KR102461122B1 - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
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- KR102461122B1 KR102461122B1 KR1020200134420A KR20200134420A KR102461122B1 KR 102461122 B1 KR102461122 B1 KR 102461122B1 KR 1020200134420 A KR1020200134420 A KR 1020200134420A KR 20200134420 A KR20200134420 A KR 20200134420A KR 102461122 B1 KR102461122 B1 KR 102461122B1
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- South Korea
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- compound
- light emitting
- substituted
- unsubstituted
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- 150000001875 compounds Chemical class 0.000 claims description 133
- -1 biphenylyl Chemical group 0.000 claims description 63
- 125000003118 aryl group Chemical group 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 229910052805 deuterium Inorganic materials 0.000 claims description 11
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- 125000006819 (C2-60) heteroaryl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
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- 230000000694 effects Effects 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
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- 125000003277 amino group Chemical group 0.000 description 5
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JLBRGNFGBDNNSF-UHFFFAOYSA-N tert-butyl(dimethyl)borane Chemical group CB(C)C(C)(C)C JLBRGNFGBDNNSF-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- RBNBDIMXFJYDLQ-UHFFFAOYSA-N thieno[3,2-d]pyrimidine Chemical compound C1=NC=C2SC=CC2=N1 RBNBDIMXFJYDLQ-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- KWQNQSDKCINQQP-UHFFFAOYSA-K tri(quinolin-8-yloxy)gallane Chemical compound C1=CN=C2C(O[Ga](OC=3C4=NC=CC=C4C=CC=3)OC=3C4=NC=CC=C4C=CC=3)=CC=CC2=C1 KWQNQSDKCINQQP-UHFFFAOYSA-K 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical group CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical group C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- HTPBWAPZAJWXKY-UHFFFAOYSA-L zinc;quinolin-8-olate Chemical compound [Zn+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 HTPBWAPZAJWXKY-UHFFFAOYSA-L 0.000 description 1
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H10K85/649—Aromatic compounds comprising a hetero atom
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Abstract
본 발명은 유기 발광 소자를 제공한다. The present invention provides an organic light emitting device.
Description
본 발명은 구동 전압, 효율 및 수명이 개선된 유기 발광 소자에 관한 것이다.The present invention relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기 에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물 층을 포함하는 구조를 가진다. 상기 유기물 층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.
상기와 같은 유기 발광 소자에서, 구동 전압, 효율 및 수명이 개선된 유기 발광 소자의 개발이 지속적으로 요구되고 있다.In the organic light emitting device as described above, the development of an organic light emitting device having improved driving voltage, efficiency, and lifespan is continuously required.
본 발명은 구동 전압, 효율 및 수명이 개선된 유기 발광 소자에 관한 것이다. The present invention relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.
본 발명은 하기의 유기 발광 소자를 제공한다:The present invention provides the following organic light emitting device:
양극, anode,
음극, cathode,
상기 양극과 음극 사이에 발광층을 포함하고, a light emitting layer between the anode and the cathode;
상기 발광층은 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물을 포함하는,The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),
유기 발광 소자:Organic light emitting device:
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
X는 O 또는 S이고,X is O or S;
Y1 내지 Y3는 각각 독립적으로, CH 또는 N이고, 단 Y1 내지 Y3 중 적어도 하나는 N이고,Y 1 to Y 3 are each independently CH or N, provided that at least one of Y 1 to Y 3 is N,
Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴이고,Ar 1 and Ar 2 are each independently, substituted or unsubstituted C 6-60 aryl,
R1 및 R2는 각각 독립적으로, 수소; 중수소; 할로겐; 시아노; 니트로; 아미노; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C2-60 알케닐; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,R 1 and R 2 are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C 1-60 alkyl; substituted or unsubstituted C 3-60 cycloalkyl; substituted or unsubstituted C 2-60 alkenyl; substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,
R3는 각각 독립적으로, 수소; 중수소; 할로겐; 시아노; 니트로; 아미노; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C2-60 알케닐; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고, 또는 인접한 2개의 R3가 서로 결합하여 C6-60 방향족 고리; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로방향족 고리를 형성하고,R 3 are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C 1-60 alkyl; substituted or unsubstituted C 3-60 cycloalkyl; substituted or unsubstituted C 2-60 alkenyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C 2-60 heteroaryl including at least one selected from the group consisting of N, O and S, or two adjacent R 3 are bonded to each other to form a C 6-60 aromatic ring; Or to form a C 2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
a1 및 a2는 각각 독립적으로, 0 내지 3의 정수이고,a1 and a2 are each independently an integer of 0 to 3,
a3은 0 내지 8의 정수이고,a3 is an integer from 0 to 8,
[화학식 2] [Formula 2]
상기 화학식 2에서,In Formula 2,
Ar3는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고, 단 Ar3는 N을 적어도 하나 이상 포함하고,Ar 3 is C 2-60 heteroaryl including at least one selected from the group consisting of substituted or unsubstituted N, O and S, provided that Ar 3 includes at least one or more N,
L1은 단일결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴렌이고,L 1 is a single bond; substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene comprising any one or more selected from the group consisting of N, O and S,
R4는 인접한 2개의 R4가 서로 결합하여 C6-60 방향족 고리; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로방향족 고리를 형성하고,R 4 is a C 6-60 aromatic ring in which two adjacent R 4 are bonded to each other; Or to form a C 2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
R5는 각각 독립적으로, 수소; 중수소; 할로겐; 시아노; 니트로; 아미노; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C2-60 알케닐; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고, 또는 인접한 2개 또는 3개의 R5가 서로 결합하여 C6-60 방향족 고리; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로방향족 고리를 형성하고,R 5 are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C 1-60 alkyl; substituted or unsubstituted C 3-60 cycloalkyl; substituted or unsubstituted C 2-60 alkenyl; substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, or two or three adjacent R 5 are bonded to each other to C 6-60 aromatic ring; Or to form a C 2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
a4는 2이고,a4 is 2,
a5는 0 내지 6의 정수이다.a5 is an integer from 0 to 6.
상술한 유기 발광 소자는 발광층에 포함되는 화합물을 조절하여, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. In the above-described organic light emitting device, by controlling a compound included in the light emitting layer, efficiency, low driving voltage, and/or lifespan characteristics may be improved in the organic light emitting device.
도 1은, 기판(1), 양극(2), 발광층(3) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.
도 2는, 기판(1), 양극(2), 정공주입층(5), 정공수송층(6), 전자저지층(7), 발광층(3), 전자수송층(8), 전자주입층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.FIG. 1 shows an example of an organic light emitting device including a
2 shows a
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다. Hereinafter, it will be described in more detail to help the understanding of the present invention. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, it will be described in more detail to help the understanding of the present invention.
본 명세서에서, 또는 는 다른 치환기에 연결되는 결합을 의미한다. In this specification, or means a bond connected to another substituent.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아미노기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 사이클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴포스핀기; 또는 N, O 및 S 원자 중 1개 이상을 포함하는 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다.As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an aryl phosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, in which two or more substituents of the above-exemplified substituents are connected . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably from 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 25의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 25의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 25인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다. In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.
본 명세서에 있어서, 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸,사이클로헥틸메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. 상기 플루오레닐기가 치환되는 경우, 등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted, etc. can be However, the present invention is not limited thereto.
본 명세서에 있어서, 헤테로고리기는 이종 원소로 O, N, Si 및 S 중 1개 이상을 포함하는 헤테로고리기로서, 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하다. 일 실시상태에 따르면, 상기 헤테로고리기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 헤테로고리기의 탄소수는 6 내지 20이다. 헤테로고리기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 비피리딜기, 피리미딜기, 트리아진기, 트리아졸기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀리닐기, 퀴나졸린기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 6 to 30 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 6 to 20 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , indole group, carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.
