KR101929238B1 - Organic light-emitting compounds and organic light-emitting devices comprising the same - Google Patents
Organic light-emitting compounds and organic light-emitting devices comprising the same Download PDFInfo
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- KR101929238B1 KR101929238B1 KR1020160004516A KR20160004516A KR101929238B1 KR 101929238 B1 KR101929238 B1 KR 101929238B1 KR 1020160004516 A KR1020160004516 A KR 1020160004516A KR 20160004516 A KR20160004516 A KR 20160004516A KR 101929238 B1 KR101929238 B1 KR 101929238B1
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- light emitting
- layer
- organic light
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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Abstract
본 발명은 페닐 피리딘 계열의 주 리간드와 3-hydroxy-picolinato ligand 보조 리간드로 이루어진 헤데로렙틱(heteroleptic) 구조를 가지는 금속 착화합물의 3-hydroxy-picolinato ligand 보조 리간드 분자내에 OHO=C 수소결합을 추가하여 안정화된 하기 [화학식 1]로 표시되는 금속 착화합물 및 이를 발광층 내의 도판트로 채용하여 우수한 색좌표와 함께, 효율 저하 방지 및 비발광 분열에 대한 내구성을 가져 수명 특성이 현저히 향상된 청색 인광 유기발광소자에 관한 것이다.
[화학식 1]
[Chemical Formula 1]
Description
본 발명은 유기 발광 화합물에 관한 것으로서, 더욱 상세하게는 보조 리간드 분자내의 수소결합에 의해서 안정화된 것을 특징으로 하는 금속 착화합물과 이를 포함하는 청색 인광 유기발광소자에 관한 것이다.The present invention relates to an organic light emitting compound, and more particularly, to a metal complex compound and a blue phosphorescent organic light emitting device containing the same, which are stabilized by hydrogen bonding in an auxiliary ligand molecule.
차세대 디스플레이로 각광을 받는 유기발광소자(OLED; Organic Light Emitting Device)는 전기, 전자, 재료, 화학, 물리, 광학 등 여러 분야에 걸쳐 학문적, 산업적 연구가 활발히 진행되고 있다. 이러한 연구의 성과로 PM 방식의 유기발광소자(OLED)가 핸드폰의 외부 창에 사용되는 등 일부 전자 기기에 도입되기도 하였으며, 최근에는 AM 방식의 유기발광소자(OLED)를 PDA, 핸드폰, 게임기 등의 모바일 디스플레이에서 TV까지 적용하기 위한 연구와 사업화가 진행되고 있다.Background Art Organic light emitting devices (OLEDs), which receive the spotlight as a next generation display, are actively and academically studied in various fields such as electricity, electronics, materials, chemistry, physics and optics. In recent years, OLEDs have been widely used in PDAs, mobile phones, game machines, and the like. [0004] In recent years, organic light emitting devices (OLEDs) Research and commercialization for applying from mobile display to TV are underway.
또한, 형광 물질뿐만 아니라 인광 물질도 유기발광소자(OLED)로 사용될 수 있음이 알려졌으며, 최근에는 적색과 녹색의 인광 물질이 상업적으로 사용되며, 청색 인광 물질은 아직 수명, 색좌표, 효율 문제로 적용되지 못하고 있으며, 따라서 이에 대한 연구가 지속 중이다. 인광 발광은 바닥상태(ground states)에서 여기 상태로 전자가 전이한 후, 계간 전이(intersystem crossing)를 통해 단일항 여기자가 삼중항 여기자로 비발광 전이된 다음, 삼중항 여기자(Triple exciton)가 바닥상태로 전이하면서 발광하는 메카니즘(mechanism)으로 이루어진다. 이러한 인광 발광은 삼중항 여기자의 전이 시, 직접 바닥상태로 전이할 수 없어 전자스핀의 뒤바뀜이 진행된 이후에 바닥상태로 전이되는 과정을 거치기 때문에 형광보다 수명(발광시간)이 길어지는 특성을 갖는다. 즉, 형광 발광의 발광 지속기간은 수 나노초(several nano seconds)에 불과하지만, 인광 발광의 경우는 상대적으로 긴 시간인 수 마이크로초(several micro seconds)에 해당한다.In addition, it has been known that not only fluorescent materials but also phosphorescent materials can be used as organic light emitting devices (OLEDs). In recent years, red and green phosphorescent materials are commercially used, and blue phosphorescent materials are still used for life, And therefore research on this is continuing. Phosphorescent luminescence is a phenomenon in which electrons are transferred from ground states to excited states, and then single-excitons are non-luminescent transitioned to triplet excitons through intersystem crossing, and then triple excitons And a light emitting mechanism. This phosphorescence emission can not transfer to the ground state when the triplet exciton is transited, and the lifetime (luminescence time) of the phosphorescence is longer than that of fluorescence because the phosphorescence is transferred to the bottom state after the reversal of the electron spin proceeds. That is, the emission duration of fluorescence emission is only several nanoseconds, but in the case of phosphorescence emission, it corresponds to a relatively long time of several microseconds.
일반적으로, 인광 유기발광소자(PhOLED)는 ITO 투명전극으로 이루어진 양극(anode); 상기 양극 상에 형성된 정공 수송층(hole transport layer, HTL); 상기 정공 수송층(HTL) 상에 형성된 발광층(emitting layer, EML); 상기 발광층(EML) 상에 형성된 전자 수송층(electron transport layer, ETL); 및 상기 전자 수송층(ETL) 상에 형성된 음극(cathode)을 포함하는 다층 구조를 가지며, 이들은 진공증착 또는 잉크젯 프린팅 등의 방법을 통해 기판 상에 순차적으로 적층 형성된다. 그리고, 상기 발광층(EML)은 전하 수송 재료로서의 호스트(host)와 인광 물질로서의 도판트(dopant)를 포함하고 있다.In general, the phosphorescent organic light emitting device (PHOLED) includes an anode made of an ITO transparent electrode; A hole transport layer (HTL) formed on the anode; An emission layer (EML) formed on the hole transport layer (HTL); An electron transport layer (ETL) formed on the emission layer (EML); And a cathode formed on the electron transport layer (ETL), which are sequentially laminated on a substrate through a method such as vacuum deposition or inkjet printing. The light emitting layer (EML) includes a host as a charge transporting material and a dopant as a phosphorescent material.
위와 같은 구조의 인광 유기발광소자(PhOLED)에 전압이 가해지면 양극으로부터 정공이 주입되고 음극으로부터 전자가 주입되며, 주입된 정공과 전자는 각각 정공 수송층(HTL)과 전자 수송층(ETL)을 거쳐 발광층(EML)에서 재조합(recombination)하여 발광 여기자를 형성한다. 그리고, 형성된 발광 여기자는 바닥상태로 전이하면서 빛을 방출한다.When a voltage is applied to the phosphorescent organic light emitting device (PhOLED) having the above structure, holes are injected from the anode and electrons are injected from the cathode. The injected holes and electrons are injected through the hole transport layer (HTL) and the electron transport layer (EML) to form luminescent excitons. Then, the formed luminescent excitons emit light while transitioning to the bottom state.
최근, 인광 유기발광소자(PhOLED)의 발광 효율을 높이기 위한 노력이 많이 시도되었다. 그 결과, 녹색의 경우 20%, 그리고 적색의 경우 15% 이상의 높은 외부 발광 효율을 가지는 기술이 보고되었다. 그러나 청색의 경우 녹색과 적색에 비해 발광 효율, 색좌표 특성 및 수명이 나쁜 것으로 나타나고 있다. 이를 해결하기 위해서 현재 많은 연구가 진행되고 있다. 주로, 소자의 층 구조의 개선과, 호스트와 도판트의 새로운 물질에 대한 연구가 많이 진행되고 있다.In recent years, efforts have been made to increase the luminous efficiency of the phosphorescent organic light emitting device (PhOLED). As a result, a technique has been reported that has a high external luminous efficiency of 20% for green and 15% for red. However, blue light has a poor luminous efficiency, color coordinate characteristic and longevity compared to green and red. A lot of researches are going on to solve this problem. Mainly, the improvement of the layer structure of the device and the research on the new material of the host and the dopant are proceeding.
