유기발광소자는전술한화합물을이용하여한증이상의
유기물층을형성하는것을제외하고는,통상의유기발광소자의제조방법및 재료에의하여제조될수있다.
발명의실시를위한형태
[158] 이하에서,실시예를통하여본명세서를더욱상세하게설명한다.그러나, 이하의실시예는본명세서를예시하기위한것일뿐,본명세서를한정하기 위한것은아니다.
[159] ＜실시예＞
[160] 본발명의화합물은대표적인반응으로 B uchwald-Hartwig coupling reaction, Heck coupling reaction, Suzuki coupling reaction등을이용하여제조되었다.
Figure imgf000043_0001
a-1 a
[163] 1)화학식 a-1의제조
[164] 질소분위기에서 naphthalen- 1 -ylboronic acid(100g, 581.2mmol)와
l-bromo-4-chloro-2-nitrobenzene(150.2g, 639.3mmol)를 THF 2,000ml에넣고교반 및환류하였다.이후 potassium carbonate(321.3g, 2324.6mmol)를물 964ml에녹여 투입하고중분히교반한후 bis(tri-tert-butylphosphine)palladium(C))(3g, 5.8mmol)을 투입하였다. 2시간반응후상온으로식히고유기층과물층을분리후유기층을 증류하였다.이를다시클로로포름에녹이고,물로 2회세척후에유기층을 분리하여,무수황산마그네슘을넣고교반한후여과하여여액을감압
증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제하여 화학식 a-1를 111.9g제조하였다 (수율 68%, MS: [M+H]+= 284).
[165] 2)화학식 a의제조
[166] 화학식 a-1 111.9g(1.0 eq)을 P(OEt)3 500mL에넣고환류하여교반하였다. 3시간 후반응물을물에부어서결정을떨어트리고여과하였다.여과한고체를 클로로포름에완전히녹인후물로씻어주고생성물이녹아있는용액을감압 농축하여결정을떨어트려식힌후여과하였다.이를컬럼크로마토그래피로 정제하여 화학식 & 50 (수율 51 %)을얻었다. +印=252
Figure imgf000044_0001
[172] 1)중간체 1의합성
[173] 질소분위기에서 화학식 a(20g, 79.7mmol), 2-chloro- 3 -pheny lquinoxaline( 19.1 g , 79.7mmol), tripotassium phosphate(15.3g, 159.3mmol)을 Toluene 400ml에 넣고 교반및환류하였다.이후 bis(tri-tert-butylphosphine)palladium(0)(().8 g, 1.6 mmol)을투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여 용매를제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회 세척후에유기층을분리하여무수황산마그네슘처리후여과하여 여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 중간체 1 21.8g을얻었다 (수율 60%, MS: [M+H]+= 456).
[174] 2)화합물 1의합성
[175] 질소분위기에서중간체 l(20g, 43.9mmol), 9H-carbazole(7.3g, 43.9mmol),
sodium tert-butoxide(8.4g, 87.9mmol)을 Xylene 400ml에 넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.4g , 0.9mmol)을투입하였다. 2시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에 완전히녹이고물로 2회 세척후에유기층을 분리하여무수황산마그네슘처리후여과하여 여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 1 15.2g을
얻었다 (수율 59%, MS: [M+H]+= 587).
[176] <합성예 2>화합물 2의합성 [177]
[178] 질소분위기에서중간체 2(10g, 19.8mmol), 9H-carbazole(3.5g, 20.8mmol),
sodium tert-butoxide (3.8g, 39.6mmol)을 Xylene 200ml에넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 2시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 2 8.2g을
얻었다 (수율 65%, MS: [M+H]+= 637).
Figure imgf000045_0001
[181] 질소분위기에서중간체 3(10g, 18.3mmol), 5H-benzo [b] carbazole(4.2g,
19.3mmol), sodium tert-butoxide (3.5g, 36.7mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 3 7.3g을얻었다 (수율 55%, MS: [M+H]+= 727).
Figure imgf000045_0002
[184] 질소분위기에서중간체 4 0은, 17.811111101), 1113七6112:0[0|。표1¾&2：016(4.1은, 18.7mmol), sodium tert-butoxide(3.4g, 35.6mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 4 8.9g을얻었다 (수율 67%, MS: [M+H]+= 743).