본 명세서에 있어서, 아르알킬기, 아르알케닐기, 알킬아릴기, 아릴아민기 중의 아릴기는 전술한 아릴기의 예시와 같다. 본 명세서에 있어서, 아르알킬기, 알킬아릴기, 알킬아민기 중 알킬기는 전술한 알킬기의 예시와 같다. 본 명세서에 있어서, 헤테로아릴아민 중 헤테로아릴은 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 아르알케닐기 중 알케닐기는 전술한 알케닐기의 예시와 같다. 본 명세서에 있어서, 아릴렌은 2가기인 것을 제외하고는 전술한 아릴기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로아릴렌은 2가기인 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 탄화수소 고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 아릴기 또는 사이클로알킬기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다.In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, the description of the heterocyclic group described above for heteroaryl among heteroarylamines may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the above-described alkenyl groups. In the present specification, the description of the above-described aryl group may be applied except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.
본 발명은, 양극, 발광층 및 음극을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물 및 상기 화학식 2로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다.The present invention provides an organic light emitting device comprising an anode, a light emitting layer, and a cathode, wherein the light emitting layer includes the compound represented by
본 발명에 따른 유기 발광 소자는 발광층에 포함되는 화합물을 조절하여, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. In the organic light emitting device according to the present invention, by controlling a compound included in the light emitting layer, it is possible to improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.
이하, 각 구성 별로 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail for each configuration.
양극 및 음극positive and negative
본 발명에서 사용되는 양극 및 음극은, 유기 발광 소자에서 사용되는 전극을 의미한다. The anode and cathode used in the present invention mean electrodes used in an organic light emitting device.
상기 양극 물질로는 통상 유기물 층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or 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 or SnO 2 :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 상기 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
또한, 상기 양극 상에는 정공주입층이 추가로 포함될 수 있다. 상기 정공주입층은 정공 주입 물질로 이루어져 있으며, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. In addition, a hole injection layer may be additionally included on the anode. The hole injection layer is made of a hole injection material, and the hole injection material has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and the excitons generated in the light emitting layer A compound which prevents movement to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable.
정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물 층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는, 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. It is preferable that the highest occupied molecular orbital (HOMO) 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 the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene. organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.
정공주입층hole injection layer
본 발명에 따른 유기 발광 소자는 필요에 따라 상기 양극과 후술할 정공수송층 사이에 정공주입층을 추가로 포함할 수 있다. The organic light emitting diode according to the present invention may further include a hole injection layer between the anode and a hole transport layer to be described later, if necessary.
상기 정공 주입 물질로는 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물 층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는, 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정 되는 것은 아니다. The hole injection material is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is generated in the light emitting layer A compound that prevents the excitons from moving to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) 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 the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene. organic materials, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.
정공수송층hole transport layer
본 발명에서 사용되는 정공수송층은 양극 또는 양극 상에 형성된 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 정공 수송 물질의 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. The hole transport layer used in the present invention is a layer that receives holes from the hole injection layer formed on the anode or the anode and transports them to the light emitting layer. As a material with high hole mobility, it is suitable. Specific examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.
전자저지층electronic barrier layer
본 발명에서 사용되는 전자저지층은 음극에서 주입된 전자가 발광층에서 재결합되지 않고 정공수송층으로 넘어가는 것을 방지하기 위해 정공수송층과 발광층의 사이에 두는 층으로, 전자억제층으로 불리기도 한다. 전자저지층에는 전자수송층보다 전자 친화력이 작은 물질이 바람직하다.The electron blocking layer used in the present invention is a layer placed between the hole transport layer and the emission layer in order to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the emission layer, and is also called an electron blocking layer. For the electron blocking layer, a material having an electron affinity lower than that of the electron transport layer is preferable.
발광층light emitting layer
상기 발광층에 포함되는 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다.The light emitting material included in the light emitting layer is a material capable of emitting light in the visible ray region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.
일반적으로, 발광층은 호스트 재료와 도펀트 재료를 포함하며, 상기 화학식 1 및 상기 화학식 2로 표시되는 화합물을 호스트로 포함할 수 있다. 상기 화학식 1로 표시되는 화합물 및 상기 화학식 2로 표시되는 화합물의 중량비는 99:1 내지 1:99, 또는 90:10 내지 20:80일 수 있으나, 이에 한정되는 것은 아니다.In general, the emission layer includes a host material and a dopant material, and may include the compound represented by
본 발명에 있어서, a1은 R1의 개수를 나타낸 것으로서, a1이 2 이상일 경우, 2 이상의 R1은 서로 동일하거나 상이할 수 있다. a2 내지 a5에 대한 설명은 상기 a1에 대한 설명과 상기 화학식 1 및 화학식 2의 구조를 참조하여 이해될 수 있다.In the present invention, a1 represents the number of R 1 , and when a1 is 2 or more, two or more R 1 may be the same or different from each other. Descriptions of a2 to a5 may be understood with reference to the description of a1 and the structures of
바람직하게는, Y1 내지 Y3는 각각 N일 수 있다.Preferably, Y 1 to Y 3 may each be N.
바람직하게는, Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-20 아릴일 수 있고,Preferably, Ar 1 and Ar 2 may each independently be a substituted or unsubstituted C 6-20 aryl,
보다 바람직하게는, Ar1 및 Ar2는 각각 독립적으로, 페닐, 5개의 중수소로 치환된 페닐, 또는 비페닐릴일 수 있다.More preferably, Ar 1 and Ar 2 may each independently be phenyl, phenyl substituted with 5 deuterium, or biphenylyl.
바람직하게는, R1 및 R2는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C1-10 알킬; 치환 또는 비치환된 C3-20 사이클로알킬; 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴일 수 있고,Preferably, R 1 and R 2 are each independently hydrogen; heavy hydrogen; substituted or unsubstituted C 1-10 alkyl; substituted or unsubstituted C 3-20 cycloalkyl; substituted or unsubstituted C 6-20 aryl; Or it may be a C 2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
보다 바람직하게는, R1 및 R2는 각각 독립적으로, 수소, 중수소, 또는 페닐일 수 있다.More preferably, R 1 and R 2 may each independently be hydrogen, deuterium, or phenyl.
바람직하게는, R3는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C1-10 알킬; 치환 또는 비치환된 C3-20 사이클로알킬; 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴일 수 있고, 또는 인접한 2개의 R3가 서로 결합하여 C6-20 방향족 고리; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로방향족 고리를 형성할 수 있고,Preferably, each R 3 is independently hydrogen; heavy hydrogen; substituted or unsubstituted C 1-10 alkyl; substituted or unsubstituted C 3-20 cycloalkyl; substituted or unsubstituted C 6-20 aryl; Or it may be a C 2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, or two adjacent R 3 are bonded to each other to form a C 6-20 aromatic ring ; Or it may form a C 2-20 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
보다 바람직하게는, R3는 각각 독립적으로, 수소, 중수소, 페닐, 또는 5개의 중수소로 치환된 페닐이거나, 인접한 2개의 R3가 서로 결합하여, , 또는 을 형성할 수 있다.More preferably, each R 3 is independently hydrogen, deuterium, phenyl, or phenyl substituted with 5 deuterium, or two adjacent R 3 are bonded to each other , , or can form.
상기 화학식 1로 표시되는 화합물의 대표적인 예는 하기와 같다:Representative examples of the compound represented by
. .