발광층(EML)을 구성하는 도판트는 금속 착화합물이 유용하다. 최근에는 도판트에 대해서도 많은 연구가 진행되고 있으며, 예를 들어, 대한민국 공개특허 제10-2010-0061831호와 미국 공개특허 US 2005/0214576에 도판트로서의 금속 착화합물에 대한 기술이 제시되어 있다. 특히 미국 공개특허 US 2005/0214576에 본 발명의 비교예가 되는 3-hydroxy-picolinato ligand 보조 리간드를 사용한 헤데로렙틱(heteroleptic) 구조의 금속 착화합물(FIrpic)이 인광 도판트로 제시되어 있다. 그리고, 미국 공개특허 US 2006/0237715에 호스트 물질과 인광 도판트가 연결되어 하나의 물질 형태를 이루는 것이 제시되어 있으며, 이러한 물질을 합성하는 단계의 중간체로 본 발명과 관련된 3-hydroxy-picolinato ligand 보조 리간드 분자내의 OH···O=C 수소결합한 금속 착화합물(FIrpic-OH)이 제시되어 있다.The dopant constituting the light-emitting layer (EML) is useful as a metal complex. In recent years, much research has been conducted on dopants. For example, Korean Patent Laid-Open No. 10-2010-0061831 and US Patent Publication No. 2005/0214576 disclose techniques for metal complexes as dopants. In particular, US Patent Publication No. 2005/0214576 discloses a metal complex (FIrpic) having a heteroleptic structure using a 3-hydroxy-picolinato ligand auxiliary ligand, which is a comparative example of the present invention, as a phosphorescent dopant. In US Publication No. 2006/0237715, a host material and a phosphorescent dopant are connected to form a single material. As an intermediate in the synthesis of such a material, 3-hydroxy-picolinato ligand auxiliary OH ··· O = C hydrogen bond metal complex in the ligand molecule (FIrpic-OH) is presented.
종래 기술에 따른 도판트, 즉 청색 인광 물질로 사용되는 종래의 금속 착화합물은 색좌표가 나쁘며 도판트의 효율 저하 및 여기자에 의한 비발광 분열이 쉽게 발생하여 소재의 안정성이 떨어진다. 특히, 3-hydroxy-picolinato ligand 보조 리간드로 이루어진 헤데로렙틱(heteroleptic) 구조를 가지는 금속 착화합물을 도판트로 사용한 청색 인광 유기발광소자(PhOLED)의 경우 3-hydroxy-picolinato ligand 보조 리간드의 분열로 소자의 수명이 매우 짧은 문제점을 갖고 있다.Conventional metal complexes used as dopants, that is, blue phosphorescent materials according to the related art, have poor color coordinates and the stability of the material is deteriorated due to the deterioration of the efficiency of the dopant and the non-emission cleavage by excitons. In particular, in the case of a blue phosphorescent organic light emitting device (PhOLED) using a metal complex having a heteroleptic structure consisting of a 3-hydroxy-picolinato ligand ancillary ligand as a dopant, a 3-hydroxy-picolinato ligand secondary ligand And has a very short life span.
이에 따라, 본 발명은 페닐 피리딘 계열의 주 리간드와 3-hydroxy-picolinato ligand 보조 리간드로 이루어진 헤데로렙틱(heteroleptic) 구조를 가지는 금속 착화합물의 3-hydroxy-picolinato ligand 보조 리간드 분자내에 OH···O=C 수소결합을 추가하여 안정화된 금속 착화합물을 제공하자 한다.Accordingly, the present invention relates to a 3-hydroxy-picolinato ligand auxiliary ligand molecule of a metal complex having a heteroleptic structure consisting of a phenylpyridine-based primary ligand and a 3-hydroxy-picolinato ligand ancillary ligand. = C hydrogen bond to provide a stabilized metal complex.
또한, 본 발명에 따른 금속 착화합물을 도판트로 사용하여 우수한 색좌표와 함께, 효율 저하 방지 및 비발광 분열에 대한 내구성을 가져 수명 특성이 현저히 향상된 청색 인광 유기발광소자(PhOLED)를 제공하고자 한다.Also, it is intended to provide a blue phosphorescent organic light emitting device (PhOLED) using metal complex according to the present invention as a dopant, having excellent color coordinates, durability against non-emission breakdown, and significantly improved lifetime characteristics.
본 발명은 상기 과제를 해결하기 위하여 하기 [화학식 1]로 표시되는 유기발광 금속 착화합물을 제공한다.The present invention provides an organic light emitting metal complex represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 [화학식 1]의 치환기 및 구체적인 구조는 후술한다.
The substituent and the specific structure of the above-mentioned formula (1) will be described later.
또한, 본 발명은 상기 [화학식 1]로 표시되는 유기발광 금속 착화합물을 포함하는 청색 인광 유기발광소자를 제공한다.The present invention also provides a blue phosphorescent organic electroluminescent device comprising the organic electroluminescent metal complex represented by the general formula (1).
본 발명에 따른 유기발광 금속 착화합물은 페닐 피리딘 계열의 주 리간드와 3-hydroxy-picolinato ligand 보조 리간드로 이루어진 헤데로렙틱 구조를 가지는 금속 착화합물의 3-hydroxy-picolinato ligand 보조 리간드 분자내에 OH···O=C 수소결합을 추가하여 안정화된 것을 특징으로 하는 금속 착화합물로서, 이를 포함하는 청색 인광 유기발광소자는 우수한 색좌표, 고효율 및 장수명 등 현저 향상된 발광 특성을 가져 다양한 디스플레이 소자에 유용하여 사용될 수 있다.The organic luminescent metal complex according to the present invention is characterized in that a 3-hydroxy-picolinato ligand auxiliary ligand molecule of a metal complex having a hederoleptic structure comprising a phenylpyridine main ligand and a 3-hydroxy-picolinato ligand ancillary ligand has OH = C hydrogen bond. The blue phosphorescent organic light emitting device including the blue phosphorescent organic light emitting device has remarkably improved light emission characteristics such as excellent color coordinates, high efficiency and long life, and can be used for various display devices.
도 1a 내지 도 1d는 본 발명의 합성예 1 내지 4에 따른 금속 착화합물과 비교 화합물의 상온 PL 스펙트럼이다.
도 2는 본 발명의 합성예 1에 따른 Firpic-OH와 이의 비교 화합물 Firpic에 대해서 상온(298 K, DCM)에서 인광 decay lifetime을 측정한 결과이다.
도 3a 내지 도 3d는 본 발명의 실시예에 따른 소자 Ⅰ 및 Ⅱ에 대해서 발광 특성 확인한 결과이다. (도 3a, J-V-L characteristics; 도 3b, current efficiency-current density curves; 도 3c, power efficiency-current density curves; 도 3d, external quantum efficiency as a function of current density)
도 4는 본 발명의 실시예에 따른 소자 Ⅲ 및 Ⅳ에 대해서 400 nits 정전류 구동에서 휘도 반감수명을 측정한 결과이다.
도 5는 본 발명에 따른 유기발광 화합물의 구조를 나타낸 대표도이다.1A to 1D are PL spectra at room temperature of the metal complexes and the comparative compounds according to Synthesis Examples 1 to 4 of the present invention.
FIG. 2 shows the result of measuring phosphorescence decay lifetime at room temperature (298 K, DCM) against Firpic-OH and its comparative compound Firpic according to Synthesis Example 1 of the present invention.
FIGS. 3A to 3D are the results of checking emission characteristics of the devices I and II according to the embodiment of the present invention. (Fig. 3a, J - VL characteristics; Fig. 3b, current efficiency-current density curves ; Fig. 3c, power efficiency-current density curves ; Fig. 3d, external quantum efficiency as a function of current density)
FIG. 4 is a graph illustrating the results of measurement of half-life half-life at 400 nits constant-current driving for devices III and IV according to an embodiment of the present invention.
5 is a schematic diagram showing the structure of an organic luminescent compound according to the present invention.
이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 측면은 페닐 피리딘 계열의 주 리간드와 3-hydroxy-picolinato ligand 보조 리간드로 이루어진 헤데로렙틱 구조를 가지는 금속 착화합물의 3-hydroxy-picolinato ligand 보조 리간드 분자내에 OH···O=C 수소결합을 추가하여 안정화된 것을 특징으로 하고, 하기 [화학식 1]로 표시되는 유기발광 금속 착화합물에 관한 것이다.One aspect of the present invention relates to a 3-hydroxy-picolinato ligand auxiliary ligand molecule of a metal complex having a hederoleptic structure consisting of a primary phenylpyridine ligand and a 3-hydroxy-picolinato ligand ancillary ligand OH ... O = C hydrogen And the organic light emitting metal complex compound represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 [화학식 1]에서,In the above formula (1)
M은 이리듐(Ir), 백금(Pt), 오스뮴(Os) 및 루테늄(Ru) 중에서 선택되는 어느 하나일 수 있으며, X는 N 또는 C-R4이다.M may be any one selected from iridium (Ir), platinum (Pt), osmium (Os), and ruthenium (Ru), and X is N or CR 4 .