[185] <합성예 5>화합물 5의합성
[186]
Figure imgf000046_0001
[187] 질소분위기에서중간체 5(Wg, 18.3mmol), 1 lH-benzo[a]carbazole(4.2g,
19.3mmol), sodium tert-butoxide(3.5g, 36.7mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(0.2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 5 9.3g을얻었다 (수율 70%, MS: [M+H]+= 727).
Figure imgf000046_0002
[19이 질소분위기에서중간체 6(10g, 16.1mmol), 5H-benzo[b]carbazole(3.7g,
16.9mmol), sodium tert-butoxide (3.1g, 32.2mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.3mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 6 8.1g을얻었다 (수율 63%, MS: [M+H]+= 802). [191] <합성예 7>화합물 7의합성
[192]
Figure imgf000047_0001
[193] 질소분위기에서중간체 7(10g, 17.5mmol) , 7H-benzo [c] carbazole(4g, 18.4mmol), sodium tert-butoxide(3.4g, 35mmol)을 Xylene 200ml에넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 2시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 7 7.6g을
얻었다 (수율 58%, MS: [M+H]+= 753).
[194] <합성예 8>화합물 8의합성
[195]
Figure imgf000047_0002
[196] 질소분위기에서중간체 8(10g, 18.8mmol), 9H-carbazole(3.3g, 19.8mmol),
sodium tert-butoxide(3.6g, 37.7mmol)을 Xylene 200ml에넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 3시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 8 6.5g을
얻었다 (수율 52%, MS: [M+H]+= 663).
[197] <합성예 9>화합물 9의합성
[198]
Figure imgf000047_0003
[199] 질소분위기에서중간체 9(10g, 16.5mmol), 9H-carbazole(2.9g, 17.3mmol), sodium tert-butoxide (3.2g, 32.9mmol)을 Xylene 200ml에넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.3mmol)을투입하였다. 3시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 9 6.9g을
얻었다 (수율 57%, MS: [M+H]+= 739).
[200] <합성예 10>화합물 10의합성
[201]
Figure imgf000048_0001
[202] 질소분위기에서중간체 10(10g, 18mmol), 1 lH-benzo[a]carbazole(4. lg,
18.9mmol), sodium tert-butoxide(3.5g, 36mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 10 8.2g을얻었다 (수율 62%, MS: [M+H]+= 737).
Figure imgf000048_0002
[205] 질소분위기에서중간체 1 l(10g, 17.2mmol), 5H-benzo[b]carbazole(3.9g,
18.1mmol), sodium tert-butoxide(3.3g, 34.4mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.3mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 11 8 을얻었다 (수율
<합성예 12>화합물 12의합
Figure imgf000049_0001
Figure imgf000049_0002
[208] 질소분위기에서중간체 12(10g, 17.2mmol), 7H-benzo[c]carbazole(3.9g, 18.1 mmol), sodium tert-butoxide(3.3g, 34.4mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.3mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 12 8g을얻었다 (수율 61%, MS: [M+H]+= 763).
[209] <합성예 13>화합물 13의합성
[21이
Figure imgf000049_0003
[211] 질소분위기에서중간체 13(10g, 18.8mmol), 9H-carbazole(3.3g, 19.8mmol), sodium tert-butoxide(3.6g, 37.7mmol)을 Xylene 200ml에넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 3시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 13 7.9g을
얻었다 (수율 63%, MS: [M+H]+= 663).
[212] <합성예 14>화합물 14의합성 [214] 질소분위기에서중간체 14(10g, 17.8mmol), 9H-carbazole(3.1g, 18.7mmol), sodium tert-butoxide(3.4g, 35.6mmol)을 Xylene 200ml에넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 3시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 14 7.3g을 얻었다 (수율 59%, MS: [M+H]+= 693).
[215] <합성예 15>화합물 15의합성
[216]
Figure imgf000050_0001
[217] 질소분위기에서중간체 15(10g, 16.1mmol), 9H-carbazole(2.8g, 16.9mmol), sodium tert-butoxide(3.1g, 32.2mmol)을 Xylene 200ml에넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.3mmol)을투입하였다. 3시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 15 7. 을 얻었다 (수율 59%, MS: [M+H]+= 752).