상기 화학식 1로 표시되는 화합물은 일례로 하기 반응식 1-1 또는 반응식 1-2와 같은 제조 방법으로 제조할 수 있으며, 그 외 나머지 화합물도 유사하게 제조할 수 있다.The compound represented by
[반응식 1-1][Scheme 1-1]
[반응식 1-2][Scheme 1-2]
상기 반응식 1-1 및 1-2에서, X, Y1 내지 Y3, Ar1, Ar2, R1 내지 R3 및 a1 내지 a3는 상기 화학식 1에서 정의한 바와 같으며, Z1 및 Z2는 각각 독립적으로 할로겐이고, 바람직하게는 Z1 및 Z2는 각각 독립적으로 플루오로, 클로로 또는 브로모이다.In Schemes 1-1 and 1-2, X, Y 1 to Y 3 , Ar 1 , Ar 2 , R 1 to R 3 and a1 to a3 are as defined in
상기 반응식 1-1은 스즈키 커플링 반응으로서, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 스즈키 커플링 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 또한, 상기 반응식 1-2는 아민 치환 반응으로서, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 아민 치환 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.The Suzuki coupling reaction in Scheme 1-1 is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. In addition, Scheme 1-2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.
바람직하게는, 상기 화학식 2는 하기 화학식 2-1 내지 화학식 2-3 중 어느 하나로 표시될 수 있다:Preferably,
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
상기 화학식 2-1 내지 화학식 2-3에 있어서,In Formulas 2-1 to 2-3,
Ar3, L1, R5 및 a5에 대한 설명은 상기 화학식 2에서 정의한 바와 같다.Ar 3 , L 1 , R 5 and a5 are the same as defined in
바람직하게는, Ar3는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴일 수 있고, 단 Ar5는 N을 적어도 하나 이상 포함하고,Preferably, Ar 3 may be C 2-20 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S, provided that Ar 5 includes at least one or more N do,
보다 바람직하게는, Ar3는 퀴나졸리닐, 벤조[h]퀴나졸리닐, 트리아지닐, 피리미디닐, 퀴녹살리닐, 또는 일 수 있고, 상기 Ar3는 비치환되거나, 또는 페닐, 비페닐릴, 나프틸, 디메틸플루오레닐, 디벤조퓨라닐, 디벤조티오페닐 및 페닐 카바졸릴로 구성되는 군으로부터 선택되는 1개 내지 3개의 치환기로 치환될 수 있고,More preferably, Ar 3 is quinazolinyl, benzo[h]quinazolinyl, triazinyl, pyrimidinyl, quinoxalinyl, or may be, wherein Ar 3 is unsubstituted, or one selected from the group consisting of phenyl, biphenylyl, naphthyl, dimethyl fluorenyl, dibenzofuranyl, dibenzothiophenyl and phenyl carbazolyl may be substituted with three substituents,
가장 바람직하게는, Ar3는 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다:Most preferably, Ar 3 may be any one selected from the group consisting of:
. .
바람직하게는, L1은 단일결합; 치환 또는 비치환된 C6-20 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴렌일 수 있고,Preferably, L 1 is a single bond; substituted or unsubstituted C 6-20 arylene; Or it may be a C 2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,
보다 바람직하게는, L1은 단일결합, 페닐렌, 나프틸렌, 또는 디벤조퓨라닐렌일 수 있다.More preferably, L 1 may be a single bond, phenylene, naphthylene, or dibenzofuranylene.
바람직하게는, R5는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C1-10 알킬; 치환 또는 비치환된 C3-20 사이클로알킬; 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴일 수 있고, 또는 인접한 2개 또는 3개의 R5가 서로 결합하여 C6-20 방향족 고리; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로방향족 고리를 형성할 수 있고,Preferably, each R 5 is independently hydrogen; heavy hydrogen; substituted or unsubstituted C 1-10 alkyl; substituted or unsubstituted C 3-20 cycloalkyl; substituted or unsubstituted C 6-20 aryl; Or it may be C 2-20 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S, or two or three adjacent R 5 are bonded to each other to C 6- 20 aromatic rings; Or it may form a C 2-20 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
보다 바람직하게는, R5는 각각 독립적으로, 수소, 중수소, 페닐, 카바졸릴, 페닐 카바졸릴이거나, 인접한 2개 또는 3개의 R5가 서로 결합하여 벤젠고리, , , , , , , 또는 을 형성할 수 있다.More preferably, R 5 is each independently hydrogen, deuterium, phenyl, carbazolyl, phenyl carbazolyl, or two or three adjacent R 5 are bonded to each other to form a benzene ring, , , , , , , or can form.
상기 화학식 2로 표시되는 화합물의 대표적인 예는 하기와 같다:Representative examples of the compound represented by
. .
상기 화학식 2로 표시되는 화합물은 일례로 하기 반응식 2와 같은 제조 방법으로 제조할 수 있으며, 그 외 나머지 화합물도 유사하게 제조할 수 있다.The compound represented by
[반응식 2][Scheme 2]
상기 반응식 2에서, Ar3, L1, R4, R5, a4 및 a5는 상기 화학식 2에서 정의한 바와 같으며, Z3는 할로겐이고, 바람직하게는 Z3는 클로로 또는 브로모이다.In
상기 반응식 2는 아민 치환 반응으로서, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 아민 치환 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.
상기 도펀트 재료로는 유기 발광 소자에 사용되는 물질이면 특별히 제한되지 않는다. 일례로, 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 사이클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.
전자수송층electron transport layer
본 발명에 따른 유기 발광 소자는, 상기 발광층과 음극 사이에 전자수송층을 포함할 수 있다. The organic light emitting diode according to the present invention may include an electron transport layer between the light emitting layer and the cathode.
상기 전자수송층은, 음극 또는 음극 상에 형성된 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하고, 또한 발광층에서 정공이 전달되는 것을 억제하는 층으로, 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode, transports electrons to the light emitting layer, and inhibits the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode As a material that can receive and transfer to the light emitting layer, a material with high electron mobility is suitable. As the electron transport material, a material capable of well injecting electrons from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable.
상기 전자 수송 물질의 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.Specific examples of the electron transport material include an Al complex of 8-hydroxyquinoline; complexes comprising Alq 3 ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.
전자주입층electron injection layer
본 발명에 따른 유기 발광 소자는 상기 전자수송층과 음극 사이에 전자주입층을 추가로 포함할 수 있다. 상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. The organic light emitting diode according to the present invention may further include an electron injection layer between the electron transport layer and the cathode. 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, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable.
상기 전자주입층으로 사용될 수 있는 물질의 구체적인 예로는, 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 있으나, 이에 한정되지 않는다. Specific examples of the material that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preole nylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 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[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.
한편, 본 발명에 있어서 "전자 주입 및 수송층"은 상기 전자주입층과 상기 전자수송층의 역할을 모두 수행하는 층으로 상기 각 층의 역할을 하는 물질을 단독으로, 혹은 혼합하여 사용할 수 있으나, 이에 한정되지 않는다.On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the role of the electron injection layer and the electron transport layer, and the materials serving the respective layers may be used alone or in combination, but limited thereto. doesn't happen
유기 발광 소자organic light emitting device
본 발명에 따른 유기 발광 소자의 구조를 도 1 및 도 2에 예시하였다. 도 1은, 기판(1), 양극(2), 발광층(3) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 도 2는, 기판(1), 양극(2), 정공주입층(5), 정공수송층(6), 전자저지층(7), 발광층(3), 전자수송층(8), 전자주입층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2 . FIG. 1 shows an example of an organic light emitting device including a
본 발명에 따른 유기 발광 소자는 상술한 구성을 순차적으로 적층시켜 제조할 수 있다. 이때, 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition)방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 상술한 각 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. 또한, 발광층은 호스트 및 도펀트를 진공 증착법 뿐만 아니라 용액 도포법에 의하여 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. And, after forming each of the above-mentioned layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
한편, 본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.