R1 내지 R4는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 할로겐, 시아노기, 히드록시기, 니트로기, 치환 또는 비치환된 탄소수 1 내지 10의 알킬기, 치환 또는 비치환된 탄소수 2 내지 10의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 10의 알키닐기, 치환 또는 비치환된 탄소수 6 내지 24의 아릴기, 치환 또는 비치환된 탄소수 6 내지 24의 아릴알킬기, 치환 또는 비치환된 탄소수 2 내지 24의 헤테로아릴기, 치환 또는 비치환된 탄소수 2 내지 24의 헤테로아릴알킬기, 치환 또는 비치환된 탄소수 3 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 헤테로시클로알킬기, CO2R, C(O)R 및 OR (여기서, R은 탄소수 1 내지 20의 알킬기) 중에서 선택되는 어느 하나일 수 있다.R 1 To R < 4 > are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, A substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 24 carbon atoms, a substituted or unsubstituted C2 to C24 heteroaryl group having 2 to 24 carbon atoms, A substituted or unsubstituted C2-C30 heteroarylalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a CO 2 R, a C O) R and OR wherein R is an alkyl group having 1 to 20 carbon atoms.
n은 1 내지 2의 정수이고, m은 0 내지 3의 정수이다.n is an integer of 1 to 2, and m is an integer of 0 to 3.
삭제delete
본 발명의 일 실시예에 의하면, 상기 R1 내지 R4는 서로 동일하거나 상이하고, 각각 독립적으로 수소, 플루오르, 탄소수 1 내지 10의 알킬기, 탄소수 2 내지 10의 알케닐기, 탄소수 2 내지 10의 알키닐기, 탄소수 6 내지 24의 아릴알킬기, 시아노기(CN), 플루오르카본(CnF2n +1, n은 1 내지 10의 정수이다.), 트리플루오로비닐기, 탄소수 2 내지 24의 헤테로아릴기, 탄소수 2 내지 24의 헤테로아릴알킬기, 탄소수 3 내지 30의 시클로알킬기, 탄소수 2 내지 30의 헤테로시클로알킬기, CO2R, C(O)R 및 OR (여기서, R은 탄소수 1 내지 20의 알킬기) 중에서 선택되는 어느 하나일 수 있다.
According to an embodiment of the present invention, the R 1 To R < 4 > are the same or different from each other and each independently represents hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, (CN), fluorocarbon (C n F 2n +1 , n is an integer of 1 to 10), trifluorovinyl group, heteroaryl group having 2 to 24 carbon atoms, heteroarylalkyl group having 2 to 24 carbon atoms, A cycloalkyl group having 3 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, CO 2 R, C (O) R and OR (wherein R is an alkyl group having 1 to 20 carbon atoms).
또한, 본 발명에 있어서, 상기 치환기들의 예시들에 대해서 아래에서 구체적으로 설명하나, 이에 한정되는 것은 아니다.In the present invention, examples of the substituents will be specifically described below, but the present invention is not limited thereto.
본 발명에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 구체적인 예로는 메틸기, 에틸기, 프로필기, n-프로필기, 이소프로필기, 부틸기, n-부틸기, 이소부틸기, tert-부틸기, sec-부틸기, 1-메틸-부틸기, 1-에틸-부틸기, 펜틸기, n-펜틸기, 이소펜틸기, 네오펜틸기, tert-펜틸기, 헥실기, n-헥실기, 1-메틸펜틸기, 2-메틸펜틸기, 4-메틸-2-펜틸기, 3,3-디메틸부틸기, 2-에틸부틸기, 헵틸기, n-헵틸기, 1-메틸헥실기, 시클로펜틸메틸기, 시클로헥틸메틸기, 옥틸기, n-옥틸기, tert-옥틸기, 1-메틸헵틸기, 2-에틸헥실기, 2-프로필펜틸기, n-노닐기, 2,2-디메틸헵틸기, 1-에틸-프로필기, 1,1-디메틸-프로필기, 이소헥실기, 2-메틸펜틸기, 4-메틸헥실기, 5-메틸헥실기 등이 있으나, 이들에 한정되지 않는다.In the present invention, the alkyl group may be linear or branched, and specific examples thereof include a methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n- Methylpentyl, 4-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentyl An ethylhexyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a n-nonyl group, a 2,2-dimethylheptyl group, But are not limited to, 1-ethyl-propyl group, 1,1-dimethylpropyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group and 5-methylhexyl group.
본 발명에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 구체적인 예로는 비닐기, 1-프로페닐기, 이소프로페닐기, 1-부테닐기, 2-부테닐기, 3-부테닐기, 1-펜테닐기, 2-펜테닐기, 3-펜테닐기, 3-메틸-1-부테닐기, 1,3-부타디에닐기, 알릴기, 1-페닐비닐-1-일기, 2-페닐비닐-1-일기, 2,2-디페닐비닐-1-일기, 2-페닐-2-(나프틸-1-일)비닐-1-일기, 2,2-비스(디페닐-1-일)비닐-1-일기, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present invention, the alkenyl group may be linear or branched, and specific examples thereof include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, , A 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl- 1-yl group, 2-diphenyl-1-yl group, 2-phenyl-2- (naphthyl- A stilbenyl group, a styryl group, and the like, but are not limited thereto.
본 발명에 있어서, 아릴기는 단환식 또는 다환식일 수 있고, 단환식 아릴기의 예로는 페닐기, 비페닐기, 터페닐기, 스틸벤기 등이 있고, 다환식 아릴기의 예로는 나프틸기, 안트라세닐기, 페난트레닐기, 파이레닐기, 페릴레닐기, 테트라세닐기, 크라이세닐기, 플루오레닐기, 아세나프타센닐기, 트리페닐렌기, 플루오안트렌(fluoranthrene)기 등이 있으나, 본 발명의 범위가 이들 예로만 한정되는 것은 아니다.In the present invention, the aryl group may be monocyclic or polycyclic. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group , A phenanthrenyl group, a pyrenyl group, a perylenyl group, a tetracenyl group, a klychenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluororanthrene group. However, The present invention is not limited to these examples.
본 발명에 있어서, 헤테로고리기는 이종원자로 O, N 또는 S를 포함하는 헤테로고리기로서, 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, 디벤조퓨라닐기, 페난트롤린기, 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present invention, the heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom and examples of the heterocyclic group include a thiophene group, a furane group, a pyrrolyl group, an imidazole group, a thiazole group, A thiazolyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a thiazolyl group, a thiazolyl group, a pyrazyl group, a bipyridyl group, a pyrimidyl group, A benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a benzothiophene group, a benzothiophene group, a benzothiophene group, a benzothiophene group, a benzothiophene group, A thiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, or the like, which may be substituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, But are not limited to these.
본 발명에 있어서, 시클로알킬기는 특별히 한정되지 않으나,구체적으로 시클로프로필기 시클로부틸기 시클로펜틸기 3-메틸시클로펜틸기 2,3-디메틸시클로펜틸기, 시클로헥실기, 3-메틸시클로헥실기, 4-메틸시클로헥실기, 2,3-디메틸시클로헥실기, 3,4,5-트리메틸시클로헥실기, 4-tert-부틸시클로헥실기, 시클로헵틸기, 시클로옥틸기 등이 있으나, 이에 한정되지 않는다.In the present invention, the cycloalkyl group is not particularly limited, but specifically includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, But are not limited to, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group and the like Do not.
본 발명에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 발명에 있어서, 아릴아민기의 예로는 치환 또는 비치환된 모노아릴아민기, 치환 또는 비치환된 디아릴아민기, 또는 치환 또는 비치환된 트리아릴아민기가 있다. 상기 아릴아민기 중의 아릴기는 단환식 아릴기일 수 있고, 다환식 아릴기일 수 있다. 상기 아릴기가 2 이상을 포함하는 아릴아민기는 단환식 아릴기, 다환식 아릴기, 또는 단환식 아릴기와 다환식 아릴기를 동시에 포함할 수 있다.
In the present invention, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.
상기 [화학식 1]로 표시되는 본 발명에 따른 유기발광 금속 착화합물은 그 구조적 특이성으로 인하여 유기발광소자의 유기물층으로 사용될 수 있고, 보다 구체적으로 발광층 내의 도판트로 사용될 수 있으며, 구체적인 예로는 하기 화합물들이 있으나, 이들에만 한정되는 것은 아니다.The organic luminescent metal complex according to the present invention represented by the above formula (1) can be used as an organic material layer of an organic light emitting device due to its structural specificity, and more specifically, it can be used as a dopant in a light emitting layer. , But are not limited thereto.