[218] <합성예 16>화합물 16의합성 [220] 질소분위기에서중간체 16(10g, 18mmol), 7H-benzo[c]carbazole(4.1g, 18.9mmol), sodium tert-butoxide(3.5g, 36mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입했다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 16 8.9g을얻었다 (수율 67%, MS: [M+H]+= 737).
Figure imgf000051_0001
[223] 질소분위기에서중간체 17(10g, 17.8mmol), 5H-benzo[b]carbazole(4. lg, 18.7mmol), sodium tert-butoxide(3.4g, 35.6mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 17 7g을얻었다 (수율 53%, MS: [M+H]+= 743).
[224] <합성예 18>화합물 18의합성 [225]
[226] 질소분위기에서중간체 18(10g, 16.5mmol), 1 lH-benzo[a]carbazole(3.8g, 17.3mmol), sodium tert-butoxide(3.2g, 32.9mmol)을 Xylene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.3mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 18 7.5g을얻었다 (수율 58%, MS: [M+H]+= 789).
[227] <합성예 19>화합물 19의합성
[228]
Figure imgf000052_0001
[229] 질소분위기에서중간체 19(10g, 22.5mmol), 2-bromonaphthalene(4.6g,
22.5mmol), sodium tert-butoxide(4.3g, 44.9mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 19 8 을얻었다 (수율 66%, MS: +印+= 572).
[23이 <합성예 20>화합물 20의합성 [231]
[232] 질소분위기에서중간체 20( 10g, 22.5mmol),
2-bromo-9, 9-dime比 iyl-9H-fluorene(6.1g, 22.5mmol), sodium tert-butoxide(4.3g, 44.9mmol)을 Toluene 200ml에넣고교반및환류하였다.이후
bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 2시간후 반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 20 9g을 얻었다 (수율 63%, MS: [M+H]+= 638).
[233] <합성예 21>화합물 21의합성
[234]
Figure imgf000053_0001
[235] 질소분위기에서중간체 21(10g, 22.5mmol),
3-(4-bromophenyl)-9-phenyl-9H-carbazole(8.9g, 22.5mmol), sodium
tert-butoxide(4.3g, 44.9mmol)을 Toluene 200ml에넣고교반및환류하였다.이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 2시간후 반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 21 11.3g을 얻었다 (수율 66%, MS: [M+H]+= 763).
[236] <합성예 22>화합물 22의합성 [238] 질소분위기에서중간체 22( 10g, 22.5mmol), 3-bromo- 1 , 1 '-biphenyl(5.2g, 22.5 mmol), sodium tert-butoxide(4.3g, 44.9mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 22 8.3g을얻었다 (수율 62%, MS: [M+H]+= 598).
Figure imgf000054_0001
[241] 질소분위기에서중간체 23(10g, 22.5mmol), 2-(4-bromophenyl)naphthalene(6.3g, 22.5mmol), sodium tert-butoxide(4.3g, 44.9mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 23 10g을얻었다 (수율 69%, MS: [M+H]+= 648).
[242] <합성예 24>화합물 24의합성 [243]
[244] 질소분위기에서중간체 24( 10g, 22.5mmol),
4 - (4-bromopheny l)dibenzo [b ,d] f uran(7.2g , 22.5mmol), sodium tert-butoxide(4.3g, 44.9mmol)을 Toluene 200ml에넣고교반및환류하였다.이후
bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 2시간후 반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 24 10g을 얻었다 (수율 65%, MS: [M+H]+= 688).
Figure imgf000055_0001
[247] 질소분위기에서중간체 25(10g, 19.2mmol), 4-bromo- 1,1 ' :2', 1 "-terphenyl(5 ,9g, 19.2mmol), sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 25 8.8g을얻었다 (수율 61%, MS: [M+H]+= 750).