[제조예][Production Example]
제조예 1: 화합물 1-1의 제조Preparation Example 1: Preparation of compound 1-1
단계 1) 화합물 1-1-a의 제조Step 1) Preparation of compound 1-1-a
질소 분위기에서 8-bromo-1-chlorodibenzo[b,d]furan(15.0 g, 53.3 mmol)와 9H-carbazole(9.8 g, 58.6 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(7.7 g, 79.9 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.8 g, 1.6 mmol)을 투입하였다. 6 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1-a를 12.0 g 제조하였다. (수율 61 %, MS: [M+H]+= 369).In a nitrogen atmosphere, 8-bromo-1-chlorodibenzo[b,d]furan (15.0 g, 53.3 mmol) and 9H-carbazole (9.8 g, 58.6 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (7.7 g, 79.9 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.6 mmol) were added. After the reaction for 6 hours, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.0 g of compound 1-1-a. (Yield 61%, MS: [M+H]+=369).
단계 2) 화합물 1-1-b의 제조Step 2) Preparation of compound 1-1-b
질소 분위기에서 화합물 1-1-a(15.0 g, 40.8 mmol)와 bis(pinacolato)diboron(11.4 g, 44.9 mmol)를 1,4-dioxane 300 ml에 환류시키며 교반하였다. 이 후 potassium acetate(6.0 g, 61.2 mmol)를 투입하고 충분히 교반한 후 bis(dibenzylideneacetone)palladium(0)(0.7 g, 1.2 mmol) 및 tricyclohexylphosphine(0.7 g, 2.4 mmol)을 투입하였다. 7 시간 반응하고 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-1-b를 11.6 g 제조하였다. (수율 62 %, MS: [M+H]+= 460)Compound 1-1-a (15.0 g, 40.8 mmol) and bis(pinacolato)diboron (11.4 g, 44.9 mmol) were stirred in 300 ml of 1,4-dioxane under reflux in a nitrogen atmosphere. After that, potassium acetate (6.0 g, 61.2 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.2 mmol) and tricyclohexylphosphine (0.7 g, 2.4 mmol) were added. After reacting for 7 hours, cooling to room temperature, and separating the organic layer using chloroform and water, the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of compound 1-1-b. (Yield 62%, MS: [M+H]+=460)
단계 3) 화합물 1-1의 제조Step 3) Preparation of compound 1-1
질소 분위기에서 화합물 1-1-b(15.0 g, 32.7 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(9.6 g, 35.9 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(18.1 g, 130.6 mmol)를 물 54 ml에 녹여 투입하고 충분히 교반한 후 tetrakis(triphenylphosphine)palladium(0)(1.1 g, 1.0 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 1-1을 5.5 g 제조하였다. (수율 30 %, MS: [M+H]+= 566)In a nitrogen atmosphere, compound 1-1-b (15.0 g, 32.7 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (9.6 g, 35.9 mmol) were added to 300 ml of THF, stirred and refluxed. did. Thereafter, potassium carbonate (18.1 g, 130.6 mmol) was dissolved in 54 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0)(1.1 g, 1.0 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 5.5 g of compound 1-1 was prepared through sublimation purification. (Yield 30%, MS: [M+H]+= 566)
제조예 2: 화합물 1-2의 제조Preparation Example 2: Preparation of compound 1-2
제조예 1에서, 8-bromo-1-chlorodibenzo[b,d]furan을 3-bromo-7-chlorodibenzo[b,d]furan으로, 9H-carbazole을 2-(phenyl-d5)-9H-carbazole로 변경하여 사용한 것을 제외하고는, 화합물 1-1의 제조 방법과 동일한 제조 방법으로 화합물 1-2를 제조하였다. (MS[M+H]+= 647)In Preparation Example 1, 8-bromo-1-chlorodibenzo[b,d]furan to 3-bromo-7-chlorodibenzo[b,d]furan, 9H-carbazole to 2-(phenyl-d5)-9H-carbazole Compound 1-2 was prepared in the same manner as in the preparation method of compound 1-1, except that it was changed and used. (MS[M+H] + = 647)
제조예 3: 화합물 1-3의 제조Preparation Example 3: Preparation of compound 1-3
단계 1) 화합물 1-3-a의 제조Step 1) Preparation of compound 1-3-a
질소 분위기에서 1-chloro-7-fluorodibenzo[b,d]furan(15.0 g, 68 mmol)와 bis(pinacolato)diboron(19.0 g, 74.8 mmol)를 1,4-dioxane 300 ml에 환류시키며 교반하였다. 이 후 potassium acetate(10.0 g, 102.0 mmol)를 투입하고 충분히 교반한 후 bis(dibenzylideneacetone)palladium(0)(1.2 g, 2.0 mmol) 및 tricyclohexylphosphine(1.1 g, 4.1 mmol)을 투입하였다. 7 시간 반응하고 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-3-a를 15.9 g 제조하였다. (수율 75 %, MS: [M+H]+= 313)In a nitrogen atmosphere, 1-chloro-7-fluorodibenzo[b,d]furan (15.0 g, 68 mmol) and bis(pinacolato)diboron (19.0 g, 74.8 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Thereafter, potassium acetate (10.0 g, 102.0 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1.2 g, 2.0 mmol) and tricyclohexylphosphine (1.1 g, 4.1 mmol) were added. After reacting for 7 hours, cooling to room temperature, and separating the organic layer using chloroform and water, the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of compound 1-3a. (yield 75%, MS: [M+H]+= 313)
단계 2) 화합물 1-3-b의 제조Step 2) Preparation of compound 1-3b
질소 분위기에서 화합물 1-3-a(15.0 g, 48.1 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(14.2 g, 52.9 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(26.6 g, 192.2 mmol)를 물 80 ml에 녹여 투입하고 충분히 교반한 후 tetrakis(triphenylphosphine)palladium(0)(1.7 g, 1.4 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-3-b를 14.8 g 제조하였다. (수율 74 %, MS: [M+H]+= 418)In a nitrogen atmosphere, compound 1-3a (15.0 g, 48.1 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (14.2 g, 52.9 mmol) were added to 300 ml of THF, stirred and refluxed. did. Thereafter, potassium carbonate (26.6 g, 192.2 mmol) was dissolved in 80 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0) (1.7 g, 1.4 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of compound 1-3b. (Yield 74%, MS: [M+H]+= 418)
단계 3) 화합물 1-3의 제조Step 3) Preparation of compound 1-3
질소 분위기에서 화합물 1-3-b(20.0 g, 47.9 mmol)와 3-phenyl-9H-carbazole(12.8 g, 52.7 mmol)를 DMF 400 ml에 넣고 환류시키며 교반하였다. 이 후 cesium carbonate(46.8 g, 143.7 mmol)를 투입하고 교반하였다. 10 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 1-3을 15.3 g 제조하였다. (수율 50 %, MS: [M+H]+= 642)In a nitrogen atmosphere, compound 1-3b (20.0 g, 47.9 mmol) and 3-phenyl-9H-carbazole (12.8 g, 52.7 mmol) were added to 400 ml of DMF and stirred under reflux. After that, cesium carbonate (46.8 g, 143.7 mmol) was added and stirred. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 15.3 g of compound 1-3 was prepared through sublimation purification. (Yield 50%, MS: [M+H]+= 642)
제조예 4: 화합물 1-4의 제조Preparation Example 4: Preparation of compound 1-4