[화학식 2] [화학식 3][Chemical Formula 2] < EMI ID =
[화학식 4] [화학식 5][Chemical Formula 4]
또한, 본 발명의 다른 일 측면은 제1 전극, 제2 전극 및 상기 제1 전극 및 제2 전극 사이에 개재되는 1층 이상의 유기물층으로 이루어진 유기발광소자에 관한 것이고, 구체적으로는 양극, 상기 양극 상에 형성된 발광층 및 상기 발광층 상에 형성된 음극을 포함하는 청색 인광 유기발광소자에 관한 것이다.According to another aspect of the present invention, there is provided an organic light emitting device including a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, Emitting layer and a cathode formed on the light-emitting layer.
더욱 구체적으로는 양극, 상기 양극 상에 형성된 정공 수송층, 상기 정공 수송층 상에 형성된 발광층, 상기 발광층 상에 형성된 전자 수송층 및 상기 전자 수송층 상에 형성된 음극을 포함하는 청색 인광 유기발광소자에 관한 것이다.More specifically, the present invention relates to a blue phosphorescent organic light emitting device comprising a cathode, a hole transport layer formed on the anode, a light emitting layer formed on the hole transport layer, an electron transport layer formed on the light emitting layer, and a cathode formed on the electron transport layer.
즉, 본 발명의 일 실시예에 따른 유기발광소자는 양극과 음극 및 이 사이에 배치된 유기물층을 포함하는 구조로 이루어질 수 있으며, 본 발명에 따른 [화학식 1]의 유기발광 금속 착화합물을 소자의 유기물층에 사용한다는 것을 제외하고는 통상의 소자의 제조 방법 및 재료를 사용하여 제조될 수 있다.That is, the organic light emitting device according to an embodiment of the present invention may have a structure including an anode, a cathode, and an organic material layer disposed therebetween. The organic light emitting metal complex according to the present invention may be applied to an organic material layer Except that it is used in a conventional method for manufacturing a semiconductor device.
본 발명에 따른 유기발광소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등을 포함하는 구조를 가질 수 있다. 그러나, 이에 한정되지 않고 더 적은 수 또는 더 많은 수의 유기물층을 포함할 수도 있다.The organic material layer of the organic light emitting device according to the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. However, it is not so limited and may include fewer or greater numbers of organic layers.
따라서, 상기 유기물층은 발광층을 포함할 수 있고, 상기 발광층이 상기 [화학식 1]로 표시되는 화합물을 포함할 수 있다. 여기서, 상기 [화학식 1]로 표시되는 화합물은 발광층 내 도판트 물질로서 포함될 수 있다. 상기 [화학식 1]로 표시되는 화합물이 발광층 내 도판트 물질로서 포함되는 경우에, 상기 발광층은 1종 이상의 호스트 화합물을 더 포함할 수 있다. 이와 같이, 본 발명에서 상기 발광층에는 호스트와 더불어 도판트 재료가 사용될 수 있다. 상기 발광층이 호스트 및 도판트를 포함할 경우, 도판트의 함량은 통상적으로 호스트 약 100 중량부를 기준으로 하여 약 0.01 내지 약 20 중량부의 범위에서 선택될 수 있다.
Accordingly, the organic layer may include a light emitting layer, and the light emitting layer may include a compound represented by the formula (1). Here, the compound represented by
이하, 본 발명에 따른 유기발광소자를 보다 상세히 설명하고자 한다.Hereinafter, the organic light emitting device according to the present invention will be described in more detail.
본 발명에 따른 유기발광소자는 애노드, 정공수송층, 유기발광층, 전자수송층 및 캐소드을 포함하며, 필요에 따라 정공주입층과 전자주입층을 더 포함할 수 있으며, 그 이외에도 1층 또는 2층의 중간층을 더 형성하는 것도 가능하며, 정공저지층 또는 전자저지층을 더 형성시킬 수도 있으며, 소자의 특성에 따라 다양한 기능을 갖는 유기층을 더 포함할 수 있다.The organic light emitting device according to the present invention may include an anode, a hole transporting layer, an organic light emitting layer, an electron transporting layer, and a cathode, and may further include a hole injection layer and an electron injection layer as necessary. Further, a hole blocking layer or an electron blocking layer may be further formed, or an organic layer having various functions may be further included depending on the characteristics of the device.
본 발명의 유기발광소자 및 그 제조방법에 대하여 살펴보면 다음과 같다.The organic light emitting device of the present invention and its manufacturing method will be described as follows.
먼저 기판 상부에 애노드 전극용 물질을 코팅하여 애노드를 형성한다. 여기에서 기판으로는 통상적인 유기발광소자에서 사용되는 기판을 사용하는데 투명성, 표면 평활성, 취급 용이성 및 방수성이 우수한 유기 기판 또는 투명 플라스틱 기판이 바람직하다. 그리고, 애노드 전극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2),산화아연(ZnO) 등을 사용한다.First, an anode electrode material is coated on the substrate to form an anode. As the substrate, a substrate used in a conventional organic light emitting device is used, and an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.
상기 애노드 전극 상부에 정공 주입층 물질을 진공열 증착 또는 스핀 코팅하여 정공주입층을 형성한다. 그 다음으로 상기 정공주입층의 상부에 정공수송층 물질을 진공 열증착 또는 스핀 코팅하여 정공수송층을 형성한다.A hole injecting layer material is formed on the anode by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer is formed on the hole injection layer by vacuum thermal deposition or spin coating.
상기 정공주입층 재료는 당업계에서 통상적으로 사용되는 것이라면, 특별히 제한되지 않고 사용할 수 있으며, 구체적인 예시로서, HAT-CN [1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile], 2-TNATA [4,4',4"-tris(2- naphthylphenyl-phenylamino)-triphenylamine], NPD [N,N'-di(1-naphthyl)-N,N' -diphenylbenzid ine)], TPD [N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1' -biphenyl-4,4'-diamine], DNTPD [N,N'-diphen yl-N,N'-bis-[4-(phenyl-m-tolyl amino)-phenyl]-biphenyl-4,4'-diamine] 등을 사용할 수 있다.The material of the hole injection layer is not particularly limited as long as it is commonly used in the art. Specific examples thereof include HAT-CN [1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile], 2- TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine], NPD [N, N'-di (1-naphthyl) N'-diphenyl-N, N'-bis- (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine] 4- (phenyl-m-tolyl amino) -phenyl] -biphenyl-4,4'-diamine].
또한, 상기 정공수송층 재료 역시 업계에 통상적으로 사용되는 것이라면, 특별히 제한되지 않으며, 예를 들어, TAPC [4,4’-cyclohexyl idenebis[N,N-bis(4-methylphenyl)benzenamine]], N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD) 또는 N,N'-디(나프탈렌-1-일)-N,N'-디페닐벤지딘(α-NPD) 등을 사용할 수 있다.The hole transport layer material is not particularly limited as long as it is commonly used in the industry. For example, TAPC (4,4'-cyclohexyl idenebis [ N , N- bis (4-methylphenyl) benzenamine] (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'- -N, N'-diphenylbenzidine (? -NPD), or the like can be used.
이어서, 상기 정공수송층의 상부에 유기발광층을 적층하고 상기 유기발광층의 상부에 선택적으로 정공저지층을 진공 증착 방법, 또는 스핀 코팅 방법으로서 박막을 형성할 수 있다. 상기 정공저지층은 정공이 유기발광층을 통과하여 캐소드로 유입되는 경우에는 소자의 수명과 효율이 감소되기 때문에 HOMO(Highest Occupied Molecular Orbital) 레벨이 매우 낮은 물질을 사용함으로써 이러한 문제를 방지하는 역할을 한다. 이 때, 사용되는 정공 저지 물질은 특별히 제한되지는 않으나 전자수송능력을 가지면서 발광 화합물보다 높은 이온화 포텐셜을 가져야 하며 대표적으로 BAlq, BCP, TPBI 등이 사용될 수 있다.Then, an organic light emitting layer may be laminated on the hole transport layer, and a hole blocking layer may be selectively formed on the organic light emitting layer by a vacuum deposition method or a spin coating method. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.
이러한 정공저지층 위에 전자수송층을 진공 증착 방법, 또는 스핀 코팅 방법을 통해 증착한 후에 전자주입층을 형성하고 상기 전자주입층의 상부에 캐소드 형성용 금속을 진공 열증착하여 캐소드 전극을 형성함으로써 유기발광소자가 완성된다. 여기에서 캐소드 형성용 금속으로는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리듐(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등을 사용할 수 있으며, 전면 발광 소자를 얻기 위해서는 ITO, IZO를 사용한 투과형 캐소드를 사용할 수 있다.An electron transport layer is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, and then an electron injection layer is formed. A metal for cathode formation is vacuum deposited on the electron injection layer to form a cathode electrode, The device is completed. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.