[248] <합성예 26>화합물 26의합성
[249]
Figure imgf000055_0002
[25이 질소분위기에서중간체 26( 10g, 22.5mmol),
9-(4-bromophenyl)-9H-carbazole(7.2g, 22.5mmol), sodium tert-butoxide(4.3g, 44.9mmol)을 Toluene 200ml에넣고교반및환류하였다.이후
bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 2시간후 반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 26 9.6g을 얻었다 (수율 62%, MS: [M+H]+= 687).
[251] <합성예 27>화합물 27의합성
[252]
Figure imgf000056_0001
[253] 질소분위기에서중간체 27(10g, 19.2mmol), 2-bromophenan比 irene(4.9g,
19.2mmol), sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 27 8.4g을얻었다 (수율 63%, MS: [M+H]+= 698).
[254] <합성예 28>화합물 28의합성
[255]
Figure imgf000056_0002
[256] 질소분위기에서중간체 28(10g, 19.2mmol) , 4-bromodibenzo [b ,d] f uran(4.7 g ,
19.2mmol), sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4 mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 28 9은을얻었다 (수율 68%, MS: [M+H]+= 688).
[257] <합성예 29>화합물 29의합성
[258]
Figure imgf000057_0001
[259] 질소분위기에서중간체 29( 10g, 19.2mmol),
4 - (4-bromopheny 1)- 6-pheny ldibenzo [b ,d] f uran(7.6g , 19.2mmol), sodium
tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에넣고교반및환류하였다.이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 3시간후 반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에완전히녹이고물로 2회세척후에유기층을 분리하여무수황산마그네슘처리후여과하여여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 29 l l.lg을 얻었다 (수율 69%, MS: [M+H]+= 840).
Figure imgf000057_0002
[262] 질소분위기에서중간체 30( 10g, 19.2mmol), 4'-bromo-l,l':3',l”-terphenyl(5.9g, 19.2mmol), sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 30 lO.lg을얻었다 (수율 70%, MS: [M+H]+= 750).
[263] <합성예 31>화합물 31의합성 [264]
[265] 질소분위기에서중간체 31(10g, 19.2mmol), bromobenzene(3g, 19.2mmol),
sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에 넣고교반및환류하였다. 이후 bis (tri-tert-buty lpho sphine)palladium(O) (0.2g , 0.4mmol)을투입하였다. 2시간 후반응이종결되어서상온으로식히고감압하여용매를제거하였다.이후 화합물을다시클로로포름에 완전히녹이고물로 2회 세척후에유기층을 분리하여무수황산마그네슘처리후여과하여 여액을감압증류하였다.농축한 화합물을실리카겔컬럼크로마토그래피로정제해서화합물 31 7.8g을
얻었다 (수율 68%, MS: [M+H]+= 598)
[266] <합성예 32>화합물 32의합성
[267]
Figure imgf000058_0001
[268] 질소분위기에서중간체 32( 10g, 19.2mmol), 4-bromo-l,l'-biphenyl(4.5g,
19.2mmol), sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에 넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에 완전히녹이고물로 2회 세척 후에유기층을분리하여무수황산마그네슘처리후여과하여 여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 32 8.9g을얻었다 (수율 69%, MS: [M+H]+= 674).
[269] <합성예 33>화합물 33의합성
[27이
Figure imgf000058_0002
[271] 질소분위기에서중간체 33(10은, 19.211111101), 2-1奸01110仕 1祀11)46116(5.9은, 19.2mmol), sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 3시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 33 9g을얻었다 (수율 63%, MS: [M+H]+= 748).
[272] <합성예 34>화합물 34의합성
[273]
Figure imgf000059_0001
[274] 질소분위기에서중간체 34( 10g, 19.2mmol) , 4-bromodibenzo [b ,d] thiophene(5g , 19.2mmol), sodium tert-butoxide(3.7g, 38.4mmol)을 Toluene 200ml에넣고교반및 환류하였다·이후 bis(tri-tert-butylphosphine)palladium(0)(().2g, 0.4mmol)을 투입하였다. 2시간후반응이종결되어서상온으로식히고감압하여용매를 제거하였다.이후화합물을다시클로로포름에완전히녹이고물로 2회세척 후에유기층을분리하여무수황산마그네슘처리후여과하여여액을감압 증류하였다.농축한화합물을실리카겔컬럼크로마토그래피로정제해서 화합물 34 8.4g을얻었다 (수율 62%, MS: [M+H]+= 704).