제조예 3에서, 1-chloro-7-fluorodibenzo[b,d]furan을 1-chloro-6-fluorodibenzo[b,d]furan으로, 2-chloro-4,6-diphenyl-1,3,5-triazine을 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine으로, 3-phenyl-9H-carbazole을 9H-carbazole로 변경하여 사용한 것을 제외하고는, 화합물 3의 제조 방법과 동일한 제조 방법으로 화합물 1-4를 제조하였다. (MS[M+H]+= 642)In Preparation Example 3, 1-chloro-7-fluorodibenzo[b,d]furan to 1-chloro-6-fluorodibenzo[b,d]furan, 2-chloro-4,6-diphenyl-1,3,5- triazine to 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine and 3-phenyl-9H-carbazole to 9H-carbazole Compound 1-4 was prepared by the same preparation method as that of
제조예 5: 화합물 1-5의 제조Preparation Example 5: Preparation of compound 1-5
제조예 3에서, 1-chloro-7-fluorodibenzo[b,d]furan을 7-chloro-1-fluorodibenzo[b,d]furan으로, 2-chloro-4,6-diphenyl-1,3,5-triazine을 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine으로, 3-phenyl-9H-carbazole을 9H-carbazole로 변경하여 사용한 것을 제외하고는, 화합물 5의 제조 방법과 동일한 제조 방법으로 화합물 1-5를 제조하였다. (MS[M+H]+= 642)In Preparation Example 3, 1-chloro-7-fluorodibenzo[b,d]furan to 7-chloro-1-fluorodibenzo[b,d]furan, 2-chloro-4,6-diphenyl-1,3,5- triazine to 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine and 3-phenyl-9H-carbazole to 9H-carbazole Except for the use, Compound 1-5 was prepared in the same manner as that of
제조예 6: 화합물 1-6의 제조Preparation Example 6: Preparation of compound 1-6
단계 1) 화합물 1-6-a의 제조Step 1) Preparation of compound 1-6-a
질소 분위기에서 4,6-dibromodibenzo[b,d]furan-1,2,3,7,8,9-d6(15.0 g, 45.2 mmol)와 9H-carbazole(8.3 g, 49.7 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(6.5 g, 67.8 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.7 g, 1.4 mmol)을 투입하였다. 7 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-6-a를 14.4 g 제조하였다. (수율 76 %, MS: [M+H]+= 419)300 ml of toluene with 4,6-dibromodibenzo[b,d]furan-1,2,3,7,8,9-d6 (15.0 g, 45.2 mmol) and 9H-carbazole (8.3 g, 49.7 mmol) in nitrogen atmosphere was added, stirred and refluxed. Then, sodium tert-butoxide (6.5 g, 67.8 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) were added. After the reaction for 7 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound 1-6-a. (Yield 76%, MS: [M+H]+= 419)
단계 2) 화합물 1-6-b의 제조Step 2) Preparation of compound 1-6-b
질소 분위기에서 화합물 1-6-a(15.0 g, 35.9 mmol)와 bis(pinacolato)diboron(10.0 g, 39.4 mmol)를 1,4-dioxane 300 ml에 환류시키며 교반하였다. 이 후 potassium acetate(5.3 g, 53.8 mmol)를 투입하고 충분히 교반한 후 bis(dibenzylideneacetone)palladium(0)(0.6 g, 1.1 mmol) 및 tricyclohexylphosphine(0.6 g, 2.2 mmol)을 투입하였다. 8 시간 반응하고 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-6-b를 10.7 g 제조하였다. (수율 64 %, MS: [M+H]+= 466)Compound 1-6-a (15.0 g, 35.9 mmol) and bis(pinacolato)diboron (10.0 g, 39.4 mmol) were stirred in 300 ml of 1,4-dioxane under reflux in a nitrogen atmosphere. After that, potassium acetate (5.3 g, 53.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.2 mmol) were added. After reacting for 8 hours, cooling to room temperature, and separating the organic layer using chloroform and water, the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 1-6-b. (Yield 64%, MS: [M+H]+= 466)
단계 3) 화합물 1-6의 제조Step 3) Preparation of compound 1-6
질소 분위기에서 화합물 1-6-b(15.0 g, 32.2 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(9.5 g, 35.5 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.8 g, 128.9 mmol)를 물 53 ml에 녹여 투입하고 충분히 교반한 후 tetrakis(triphenylphosphine)palladium(0)(1.1 g, 1.0 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 1-6을 8.8 g 제조하였다. (수율 48 %, MS: [M+H]+= 572)In a nitrogen atmosphere, compound 1-6-b (15.0 g, 32.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (9.5 g, 35.5 mmol) were added to 300 ml of THF, stirred and refluxed. did. Thereafter, potassium carbonate (17.8 g, 128.9 mmol) was dissolved in 53 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0) (1.1 g, 1.0 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 8.8 g of compound 1-6 was prepared through sublimation purification. (Yield 48%, MS: [M+H]+= 572)
제조예 7: 화합물 1-7의 제조Preparation Example 7: Preparation of compound 1-7
단계 1) 화합물 1-7-a의 제조Step 1) Preparation of compound 1-7-a
질소 분위기에서 3-bromodibenzo[b,d]thiophene(15.0 g, 57 mmol)와 7H-benzofuro[2,3-b]carbazole(16.1 g, 62.7 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(8.2 g, 85.5 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.9 g, 1.7 mmol)을 투입하였다. 6 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-7-a를 17.3 g 제조하였다. (수율 69 %, MS: [M+H]+= 441)In a nitrogen atmosphere, 3-bromodibenzo[b,d]thiophene (15.0 g, 57 mmol) and 7H-benzofuro[2,3-b]carbazole (16.1 g, 62.7 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (8.2 g, 85.5 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) were added thereto. After the reaction for 6 hours, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 1-7-a. (yield 69%, MS: [M+H]+= 441)
단계 2) 화합물 1-7-b의 제조Step 2) Preparation of compound 1-7-b
플라스크에 화합물 1-7-a(10.0 g, 22.8 mmol), THF 100 ml을 넣고, -78 ℃로 냉각했다. 1.6M의 n-butyllithium in hexane(15.0ml, 23.9 mmol)을 적가하고, -78 ℃에서 20 분간 교반했다. 붕산 트라이아이소프로필(3.1 g, 29.6 mmol)을 가하여 -78 ℃에서 1 시간 교반 후, 상온에서 4 시간 더 교반하였다. 이 후 1N HCl을 가하여 실온에서 1 시간 교반후 반응액을 농축하여, 분액 깔대기에 옮기고, H2O 200 ml을 가한 후 CH2Cl2로 추출하였다. 추출액에 무수황산마그네슘을 넣고 건조후, 여과, 농축한 후, 재결정을 하여 화합물 1-7-b를 6.6 g 제조하였다. (수율 60 %, MS: [M+H]+= 484)Compound 1-7-a (10.0 g, 22.8 mmol) and 100 ml of THF were placed in a flask and cooled to -78 °C. 1.6M n-butyllithium in hexane (15.0 ml, 23.9 mmol) was added dropwise, and the mixture was stirred at -78°C for 20 minutes. Triisopropyl borate (3.1 g, 29.6 mmol) was added and stirred at -78 °C for 1 hour, followed by further stirring at room temperature for 4 hours. Then, 1N HCl was added, stirred at room temperature for 1 hour, the reaction solution was concentrated, transferred to a separatory funnel, 200 ml of H 2 O was added, and the mixture was extracted with CH 2 Cl 2 . Anhydrous magnesium sulfate was added to the extract, dried, filtered, concentrated, and recrystallized to prepare 6.6 g of compound 1-7-b. (Yield 60%, MS: [M+H] + = 484)
단계 3) 화합물 1-7의 제조Step 3) Preparation of compound 1-7
질소 분위기에서 화합물 1-7-b(15.0 g, 31 mmol)와 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine(9.5 g, 34.1 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(17.2 g, 124.1 mmol)를 물 51 ml에 녹여 투입하고 충분히 교반한 후 tetrakis(triphenylphosphine)palladium(0)(1.1 g, 0.9 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 1-7을 9.7 g 제조하였다. (수율 46 %, MS: [M+H]+= 682)Compound 1-7-b (15.0 g, 31 mmol) and 2-chloro-4,6-bis(phenyl-d5)-1,3,5-triazine (9.5 g, 34.1 mmol) in THF 300 ml in a nitrogen atmosphere was added, stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.1 mmol) was dissolved in 51 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0)(1.1 g, 0.9 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 9.7 g of compound 1-7 was prepared through sublimation purification. (Yield 46%, MS: [M+H] + = 682)