상기 전자 수송층 재료로는 전자주입전극(Cathode)로부터 주입된 전자를 안정하게 수송하는 기능을 하는 것으로서, 공지의 전자 수송 물질을 이용할 수 있다. 공지의 전자 수송 물질의 예로는, 퀴놀린 유도체, 특히 트리스(8-퀴놀리노레이트)알루미늄(Alq3), TAZ, Balq, 베릴륨 비스(벤조퀴놀리-10-노에이트)(beryllium bis(benzoquinolin-10-olate: Bebq2), TmPyPb (1,3,5-tri(m-pyridin-3-ylphenyl)benzene)등과 같은 재료를 사용할 수도 있다.The electron transport layer material serves to stably transport electrons injected from an electron injection electrode, and known electron transport materials can be used. Examples of electron transport materials are known, a quinoline derivative, in particular tris (8-quinolinolato) aluminum (Alq 3), TAZ, Balq, beryllium bis (benzo-10-quinolinyl furnace benzoate) (beryllium bis (10-benzoquinolin -olate: Bebq 2 ), and TmPyPb (1,3,5-tri ( m -pyridin-3-ylphenyl) benzene).
또한, 상기 발광층은 본 발명에 따른 도판트 화합물 이외에도 다양한 호스트와 다양한 도판트 물질을 추가로 포함할 수 있다.In addition, the light emitting layer may further include various hosts and various dopant materials in addition to the dopant compound according to the present invention.
또한, 상기 정공주입층, 정공수송층, 전자저지층, 발광층, 정공저지층, 전자수송층 및 전자주입층으로부터 선택된 하나 이상의 층은 단분자 증착방식 또는 용액공정에 의하여 형성될 수 있으며, 여기서 상기 증착 방식은 상기 각각의 층을 형성하기 위한 재료로 사용되는 물질을 진공 또는 저압상태에서 가열 등을 통해 증발시켜 박막을 형성하는 방법을 의미하고, 상기 용액공정은 상기 각각의 층을 형성하기 위한 재료로 사용되는 물질을 용매와 혼합하고 이를 잉크젯 인쇄, 롤투롤 코팅, 스크린 인쇄, 스프레이 코팅, 딥 코팅, 스핀 코팅 등과 같은 방법을 통하여 박막을 형성하는 방법을 의미한다.At least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular deposition method or a solution process, Means a method of forming a thin film by evaporating a material used as a material for forming each of the layers by heating or the like under a vacuum or a low pressure state and the solution process is used as a material for forming each of the layers Means a method of forming a thin film by a method such as ink jet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating and the like.
또한, 본 발명에 따른 유기발광소자는 평판 디스플레이 장치, 플렉시블 디스플레이 장치, 단색 또는 백색의 평판 조명용 장치 및 단색 또는 백색의 플렉시블 조명용 장치에서 선택되는 장치에 사용될 수 있다.
Further, the organic light emitting device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a monochromatic or white flat panel illumination device, and a monochromatic or white flexible illumination device.
이하, 바람직한 실시예를 들어 본 발명을 더욱 상세하게 설명한다. 그러나, 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이에 의하여 제한되지 않는다는 것은 당업계의 통상의 지식을 가진 자에게 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.
합성예 1 : 화학식 2 (Bis(4,6-difluorophenylpyridine)(3-hydroxy-pyridine carboxylato)Iridium, FIrpic-OH)의 합성Synthesis Example 1: Synthesis of bis (4,6-difluorophenylpyridine) (3-hydroxy-pyridine carboxylato) Iridium, FIrpic-OH
(1) [반응식 2-1] : [중간체 2-a]의 합성(1) [Synthesis 2-1]: Synthesis of [intermediate 2-a]
[중간체 2-a][Intermediate 2-a]
2,4-다이플르오로브르모벤젠 (5 g, 0.026 mol), 트리뷰틸틴틴피리딘 (10.5 g, 0.028 mol), 비스(트리페닐포스핀)팔라듐(II)클로라이드 (0.64 g, 0.0009 mol), 리튬클로라이드 (5.5 g, 0.13 mol)을 톨루엔 150 mL에 넣고 4시간 동안 환류시켰다. 실온으로 냉각시킨 후 에틸 아세테이트로 추출 후 컬럼크로마토그래피로 분리하여 [중간체 2-a] 4.3 g (수율 80%)을 얻었다.
(10 g, 0.028 mol), bis (triphenylphosphine) palladium (II) chloride (0.64 g, 0.0009 mol), 2,4-difluorobromobenzene (5 g, 0.026 mol), tristyltintine pyridine , Lithium chloride (5.5 g, 0.13 mol) were added to 150 mL of toluene and refluxed for 4 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, and then separated by column chromatography to obtain 4.3 g (yield 80%) of [intermediate 2-a].
(2) [반응식 2-2] : [중간체 2-b]의 합성(2) [Synthesis 2-2]: Synthesis of [intermediate 2-b]
[중간체 2-b][Intermediate 2-b]
2-(2,4-다이플루오로페닐)피리딘 (4.3 g, 0.022 mol), 이리듐트리클로라이드하이드레이트 (3.0 g, 0.01 mol)를 2-에톡시에탄올 120 mL, 물 40 mL에 넣고 8시간 동안 환류시켰다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용하여 분리하여 [중간체 2-b] 4.74 g (수율 78%)을 얻었다.
Iodide trichloride hydrate (3.0 g, 0.01 mol) was added to 120 mL of 2-ethoxyethanol and 40 mL of water, and the mixture was refluxed for 8 hours (4.3 g, 0.022 mol) . After the temperature was lowered to room temperature, water was added to precipitate a solid, which was then separated using a filter to obtain 4.74 g (yield 78%) of Intermediate 2-b.
(3) [반응식 2-3] : [화학식 2]의 합성(3) [Reaction formula 2-3]: Synthesis of [formula 2]
[화학식 2](2)
[중간체 2-b] (4.74 g, 0.0039 mol), 3-하이드록시피리딘-2-카복실릭에시드 (1.2 g, 0.0085 mol), 소듐카보네이트 (0.7 g, 0.005 mol)을 2-에톡시에탄올 80 mL에 넣고 4시간 동안 40 ℃ 교반했다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용해 분리하여 [화학식 2] 1.41 g (수율 51%)을 얻었다.
(1.2 g, 0.0085 mol) and sodium carbonate (0.7 g, 0.005 mol) were dissolved in 80 mL of 2-ethoxyethanol (4.74 g, 0.0039 mol) And stirred at 40 ° C for 4 hours. After the temperature was lowered to room temperature, water was added to precipitate a solid, which was then separated using a filter to obtain 1.41 g (yield: 51%) of the compound of the formula (2).
합성예 2 : 화학식 3 (Bis[3,5-difluoro-2-(4-methyl-2-pyridinyl)-4-(trifluoromethyl)phenyl](3-hydroxy-pyridinecarboxylato)iridum, Ir(F2CF3)2(pic-OH))의 합성Synthesis Example 2: Chemical Formula 3 (Bis [3,5-difluoro- 2- (4-methyl-2-pyridinyl) -4- (trifluoromethyl) phenyl] (3-hydroxy-pyridinecarboxylato) iridum, Ir (F2CF 3) 2 ( pic-OH))
(1) [반응식 3-1] : [중간체 3-a]의 합성(1) [Synthesis 3-1]: Synthesis of [intermediate 3-a]
[중간체 3-a][Intermediate 3-a]
다이아이소프로필아마이드 (3.3 g, 0.032 mol)를 THF 150 ml에 녹인 후에 n-뷰틸리튬 (12.96 mL, 0.032 mol)을 넣어준 후 -78 ℃에서 30분간 교반했다. 2,6-다이플루오로벤조트리플로라이드 (5 g, 0.027 mol)을 천천히 넣어준 후 -78 ℃에서 1시간 동안 교반했다. 트리아이소프로필보레이트(5.9 mL, 0.032 mol)을 넣고 -78 ℃에서 한시간 교반 후 상온에서 한시간 교반했다. KOH 1M 용액 100 mL로 워시 후 HCl을 이용하여 pH 5로 산성화시켰다. 물과 에틸아세테이트를 이용하여 추출한 후 농축하여 [중간체 3-a] 4.75 g (수율 78%)을 얻었다.