[275] <비교예 1>
[276] ITO(indium tin oxide)가 1,000A의두께로박막코팅된유리기판을세제를녹인 증류수에넣고초음파로세척하였다.이때,세제로는피셔사 (Fischer Co.)제품을 사용하였으며,증류수로는밀러포어사 (Millipore Co.)제품의필터 (Filter)로 2차로 걸러진증류수를사용하였다. ITO를 30분간세척한후증류수로 2회반복하여 초음파세척을 W분간진행하였다.증류수세척이끝난후,이소프로필알콜, 아세톤,메탄올의용제로초음파세척을하고건조시킨후플라즈마세정기로 수송시켰다.또한,산소플라즈마를이용하여상기기판을 5분간세정한후진공 증착기로기판을수송시켰다.
[277] 이렇게준비된 ITO투명전극위에정공주입층으로하기 HI-1화합물을
U50A의두께로형성하되하기 A-1화합물을 1.5%농도로 p-doping하였다. 상기정공주입층위에하기 HT-1화합물을진공증착하여막두께 1,000A의 정공수송층을형성하였다.이어서,상기정공수송층위에막두께 500A으로 하기 HT-2화합물을진공증착하여정공수송보조층을형성하였다.정공수송 보조층위에막두께 150A으로하기 EB-1화합물을진공증착하여전자 저지층을형성하였다.이어서,상기 EB-1증착막위에하기 RH-1화합물과하기 2020/175948 1»（：1^1{2020/002861
59
0]>8화합물을 98:2의중량비로진공증착하여 400人두께의적색발광증을 형성하였다.상기발광층위에막두께 30人으로하기 화합물을진공 증착하여정공저지층을형성하였다.이어서,상기정공저지층위에하기
Figure imgf000060_0001
화합물과하기 1 （3화합물을 2: 1의중량비로진공증착하여 300요의두께로전자 주입및수송층을형성하였다.상기전자주입및수송층위에순차적으로 12入 두께로리튬플로라이드山 ）와 1,000요두께로알루미늄을증착하여음극을 형성하였다.
[278] 상기의과정에서유기물의증착속도는 0.4~0.7人 를유지하였고,음극의 리튬플로라이드는 0.3入 ,알루미늄은 2人/8 의증착속도를유지하였으며, 증착시진공도는 2 X 107 ~ 5 X 106 10:0·를유지하여 ,유기발광소자를
제작하였다.
2020/175948 1»（：1/10公020/002861
60
[279]
Figure imgf000061_0001
Figure imgf000061_0002
[28이 <실시예 1 ~ 36>
[281] 비교예 1의유기발광소자에서 1내-1및/또는 £11대신에하기표 1에기재된 화합물을사용하는것을제외하고는,상기비교예 1과동일한방법으로유기 발광소자를제조하였다.
[282] <비교예 2 ~ 21>
[283] 비교예 1의유기발광소자에서 1내-1및/또는 £11대신에하기표 1에기재된 화합물을사용하는것을제외하고는,상기비교예 1과동일한방법으로유기 발광소자를제조하였다.
[284] 상기실시예및비교예에서제조한유기발광소자에 10 111쇼 1112의전류를
인가하였을때,전압,효율,수명을측정하고그결과를하기표 1에나타내었다. 2020/175948 1»(：1^1{2020/002861
61
195은휘도가초기휘도 (5,000 1出)에서 95%로감소되는데소요되는시간을 의미한다.
[285] [표 1]
[286]
Figure imgf000062_0001
2020/175948 1»（：1/10公020/002861
62
[287]
Figure imgf000063_0001
2020/175948 1»（：1^1{2020/002861
63
Figure imgf000064_0001
[289] 상기실험들의결과를나타낸표 1을검토하면,본발명의화합물조합으로 적색유기발광소자를구동하는데있어서,발광효율,구동전압,수명특성을 개선할수있다는것을확인할수있다.본발명의발광층과전자저지층의조합 실험결과는비교예화합물들간의조합실험결과보다우수한결과를나타냈다. 구동전압,효율이상승했으며특히수명결과에있어서매우우수한결과를확인 할수있었다.이것을통해본발명의발광층과전자저지층간의정공이동이 수월하고전자저지층의전자차단능력이발광층안에서생성되는엑시톤이 적색도판트로에너지전달이잘이루워지게만들어서구동전압,효율,수명 특성모두개선시켰다고판단할수있다.