제조예 8: 화합물 1-8의 제조Preparation 8: Preparation of compound 1-8
단계 1) 화합물 1-8-a의 제조Step 1) Preparation of compound 1-8-a
질소 분위기에서 dibenzo[b,d]thiophen-4-ylboronic acid(15.0 g, 65.8 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(19.4 g, 72.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(36.4 g, 263.1 mmol)를 물 109 ml에 녹여 투입하고 충분히 교반한 후 tetrakis(triphenylphosphine)palladium(0)(2.3 g, 2.0 mmol)을 투입하였다. 8 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-8-a를 19.7 g 제조하였다. (수율 72 %, MS: [M+H]+= 417)In a nitrogen atmosphere, dibenzo[b,d]thiophen-4-ylboronic acid (15.0 g, 65.8 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4 g, 72.3 mmol) were mixed with THF 300 ml, stirred and refluxed. Thereafter, potassium carbonate (36.4 g, 263.1 mmol) was dissolved in 109 ml of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0) (2.3 g, 2.0 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of compound 1-8-a. (Yield 72%, MS: [M+H]+= 417)
단계 2) 화합물 1-8-b의 제조Step 2) Preparation of compound 1-8-b
질소 분위기에서 화합물 1-8-a(20.0 g, 48.1 mmol), N-bromosuccinimide(9 g, 50.5 mmol)을 dimethylformamide 400 ml에 넣고 상온에서 교반하였다. 6 시간 반응 후, 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 1-8-b를 15.7g 제조하였다. (수율 66 %, MS: [M+H]+= 495)Compound 1-8-a (20.0 g, 48.1 mmol) and N-bromosuccinimide (9 g, 50.5 mmol) were added to 400 ml of dimethylformamide in a nitrogen atmosphere and stirred at room temperature. After the reaction for 6 hours, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of compound 1-8-b. (Yield 66%, MS: [M+H]+= 495)
단계 3) 화합물 1-8의 제조Step 3) Preparation of compounds 1-8
질소 분위기에서 화합물 1-8-b(15.0 g, 30.3 mmol)와 5H-benzofuro[3,2-c]carbazole(8.6 g, 33.4 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(4.4 g, 45.5 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 1-8을 7.9 g 제조하였다. (수율 39 %, MS: [M+H]+= 672)In a nitrogen atmosphere, compound 1-8-b (15.0 g, 30.3 mmol) and 5H-benzofuro[3,2-c]carbazole (8.6 g, 33.4 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (4.4 g, 45.5 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) were added. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 7.9 g of compound 1-8 was prepared through sublimation purification. (Yield 39%, MS: [M+H]+= 672)
제조예 9: 화합물 2-1의 제조Preparation Example 9: Preparation of compound 2-1
단계 1) 화합물 2-1-a의 제조Step 1) Preparation of compound 2-1-a
질소 분위기에서 10-bromo-7H-benzo[c]carbazole(15.0 g, 50.3 mmol)와(9-phenyl-9H-carbazol-3-yl)boronic acid(15.9 g, 55.3 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(27.8 g, 201.2 mmol)를 물 83 ml에 녹여 투입하고 충분히 교반한 후 tetrakis(triphenylphosphine)palladium(0)(1.7 g, 1.5 mmol)을 투입하였다. 11 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-1-a를 14.8 g 제조하였다. (수율 64 %, MS: [M+H]+= 460)In a nitrogen atmosphere, 10-bromo-7H-benzo[c]carbazole (15.0 g, 50.3 mmol) and (9-phenyl-9H-carbazol-3-yl)boronic acid (15.9 g, 55.3 mmol) were added to 300 ml of THF. Stirred and refluxed. After that, potassium carbonate (27.8 g, 201.2 mmol) was dissolved in 83 ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0)(1.7 g, 1.5 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of compound 2-1-a. (Yield 64%, MS: [M+H]+= 460)
단계 2) 화합물 2-1의 제조Step 2) Preparation of compound 2-1
질소 분위기에서 화합물 2-1-a(15.0 g, 32.7 mmol)와 2-chloro-4-phenylquinazoline(8.7 g, 36.0 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(4.7 g, 49.1 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 1.0 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 2-1을 10.0 g 제조하였다. (수율 46 %, MS: [M+H]+= 664)In a nitrogen atmosphere, compound 2-1-a (15.0 g, 32.7 mmol) and 2-chloro-4-phenylquinazoline (8.7 g, 36.0 mmol) were added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (4.7 g, 49.1 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) were added thereto. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 10.0 g of compound 2-1 was prepared through sublimation purification. (Yield 46%, MS: [M+H]+= 664)
제조예 10: 화합물 2-2의 제조Preparation 10: Preparation of compound 2-2
질소 분위기에서 7H-benzo[c]carbazole(15.0 g, 69.0 mmol)와 2-([1,1'-biphenyl]-4-yl)-3-chloroquinoxaline(24.1 g, 75.9 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(10.0 g, 103.6 mmol), bis(tri-tert-butylphosphine)palladium(0)(1.1 g, 2.1 mmol)을 투입하였다. 6 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 2-2를 11.0 g 제조하였다. (수율 32 %, MS: [M+H]+= 499)In a nitrogen atmosphere, 7H-benzo[c]carbazole (15.0 g, 69.0 mmol) and 2-([1,1'-biphenyl]-4-yl)-3-chloroquinoxaline (24.1 g, 75.9 mmol) were dissolved in 300 ml of toluene. added, stirred and refluxed. Then, sodium tert-butoxide (10.0 g, 103.6 mmol) and bis(tri-tert-butylphosphine)palladium(0) (1.1 g, 2.1 mmol) were added. After the reaction for 6 hours, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 11.0 g of compound 2-2 was prepared through sublimation purification. (Yield 32%, MS: [M+H]+= 499)
제조예 11: 화합물 2-3의 제조Preparation Example 11: Preparation of compound 2-3
단계 1) 화합물 2-3-a의 제조Step 1) Preparation of compound 2-3-a
질소 분위기에서 2-(4-chlorodibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(15.0 g, 45.6 mmol)와 2-chloro-4,6-diphenyl-1,3,5-triazine(13.4 g, 50.2 mmol)를 THF 300 ml에 넣고 교반 및 환류하였다. 이 후 potassium carbonate(25.2 g, 182.6 mmol)를 물 76 ml에 녹여 투입하고 충분히 교반한 후 tetrakis(triphenylphosphine)palladium(0)(1.6 g, 1.4 mmol)을 투입하였다. 12 시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 2-3-a를 12.9 g 제조하였다. (수율 65 %, MS: [M+H]+= 435)2-(4-chlorodibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (15.0 g, 45.6 mmol) and 2-chloro- 4,6-diphenyl-1,3,5-triazine (13.4 g, 50.2 mmol) was added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0)(1.6 g, 1.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 2-3-a. (Yield 65%, MS: [M+H]+= 435)
단계 2) 화합물 2-3의 제조Step 2) Preparation of compound 2-3