Diisopropylamide (3.3 g, 0.032 mol) was dissolved in 150 ml of THF, and then n -butyllithium (12.96 mL, 0.032 mol) was added thereto, followed by stirring at -78 ° C for 30 minutes. 2,6-Difluorobenzotrifluoride (5 g, 0.027 mol) was slowly added thereto, followed by stirring at -78 ° C for 1 hour. Triisopropylborate (5.9 mL, 0.032 mol) was added and the mixture was stirred at -78 째 C for one hour and then at room temperature for one hour. After washing with 100 mL of KOH 1M solution, it was acidified to
(2) [반응식 3-2] : [중간체 3-b]의 합성(2) [Synthesis 3-2]: Synthesis of [intermediate 3-b]
[중간체 3-b][Intermediate 3-b]
2-브로모-4-메틸피리딘 (3.62 g, 0.021 mol), 2,4-다이플루오로-3-트리플루오로메틸페닐보로닉에시드 (4.75 g, 0.021 mol), 테트라키스(트리페닐포스핀)팔라듐(0) (0.84 g, 0.001 mol), 소듐카보네이트 (11.1 g, 0.105 mol)을 톨루엔 200 mL, 물 80 mL에 넣고 4시간 동안 환류시켰다. 실온으로 냉각시킨 후 에틸 아세테이트로 추출 후 컬럼크로마토그래피로 분리하여 [중간체 3-b] 4.41 g (수율 77%)을 얻었다.
(3.62 g, 0.021 mol), 2,4-difluoro-3-trifluoromethylphenylboronic acid (4.75 g, 0.021 mol), tetrakis (triphenylphosphine ) Palladium (0) (0.84 g, 0.001 mol) and sodium carbonate (11.1 g, 0.105 mol) were added to 200 mL of toluene and 80 mL of water and refluxed for 4 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, and then separated by column chromatography to obtain 4.41 g (yield 77%) of Intermediate 3-b.
(3) [반응식 3-3] : [중간체 3-c]의 합성(3) [Reaction Scheme 3-3]: Synthesis of [intermediate 3-c]
[중간체 3-c][Intermediate 3-c]
[중간체 3-b] (4.41 g, 0.016 mol), 이리듐트리클로라이드하이드레이트 (3.0 g, 0.01 mol)를 2-에톡시에탄올 120 mL, 물 40 mL에 넣고 8시간 동안 환류시켰다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용하여 분리하여 [중간체 3-c] 3.47 g (수율 72%)을 얻었다.
(3.0 g, 0.01 mol) was added to 120 mL of 2-ethoxyethanol and 40 mL of water, and the mixture was refluxed for 8 hours. [Intermediate 3-b] (4.41 g, 0.016 mol) and iridium trichloride hydrate After lowering the temperature to room temperature, the reaction mixture was poured into water to precipitate a solid, which was then separated using a filter to obtain 3.47 g (yield: 72%) of Intermediate 3-c.
(4) [반응식 3-4] : [화학식 3]의 합성(4) [Reaction formula 3-4]: Synthesis of [formula 3]
[화학식 3](3)
[중간체 3-c] (3.47 g, 0.002 mol), 3-하이드록시피리딘-2-카복실릭에시드 (0.61 g, 0.005 mol), 소듐카보네이트 (0.25 g, 0.004 mol)을 2-에톡시에탄올 80 mL에 넣고 4시간 동안 40 ℃ 교반했다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용해 분리하여 [화학식 3] 1.98 g (수율 43%)을 얻었다.
(0.61 g, 0.005 mol) and sodium carbonate (0.25 g, 0.004 mol) were dissolved in 80 mL of 2-ethoxyethanol (3.70 g, 0.002 mol) And stirred at 40 ° C for 4 hours. After the temperature was lowered to room temperature, water was added to precipitate a solid, which was then separated using a filter to obtain 1.98 g (yield: 43%) of [Chemical Formula 3].
합성예 3 : 화학식 4 (Bis(2',6'-difluoro[2,3'-bipyridin]-4'-yl-)(3-hydroxy-pyridinecarboxylato)Iridium, Ir(pypy)2(pic-OH)의 합성Synthesis Example 3: Formula 4 (Bis (2 ', 6' -difluoro [2,3'-bipyridin] -4'-yl -) (3-hydroxy-pyridinecarboxylato) Iridium, Ir (pypy) 2 (pic-OH) Synthesis of
(1) [반응식 4-1] : [중간체 4-a]의 합성(1) [Reaction Scheme 4-1]: Synthesis of [intermediate 4-a]
[중간체 4-a][Intermediate 4-a]
2-브로모피리딘 (5 g, 0.031 mol), 2,6-다이플루오로-3-피리딘보로닉에시드 (5.5 g, 0.035 mol), 테트라키스(트리페닐포스핀)팔라듐(0) (1.2 g, 0.001 mol), 소듐카보네이트 (16.4 g, 0.15 mol)을 톨루엔 200 mL, 물 80 mL에 넣고 4시간 동안 환류시켰다. 실온으로 냉각시킨 후 에틸 아세테이트로 추출 후 컬럼크로마토그래피로 분리하여 [중간체 4-a] 4.4 g (수율 74%)을 얻었다.
(5 g, 0.031 mol), 2,6-difluoro-3-pyridine boronic acid (5.5 g, 0.035 mol), tetrakis (triphenylphosphine) palladium g, 0.001 mol) and sodium carbonate (16.4 g, 0.15 mol) were added to 200 mL of toluene and 80 mL of water and refluxed for 4 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, and then separated by column chromatography to obtain 4.4 g (yield: 74%) of [intermediate 4-a].
(2) [반응식 4-2] : [중간체 4-b]의 합성(2) [Synthesis 4-2]: Synthesis of [Intermediate 4-b]
[중간체 4-b][Intermediate 4-b]
[중간체 4-a] (4.4 g, 0.023 mol), 이리듐트리클로라이드하이드레이트 (3.0 g, 0.01 mol)를 2-에톡시에탄올 120 mL, 물 40 mL에 넣고 8시간 동안 환류시켰다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용하여 분리하여 [중간체 4-b] 3.95 g (수율 72%)을 얻었다.
[Intermediate 4-a] (4.4 g, 0.023 mol) and iridium trichloride hydrate (3.0 g, 0.01 mol) were placed in 120 mL of 2-ethoxyethanol and 40 mL of water and refluxed for 8 hours. After lowering the temperature to room temperature, the reaction mixture was poured into water to precipitate a solid, which was then separated using a filter to obtain 3.95 g (yield: 72%) of [Intermediate 4-b].
(3) [반응식 4-3] : [화학식 4]의 합성(3) [Reaction Scheme 4-3]: Synthesis of [Formula 4]
[화학식 4][Chemical Formula 4]
[중간체 4-b] (3.95 g, 0.003 mol), 3-하이드록시피리딘-2-카복실릭에시드 (0.99 g, 0.007 mol), 소듐카보네이트 (0.41 g, 0.004 mol)을 2-에톡시에탄올 80 mL에 넣고 4시간 동안 40 ℃ 교반했다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용해 분리하여 [화학식 4] 1.17 g (수율 51%)을 얻었다.
(0.99 g, 0.007 mol) and sodium carbonate (0.41 g, 0.004 mol) were dissolved in 80 mL of 2-ethoxyethanol (3.95 g, 0.003 mol), 3-hydroxypyridine-2-carboxylic acid And stirred at 40 ° C for 4 hours. After the temperature was lowered to room temperature, water was added to precipitate as a solid, which was then separated using a filter to obtain 1.17 g (yield: 51%) of [Chemical Formula 4].
합성예 4 : 화학식 5 (Bis[4-cyano-3,5-difluoro-2-(2-pyridinyl-)phenyl] (3-hydroxy-pyridinecarboxylato)iridium, Ir(F2CN)2(pic-OH)의 합성Synthesis Example 4 Synthesis of Bis [4-cyano-3,5-difluoro-2- (2-pyridinyl) phenyl] (3-hydroxypyridinecarboxylato) iridium and Ir (F2CN) 2 (pic-OH)
(1) [반응식 5-1] : [중간체 5-a]의 합성(1) [Reaction Scheme 5-1]: Synthesis of [intermediate 5-a]
[중간체 5-a][Intermediate 5-a]
2,6-다이플르오로벤조싸이아나이드 (5 g, 0.036 mol)를 트리플르오로메테인설포닉에시드 (27 g, 0.18 mol)에 녹였다. N-아이오도쑥신이미드 (8.1 g, 0.036 mol)를 천천히 넣은 후에 8시간 교반했다. 소듐바이카보네이트 2 M 수용액을 이용하여 중화했다. 아세테이트로 추출 후 농축하여 [중간체 5-a] 7.8 g (수율 82%)을 얻었다.