Claims

2020/175948 1»（：1/10公020/002861
64
청구범위
［청구항 1］ 제 1전극;상기제 1전극에대향하여구비된제 2전극;및상기제 1전극과 제 2전극사이에구비된유기물층을포함하는유기발광소자로서, 상기유기물층은하기화학식 1의화합물을포함하는층과,하기화학식 2의화합물을포함하는층을포함하는것인유기발광소자:
［화학식 1］
Figure imgf000065_0001
상기화학식 1에서,
은직접결합;치환또는비치환된아릴렌기 ;또는치환또는비치환된 헤테로아릴렌기이고,
쇼］1은치환또는비치환된아릴기 ;또는치환또는비치환된 헤테로아릴기이며,
III내지 1112는서로같거나상이하고,각각독립적으로수소;니트릴기 ; 할로겐기;치환또는비치환된알킬기;치환또는비치환된실릴기;치환 또는비치환된아릴기 ;또는치환또는비치환된헤테로아릴기이거나, 인접한기끼리결합하여고리를형성하고,
III내지 114중인접한어느 2개의치환기는반드시서로결합하여,치환 또는비치환된방향족고리를형성하고,
［화학식 2］
Figure imgf000065_0002
화학식 2에서,
쇼2내지쇼 는서로같거나상이하고,각각독립적으로치환또는 비치환된탄소수 6내지 20의아릴기;또는丄27이고, 2020/175948 1»（：1^1{2020/002861
65
1그는직접결합;중수소로치환또는비치환된페닐렌기 ;또는중수소로 치환또는비치환된비페닐릴렌기이며,
는치환또는비치환된탄소수 6내지 20의아릴기;또는치환또는 비치환된헤테로아릴기이다.
[청구항 2] 청구항 1에있어서,상기화학식 1은하기화학식 1-1또는화학식 1-2로 표시되는것인유기발광소자:
[화학식 1-1]
Figure imgf000066_0001
상기화학식 1-1및화학식 1-2에서,
1 ,사1,및 115내지 1112는화학식 1에서정의한바와같다.
[청구항 3] 청구항 1에있어서,상기화학식 1은하기화학식 1-3내지화학식 1-6중 어느하나로표시되는것인유기발광소자:
[화학식 1-3] 2020/175948 1»（：1/10公020/002861
66
Figure imgf000067_0001
[화학식 1-5]
2020/175948 1»（：1/10公020/002861
67
Figure imgf000068_0001
상기화학식 1-3내지화학식 1-6에서 ,
사1,및 115내지 1112는화학식 1에서정의한바와같다.
[청구항 4] 청구항 1에있어서,상기화학식 1의화합물은하기화합물중어느 0 2020/175948 1»（：1/10公020/002861
68
하나인것인유기발광소자:
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
2020/175948 1»（：1/10公020/002861
76
[청구항 5] 청구항 1에있어서,상기화학식 2의화합물은하기화합물중어느 하나인것인유기발광소자:
Figure imgf000077_0001
Figure imgf000078_0001
n ° X to
c Ctd
to U sto TL to
X
r to3
t ft rrX：； ft rr,：X x to 9o
¾to：. to X
X f\
d CX¾ XH ^ r&
' o
Figure imgf000080_0001
D
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
2020/175948 1»（：1^1{2020/002861
90
Figure imgf000091_0001
[청구항 6] 청구항 1에 있어서 ,상기유기물층은발광층을포함하고,상기발광층은 상기 화학식 1의 화합물을포함하는것인유기 발광소자.
[청구항 7] 청구항 1에 있어서 ,상기유기물층은전자저지층을포함하고,상기 전자 저지층은상기화학식 2의화합물을포함하는것인유기발광소자.
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