질소 분위기에서 화합물 2-3-a(15.0 g, 34.6 mmol)와 5H-benzo[b]carbazole(8.3 g, 38.0 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(5.0 g, 51.9 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 1.0 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 2-3을 10.4 g 제조하였다. (수율 49 %, MS: [M+H]+= 616)Compound 2-3-a (15.0 g, 34.6 mmol) and 5H-benzo[b]carbazole (8.3 g, 38.0 mmol) were added to 300 ml of toluene in a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.0 g, 51.9 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) were added thereto. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 10.4 g of compound 2-3 was prepared through sublimation purification. (Yield 49%, MS: [M+H]+= 616)
제조예 12: 화합물 2-4의 제조Preparation 12: Preparation of compound 2-4
질소 분위기에서 12,12-dimethyl-12,14-dihydrobenzo[a]indeno[1,2-h]carbazole(15.0 g, 45 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[h]quinazoline(18.2 g, 49.5 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(6.5 g, 67.5 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.7 g, 1.3 mmol)을 투입하였다. 9 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 2-4를 11.3 g 제조하였다. (수율 38 %, MS: [M+H]+= 665)12,12-dimethyl-12,14-dihydrobenzo[a]indeno[1,2-h]carbazole (15.0 g, 45 mmol) and 4-([1,1'-biphenyl]-4-yl) in nitrogen atmosphere -2-chlorobenzo[h]quinazoline (18.2 g, 49.5 mmol) was added to 300 ml of toluene, and the mixture was stirred and refluxed. Then, sodium tert-butoxide (6.5 g, 67.5 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.3 mmol) were added. After reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 11.3 g of compound 2-4 was prepared through sublimation purification. (Yield 38%, MS: [M+H]+= 665)
제조예 13: 화합물 2-5의 제조Preparation 13: Preparation of compound 2-5
질소 분위기에서 1H-14-oxa-1-aza-6,7-methanodibenzo[g,ij]naphtho[2,1,8-cde]azulene(15.0 g, 49.1 mmol)와 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine(18.7 g, 54.0 mmol)를 toluene 300 ml에 넣고 교반 및 환류하였다. 이 후 sodium tert-butoxide(7.1 g, 73.7 mmol), bis(tri-tert-butylphosphine)palladium(0)(0.8 g, 1.5 mmol)을 투입하였다. 6 시간 반응 후 상온으로 식히고 클로로포름과 물을 이용하여 유기층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2 회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제한 후, 승화정제를 통해 화합물 2-5를 11.5 g 제조하였다. (수율 38 %, MS: [M+H]+= 617)1H-14-oxa-1-aza-6,7-methanodibenzo[g,ij]naphtho[2,1,8-cde]azulene (15.0 g, 49.1 mmol) and 2-chloro-4-(naphthalen) under nitrogen atmosphere -1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (18.7 g, 54.0 mmol) was added to 300 ml of toluene, stirred and refluxed. Then, sodium tert-butoxide (7.1 g, 73.7 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.5 mmol) were added thereto. After the reaction for 6 hours, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 11.5 g of compound 2-5 was prepared through sublimation purification. (Yield 38%, MS: [M+H]+= 617)
[실시예][Example]
실시예 1Example 1
ITO(Indium Tin Oxide)가 1400 Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30 분간 세척한 후 증류수로 2 회 반복하여 초음파 세척을 10 분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with Indium Tin Oxide (ITO) to a thickness of 1400 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 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, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 화합물 HI-A과 헥사니트릴 헥사아자트리페닐렌(hexaazatriphenylene; HAT-CN)를 각각 800 Å, 50 Å의 두께로 순차적으로 열 진공 증착하여 정공주입층을 형성하였다. 그 위에 정공수송층으로 하기 화합물 HT-A를 800 Å 두께로 진공 증착한 후 전자저지층으로 하기 화합물 EB-A를 600Å의 두께로 열 진공 증착하였다. On the thus prepared ITO transparent electrode, the following compound HI-A and hexanitrile hexaazatriphenylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. On it, the following compound HT-A was vacuum-deposited to a thickness of 800 Å as a hole transport layer, and then the following compound EB-A was thermally vacuum-deposited to a thickness of 600 Å as an electron blocking layer.
이어서 발광층의 호스트로 화합물 1-1과 화합물 2-1을 50:50의 중량비로, 호스트의 2 중량%의 화합물 RD를 도펀트로 하여 400 Å의 두께로 발광층을 진공 증착하였다. Then, the light emitting layer was vacuum-deposited to a thickness of 400 Å by using Compound 1-1 and Compound 2-1 as a host of the light emitting layer in a weight ratio of 50:50 and Compound RD of 2 wt% of the host as a dopant.
이어서, 전자 수송 및 주입층으로 하기 화합물 ET-A와 Liq를 1:1의 비율로 360 Å의 두께로 열 진공 증착하고 이어서 Liq를 5 Å의 두께로 진공 증착하였다. Then, as an electron transport and injection layer, the following compound ET-A and Liq were thermally vacuum-deposited at a ratio of 1:1 to a thickness of 360 Å, followed by vacuum deposition of Liq to a thickness of 5 Å.
상기 전자주입층 위에 순차적으로 마그네슘과 은을 10:1의 중량비로 220 Å의 두께로, 알루미늄을 1000 Å 두께로 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.On the electron injection layer, magnesium and silver were sequentially deposited at a weight ratio of 10:1 to a thickness of 220 Å and aluminum to a thickness of 1000 Å to form a cathode, thereby manufacturing an organic light emitting diode.
상기의 과정에서 유기물의 증착속도는 0.4 ~ 0.7 Å/sec를 유지하였고, 음극의 마그네슘과 은의 혼합물은 0.3 Å/sec, 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착 시 진공도는 2ⅹ10-7 ~ 5ⅹ10-6 torr를 유지하여, 유기 발광 소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å/sec, the mixture of magnesium and silver at the cathode maintained the deposition rate of 0.3 Å/sec, and the aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10 - An organic light-emitting device was manufactured by maintaining 7 to 5×10 -6 torr.
실시예 2 내지 실시예 24Examples 2 to 24
상기 실시예 1-1에서 발광층의 호스트 화합물을 화합물 1-1과 화합물 2-1 대신 표 1과 같이 변경하였다는 점을 제외하고는, 상기 실시예 1과 동일한 방법을 이용하여 실시예 2 내지 실시예 24의 유기 발광 소자를 각각 제작하였다. Examples 2 to 1 using the same method as in Example 1, except that the host compound of the light emitting layer in Example 1-1 was changed as shown in Table 1 instead of Compound 1-1 and Compound 2-1. Each of the organic light emitting devices of Example 24 was fabricated.
비교예 1 내지 비교예 13Comparative Examples 1 to 13
상기 실시예 1에서 발광층의 호스트 화합물을 화합물 1-1과 화합물 2-1 대신 표 1과 같이 단독 호스트로 변경하였다는 점을 제외하고는, 상기 실시예 1과 동일한 방법을 이용하여 비교예 1 내지 비교예 13의 유기 발광 소자를 각각 제작하였다. In Example 1, the host compound of the light emitting layer was used instead of compound 1-1 and compound 2-1. Organic light emitting devices of Comparative Examples 1 to 13 were respectively manufactured using the same method as in Example 1, except that the host was changed to a single host as shown in Table 1.