2,6-Difluorobenzothianide (5 g, 0.036 mol) was dissolved in triflouromethanesulfonic acid (27 g, 0.18 mol). N-iodomugus cinimide (8.1 g, 0.036 mol) was slowly added thereto, followed by stirring for 8 hours. And neutralized with an aqueous solution of sodium bicarbonate 2M. The mixture was extracted with ethyl acetate and then concentrated to obtain 7.8 g (yield 82%) of Intermediate 5-a.
(2) [반응식 5-2] : [중간체 5-b]의 합성(2) [Reaction Scheme 5-2]: Synthesis of [Intermediate 5-b]
[중간체 5-b][Intermediate 5-b]
[중간체 5-a] (7.8 g 0.029), 트리뷰틸틴틴피리딘 (10.86 g, 0.029 mol), 비스(트리페닐포스핀)팔라듐(II)클로라이드 (0.71 g, 0.001 mol), 리튬클로라이드 (6.14 g, 0.14 mol)을 톨루엔 150 mL에 넣고 4시간 동안 환류시켰다. 실온으로 냉각시킨 후 에틸 아세테이트로 추출 후 컬럼크로마토그래피로 분리하여 [중간체 5-b] 5.07 g (수율 81%)을 얻었다.
(0.71 g, 0.001 mol), lithium chloride (6.14 g, 0.029 mol), and bis (triphenylphosphine) palladium (II) chloride (7.71 g, 0.029 mol) , 0.14 mol) were added to 150 mL of toluene and refluxed for 4 hours. The mixture was cooled to room temperature, extracted with ethyl acetate, and then separated by column chromatography to obtain 5.07 g (yield 81%) of [Intermediate 5-b].
(3) [반응식 5-3] : [중간체 5-c]의 합성(3) [Reaction formula 5-3]: Synthesis of [intermediate 5-c]
[중간체 5-c][Intermediate 5-c]
[중간체 5-b] (5.07 g, 0.023 mol), 이리듐트리클로라이드하이드레이트 (3.0 g, 0.01 mol)를 2-에톡시에탄올 120 mL, 물 40 mL에 넣고 8시간 동안 환류시켰다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용하여 분리하여 [중간체 5-c] 5.45 g (수율 80%)을 얻었다.
[Intermediate 5-b] (5.07 g, 0.023 mol) and iridium trichloride hydrate (3.0 g, 0.01 mol) were placed in 120 mL of 2-ethoxyethanol and 40 mL of water and refluxed for 8 hours. After lowering the temperature to room temperature, water was added to precipitate as a solid, and the resultant was separated using a filter to obtain 5.45 g (yield: 80%) of Intermediate 5-c.
(4) [반응식 5-4] : [화학식 5]의 합성(4) [Reaction formula 5-4]: Synthesis of [formula 5]
[화학식 5][Chemical Formula 5]
[중간체 5-c] (5.45 g, 0.004 mol), 3-하이드록시피리딘-2-카복실릭에시드 (1.2 g, 0.0088 mol), 소듐카보네이트 (0.7 g, 0.005 mol)을 2-에톡시에탄올 80 mL에 넣고 4시간 동안 40 ℃ 교반했다. 상온으로 온도를 낮춘 후 물을 넣어 고체로 석출시킨 후 필터를 이용해 분리하여 [화학식 5] 1.49 g (수율 49%)을 얻었다.
(1.2 g, 0.0088 mol) and sodium carbonate (0.7 g, 0.005 mol) were dissolved in 80 mL of 2-ethoxyethanol (5.00 g, 0.004 mol) And stirred at 40 ° C for 4 hours. After lowering the temperature to room temperature, water was added to precipitate as a solid, which was separated by using a filter to obtain 1.49 g (yield: 49%) of the compound of the formula (5).
실험예 1. PL 스펙트럼Experimental Example 1. PL spectrum
하기 도 1a 내지 도 1d에 상기 합성예 1 내지 4의 금속 착화합물에 대해서 상온 PL 특성을 확인하였으며, 또한, 각각 FIrpic, Ir(F2CF3)2(pic), Ir(pypy)2(pic), Ir(F2CN)2(pic) 화합물과 비교하였다.You were in Figure 1a to 1d make the room temperature PL characteristics for the metal complex compounds of the above Synthesis Example 1 to 4, and each of FIrpic, Ir (F2CF 3) 2 (pic), Ir (pypy) 2 (pic), Ir (F2CN) 2 (pic) compound.
하기 도 1a 내지 도 1d의 상온 PL 특성에서 확인할 수 있는 바와 같이, 3-hydroxy-picolinato ligand 보조 리간드 분자내에 OH···O=C 수소결합을 추가하면 PL 스펙트럼이 blue shift하여 청색 색좌표를 개선할 수 있음을 알 수 있다.
As can be seen from the PL characteristics at room temperature in the following FIGS. 1A to 1D, when OH ··· O = C hydrogen bonds are added in the 3-hydroxy-picolinato ligand auxiliary ligand molecule, the PL spectrum is blue shifted to improve the blue color coordinate .
실험예 2. Phosphorescence decay lifetime 측정Experimental Example 2. Measurement of Phosphorescence decay lifetime
하기 도 2는 상기 합성예 1의 Firpic-OH와 이의 비교 화합물 Firpic에 대해서 상온(298 K, DCM)에서 인광 decay lifetime을 측정한 결과로서, FIrpic-OH는 FIrpic 대비 안정화 되어 비발광 천이에 대한 활성화 에너지가 높아져 상온에서 발광 decay lifetime이 현저히 길어짐을 알 수 있다.
FIG. 2 is a result of measurement of phosphorescence decay lifetime at room temperature (298 K, DCM) against Firpic-OH and its comparative compound Firpic of Synthesis Example 1, wherein FIrpic-OH is stabilized against FIrpic It can be seen that the activation energy for the non-emission transition is increased and the decay lifetime of light emission is remarkably increased at room temperature.
소자 실시예 ⅠDevice Example I
유리(glass) 기판상에 양극으로서 ITO 박막을 증착한 다음, 상기 양극(ITO) 상에 통상과 같은 증착 방법으로 정공 주입층(HIL), 정공 수송층(HTL), 발광층(EML), 전자 수송층(ETL) 및 음극을 형성하였다.A hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), and an electron transport layer (ITO) were formed on the ITO film by a conventional deposition method. ETL) and a cathode were formed.
이때, 정공 주입층(HIL)은 HAT-CN (1,4,5,8,9,11-hexaazatriphenylene- hexacarbonitrile)를 사용하여 100 Å의 두께로 형성하고, 정공 수송층(HTL)은 TAPC (4,4’-cyclohexylidenebis[N,N-bis(4-methylphenyl)benzenamine])을 사용하여 850 Å의 두께로 형성하였다.At this time, the hole injection layer (HIL) was formed to a thickness of 100 ANGSTROM using HAT-CN (1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile), and the hole transport layer (HTL) 4'-cyclohexylidenebis [ N , N- bis (4-methylphenyl) benzenamine]).
그리고, 상기 발광층(EML)은 정공 수송층(HTL) 상에 먼저 호스트로서 mCBP (3,3'-di(9H-carbazol-9-yl)biphenyl)와 본 발명에 따른 도판트(FIrpic-OH)의 혼합물(호스트 : 도판트 = 92 : 8의 부피비)을 300 Å의 두께로 형성하였다.The light emitting layer (EML) is formed on the hole transport layer (HTL) by first using mCBP (3,3'-di (9 H -carbazol-9- yl ) biphenyl) and the dopant (FIrpic- (Host: dopant = 92: 8 by volume) was formed to a thickness of 300 ANGSTROM.
또한, 상기 전자 수송층(ETL)은 TmPyPb (1,3,5-tri(m-pyridin-3-ylphenyl) benzene)를 사용하여 300 Å두께로 형성하였다. 상기 음극은 Liq/Al을 사용하였다.The electron transport layer (ETL) was formed to a thickness of 300 Å using TmPyPb (1,3,5-tri ( m -pyridin-3-ylphenyl) benzene). Liq / Al was used as the negative electrode.
유리 기판/양극[ITO]/정공 주입층[HAT-CN]/정공 수송층[TAPC]//발광층[mCBP + Ir 도판트(8%)]/전자수송층[TmPyPb]/음극[LiF/Al]의 적층 구조를 가지는 청색 인광 OLED 소자를 제조하였으며, 이에 대해서 소자 특성을 확인하였다.
(TAPC) // luminescent layer [mCBP + Ir dopant (8%)] / electron transport layer [TmPyPb] / cathode [LiF / Al] of the glass substrate / anode [ITO] / hole injection layer [HAT-CN] / hole transport layer A blue phosphorescent OLED with a stacked structure was fabricated and the device characteristics were confirmed.
소자 실시예 Ⅱ(비교예)Device Example II (Comparative Example)
상기 소자 실시예 Ⅰ 대비 발광층의 도판트 물질로 FIrpic을 사용한 것을 제외하고는 동일한 방법으로 소자를 제조하였다.
A device was fabricated in the same manner except that FIrpic was used as a dopant material of the light emitting layer in comparison with the above-mentioned Device Example I.
상기 소자 Ⅰ 및 Ⅱ에 대해서 발광 특성을 확인하였으며, 그 결과를 하기 [표 1] 및 도 3a 내지 도 3d에 나타내었다.The luminescent characteristics were confirmed for the devices I and II, and the results are shown in Table 1 and FIGS. 3A to 3D.
(도 3a, J-V-L characteristics; 도 3b, current efficiency-current density curves; 도 3c, power efficiency-current density curves; 도 3d, external quantum efficiency as a function of current density)(Fig. 3a, J - VL characteristics; Fig. 3b, current efficiency-current density curves ; Fig. 3c, power efficiency-current density curves ; Fig. 3d, external quantum efficiency as a function of current density)
(cd/A)Maximum current efficiency
(cd / A)
(lm/W)Maximum Power Efficiency
(lm / W)
(V)Driving voltage
(V)
CIE(x,y)Color coordinates
CIE (x, y)
(%)Maximum quantum efficiency
(%)
(FIrpic-OH)Device I
(FIrpic-OH)
(Firpic)Device II
(Firpic)
상기 [표 1] 및 도 3에서 확인할 수 있는 바와 같이, 청색 인광 유기발광소자로서, 효율, 구동전압 등은 동등하게 유지되면서 색좌표가 개선되었음을 알 수 있다.
As can be seen from the above Table 1 and FIG. 3, it can be seen that the efficiency of the blue phosphorescent organic electroluminescent device, the driving voltage and the like are kept equal and the color coordinates are improved.
소자 실시예 Ⅲ 및 ⅣDevice Embodiments III and IV
본 발명에 따른 금속 착화합물을 발광층 도판트로 사용한 소자의 수명 특성을 확인하기 위하여, 안정적인 정공수송층과 전자수송층을 사용한 하기의 조건으로 소자 Ⅲ 및 Ⅳ를 제조하였다.In order to confirm the lifetime characteristics of a device using the metal complex according to the present invention as a light emitting layer dopant, Devices III and IV were fabricated under the following conditions using a stable hole transporting layer and an electron transporting layer.
소자 Ⅲ : ITO (150 ㎚) / HAT-CN (10 ㎚) / HT211 (85 ㎚) / FIrpic-OH (8%):mCBP (30 ㎚) / LG201 (50%):Liq (50%) (30 ㎚) / Liq/Al (150 ㎚)(10 nm) / HT211 (85 nm) / FIrpic-OH (8%): mCBP (30 nm) / LG201 (50%): Liq (50%) Nm) / Liq / Al (150 nm)
소자 Ⅳ : ITO (150 ㎚) / HAT-CN (10 ㎚) / HT211 (85 ㎚) / FIrpic (8%):mCBP (30 ㎚) / LG201 (50%):Liq (50%) (30 ㎚) / Liq/Al (150 ㎚)(30 nm), LiCo (50%), LiCo (50 nm), ITO (150 nm) / HAT-CN (10 nm) / HT211 (85 nm) / FIrpic (8%): mCBP / Liq / Al (150 nm)
상기 소자 Ⅲ 및 Ⅳ에 대해서 400 nits에서 정전류 구동에서 휘도 반감수명을 측정하였으며, 그 결과를 하기 도 4에 나타내었다.The luminance half-life of the devices III and IV was measured at a constant current of 400 nits. The results are shown in FIG.
하기 도 4에서 확인할 수 있는 바와 같이, 본 발명에 따른 금속 착화합물 FIrpic-OH를 도판트로 사용한 소자(Ⅲ)의 수명은 34.3 시간, FIrpic을 도판트로 사용한 소자(Ⅳ) 수명은 20.1시간으로서 본 발명에 따른 유기발광 금속 착화합물을 도판트로 사용한 경우에 소자의 수명이 현저히 향상됨을 알 수 있다.4, the lifetime of the device (III) using the metal complex FIrpic-OH according to the present invention as a dopant was 34.3 hours, and the lifetime of the device (IV) using FIrpic as a dopant was 20.1 hours. It can be seen that the lifetime of the device is remarkably improved when the organic luminescent metal complex according to the present invention is used as a dopant.
Claims (9)
[화학식 1]
상기 [화학식 1]에서,
M은 이리듐(Ir)이고, X는 N 또는 C-R4이며 (상기 R4는 시아노기 또는 플루오르카본(CnF2n+1,n은 1 내지 10의 정수임)
R1은 수소 또는 탄소수 1 내지 7의 알킬기이고, R2 내지 R3는 각각 플루오르기이며,
n은 2이고, m은 1이다.Organic luminescent metal complex represented by the following formula 1:
[Chemical Formula 1]
In the above formula (1)
M is iridium (Ir), X is N or CR 4 (wherein R 4 is cyano group or fluorocarbon (C n F 2n + 1 , n is an integer of 1 to 10)
R 1 is hydrogen or an alkyl group having 1 to 7 carbon atoms, R 2 to R 3 are each a fluorine group,
n is 2, and m is 1.
상기 [화학식 1]로 표시되는 유기발광 금속 착화합물은 하기 [화학식 3] 내지 [화학식 5] 중에서 선택되는 어느 하나인 것을 특징으로 하는 유기발광 금속 착화합물:
[화학식 3]
[화학식 4] [화학식 5]
Wherein the organic light emitting metal complex compound represented by Formula 1 is any one selected from the following Chemical Formulas 3 to 5:
(3)
[Chemical Formula 4]
상기 유기물층 중 1 층 이상은 상기 제1항에 따른 [화학식 1]의 유기발광 금속 착화합물을 포함하는 것을 특징으로 하는 유기발광소자.1. An organic light emitting device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises an organic light emitting metal complex represented by Formula 1 according to claim 1.
상기 유기물층은 정공 주입층, 정공 수송층, 정공 주입과 정공 수송을 동시에 하는 층, 전자 수송층, 발광층, 전자 주입층 및 전자 수송과 전자 주입을 동시에 하는 층 중에서 선택되는 1층 이상을 포함하는 것을 특징으로 유기발광소자.6. The method of claim 5,
The organic material layer includes at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a layer that simultaneously transports holes and holes, an electron transport layer, a light emitting layer, an electron injection layer, Organic light emitting device.
상기 발광층이 상기 [화학식 1]로 표시되는 유기발광 금속 착화합물을 포함하는 것을 특징으로 하는 유기발광소자.The method according to claim 6,
Wherein the light emitting layer comprises an organic light emitting metal complex compound represented by Formula 1 below.
상기 [화학식 1]로 표시되는 유기발광 금속 착화합물은 상기 발광층 내의 도판트 화합물로 사용되는 것을 특징으로 하는 유기발광소자.8. The method of claim 7,
Wherein the organic light emitting metal complex compound represented by Formula 1 is used as a dopant compound in the light emitting layer.
상기 유기물층에 적색, 녹색 또는 청색 발광을 하는 유기 발광층을 하나 이상을 더 포함하여 백색 발광을 하는 것을 특징으로 하는 유기발광소자.6. The method of claim 5,
Wherein at least one of the organic light emitting layers emitting red, green or blue light is further included in the organic material layer to emit white light.
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| KR100611885B1 (en) * | 2005-04-21 | 2006-08-11 | 삼성에스디아이 주식회사 | Organic metal compounds which the compound for host and the compound for dopant were connected, organic electroluminescence display devices using the compounds and method for preparation of the devices |
| JP4496357B2 (en) * | 2004-06-04 | 2010-07-07 | 独立行政法人産業技術総合研究所 | Fluorine-substituted iridium complex and light emitting material using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4496357B2 (en) * | 2004-06-04 | 2010-07-07 | 独立行政法人産業技術総合研究所 | Fluorine-substituted iridium complex and light emitting material using the same |
| KR100611885B1 (en) * | 2005-04-21 | 2006-08-11 | 삼성에스디아이 주식회사 | Organic metal compounds which the compound for host and the compound for dopant were connected, organic electroluminescence display devices using the compounds and method for preparation of the devices |
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