실험예Experimental example
상기 실시예 및 비교예에서 제조한 유기 발광 소자에 전류를 인가하여, 구동 전압, 효율, 수명을 측정하고 그 결과를 하기 표 1에 나타내었다. 이때, 구동 전압, 효율은 10 mA/cm2의 전류 밀도를 인가하여 측정되었으며, LT97은 전류 밀도 20 mA/cm2에서 초기 휘도가 97 %로 저하할 때까지의 시간을 의미한다.By applying a current to the organic light emitting diodes prepared in Examples and Comparative Examples, driving voltage, efficiency, and lifespan were measured, and the results are shown in Table 1 below. At this time, the driving voltage and efficiency were measured by applying a current density of 10 mA/cm 2 , and LT97 means the time until the initial luminance decreases to 97% at a current density of 20 mA/cm 2 .
상기 표 1의 결과로부터 화학식 1의 구조를 갖는 화합물과 화학식 2의 구조를 갖는 화합물을 발광층 호스트로 동시에 사용한 실시예의 유기 발광 소자는, 각각의 화합물을 단독으로 호스트로 사용한 비교예의 유기 발광 소자에 비하여 저전압, 고효율, 장수명의 특성을 나타냄을 확인하였다.From the results of Table 1, the organic light emitting device of the Example using the compound having the structure of
1: 기판 2: 양극
3: 발광층 4: 음극
5: 정공주입층 6: 정공수송층
7: 전자저지층 8: 전자수송층
9: 전자주입층1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: electron transport layer
9: electron injection layer
Claims (11)
음극,
상기 양극과 음극 사이에 발광층을 포함하고,
상기 발광층은 하기 화학식 1로 표시되는 화합물 및 하기 화학식 2로 표시되는 화합물을 포함하는,
유기 발광 소자:
[화학식 1]
상기 화학식 1에서,
X는 O 또는 S이고,
Y1 내지 Y3는 각각 독립적으로, CH 또는 N이고, 단 Y1 내지 Y3 중 적어도 하나는 N이고,
Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴이고,
R1 및 R2는 각각 독립적으로, 수소, 중수소, 또는 페닐이고,
R3는 각각 독립적으로, 수소, 중수소, 페닐, 또는 5개의 중수소로 치환된 페닐이거나, 인접한 2개의 R3가 서로 결합하여 , , 또는 을 형성하고,
a1 및 a2는 각각 독립적으로, 0 내지 3의 정수이고,
a3은 0 내지 8의 정수이고,
[화학식 2]
상기 화학식 2에서,
Ar3는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고, 단 Ar3는 N을 적어도 하나 이상 포함하고,
L1은 단일결합; 치환 또는 비치환된 C6-60 아릴렌; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴렌이고,
R4는 인접한 2개의 R4가 서로 결합하여 C6-60 방향족 고리; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로방향족 고리를 형성하고,
R5는 각각 독립적으로, 수소; 중수소; 할로겐; 시아노; 니트로; 아미노; 치환 또는 비치환된 C1-60 알킬; 치환 또는 비치환된 C3-60 사이클로알킬; 치환 또는 비치환된 C2-60 알케닐; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고, 또는 인접한 2개 또는 3개의 R5가 서로 결합하여 C6-60 방향족 고리; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로방향족 고리를 형성하고,
a4는 2이고,
a5는 0 내지 6의 정수이다.
anode,
cathode,
a light emitting layer between the anode and the cathode;
The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),
Organic light emitting device:
[Formula 1]
In Formula 1,
X is O or S;
Y 1 to Y 3 are each independently CH or N, provided that at least one of Y 1 to Y 3 is N,
Ar 1 and Ar 2 are each independently, substituted or unsubstituted C 6-60 aryl,
R 1 and R 2 are each independently hydrogen, deuterium, or phenyl;
R 3 is each independently hydrogen, deuterium, phenyl, or phenyl substituted with 5 deuterium, or two adjacent R 3 are bonded to each other , , or to form,
a1 and a2 are each independently an integer of 0 to 3,
a3 is an integer from 0 to 8,
[Formula 2]
In Formula 2,
Ar 3 is C 2-60 heteroaryl including at least one selected from the group consisting of substituted or unsubstituted N, O and S, provided that Ar 3 includes at least one or more N,
L 1 is a single bond; substituted or unsubstituted C 6-60 arylene; Or substituted or unsubstituted C 2-60 heteroarylene comprising any one or more selected from the group consisting of N, O and S,
R 4 is a C 6-60 aromatic ring in which two adjacent R 4 are bonded to each other; Or to form a C 2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
R 5 are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C 1-60 alkyl; substituted or unsubstituted C 3-60 cycloalkyl; substituted or unsubstituted C 2-60 alkenyl; substituted or unsubstituted C 6-60 aryl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, or two or three adjacent R 5 are bonded to each other to C 6-60 aromatic ring; Or to form a C 2-60 heteroaromatic ring comprising any one or more selected from the group consisting of N, O and S,
a4 is 2,
a5 is an integer from 0 to 6.
Y1 내지 Y3는 각각 N인,
유기 발광 소자.
According to claim 1,
Y 1 to Y 3 are each N,
organic light emitting device.
Ar1 및 Ar2는 각각 독립적으로, 페닐, 5개의 중수소로 치환된 페닐, 또는 비페닐릴인,
유기 발광 소자.
According to claim 1,
Ar 1 and Ar 2 are each independently phenyl, phenyl substituted with 5 deuterium, or biphenylyl;
organic light emitting device.
상기 화학식 1로 표시되는 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,
유기 발광 소자:
.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:
.
상기 화학식 2는 하기 화학식 2-1 내지 화학식 2-3 중 어느 하나로 표시되는,
유기 발광 소자:
[화학식 2-1]
[화학식 2-2]
[화학식 2-3]
상기 화학식 2-1 내지 화학식 2-3에 있어서,
Ar3, L1, R5 및 a5에 대한 설명은 제1항에서 정의한 바와 같다.
According to claim 1,
Formula 2 is represented by any one of the following Formulas 2-1 to 2-3,
Organic light emitting device:
[Formula 2-1]
[Formula 2-2]
[Formula 2-3]
In Formulas 2-1 to 2-3,
Ar 3 , L 1 , R 5 and a5 are the same as defined in claim 1.
Ar3는 퀴나졸리닐, 벤조[h]퀴나졸리닐, 트리아지닐, 퀴녹살리닐, 피리미디닐, 또는 이고,
상기 Ar3는 비치환되거나, 또는 페닐, 비페닐릴, 나프틸, 디메틸플루오레닐, 디벤조퓨라닐, 디벤조티오페닐 및 페닐 카바졸릴로 구성되는 군으로부터 선택되는 1개 내지 3개의 치환기로 치환되는,
유기 발광 소자.
According to claim 1,
Ar 3 is quinazolinyl, benzo [h] quinazolinyl, triazinyl, quinoxalinyl, pyrimidinyl, or ego,
Wherein Ar 3 is unsubstituted or 1 to 3 substituents selected from the group consisting of phenyl, biphenylyl, naphthyl, dimethyl fluorenyl, dibenzofuranyl, dibenzothiophenyl and phenyl carbazolyl substituted,
organic light emitting device.
L1은 단일결합, 페닐렌, 나프틸렌, 또는 디벤조퓨라닐렌인,
유기 발광 소자.
According to claim 1,
L 1 is a single bond, phenylene, naphthylene, or dibenzofuranylene,
organic light emitting device.
R5는 각각 독립적으로, 수소, 중수소, 페닐, 카바졸릴, 페닐 카바졸릴이거나, 인접한 2개 또는 3개의 R5가 서로 결합하여 벤젠고리, , , , , , , 또는 을 형성하는,
유기 발광 소자.
According to claim 1,
R 5 is each independently hydrogen, deuterium, phenyl, carbazolyl, phenyl carbazolyl, or adjacent two or three R 5 are bonded to each other to form a benzene ring, , , , , , , or to form,
organic light emitting device.
상기 화학식 2로 표시되는 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,
유기 발광 소자:
.According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:
.
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