KR100492243B1 - Organic luminescence device using novel organic boron compound, and process for producing the device - Google Patents
Organic luminescence device using novel organic boron compound, and process for producing the device Download PDFInfo
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- KR100492243B1 KR100492243B1 KR10-2001-0017215A KR20010017215A KR100492243B1 KR 100492243 B1 KR100492243 B1 KR 100492243B1 KR 20010017215 A KR20010017215 A KR 20010017215A KR 100492243 B1 KR100492243 B1 KR 100492243B1
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- light emitting
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- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005344 pyridylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000006617 triphenylamine group Chemical group 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
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
유기발광소자에 있어서 기능층을 구성하는데 유효한 유기붕소화합물은 하기 일반식(1):An organoboron compound effective for forming a functional layer in an organic light emitting device is represented by the following general formula (1):
(식중, Ar1은 치환 또는 무치환의 아릴기 또는 복소환기를 나타내고; R1-R11은 각각 수소, 할로겐, 알킬기, 알케닐기, 아미노기, 알콕시기, 포르밀기, 니트릴기, 아로일기, 알킬로일기, 아릴기, 아랄킬기, 복소환기중 어느 하나를 나타내고, 이들 각각은 R1-R11의 인접한 하나 또는 2이상의 쌍이 축합고리를 형성할 수 있다는 조건으로 치환되어 있어도 무치환되어 있어도 됨)로 표시된다. 상기 유기붕소화합물은, (A) 염화암모늄의 존재하에서 방향족 케톤화합물 X를 방향족 케톤화합물 또는 방향족 알데히드화합물과 반응시키는 공정과, (B) 상기 공정 (A)에서의 생성물을 방향족 붕산화합물과 반응시키는 공정으로 이루어진 제조방법에 의해 제조할 수 있다.(Wherein Ar 1 represents a substituted or unsubstituted aryl group or heterocyclic group; R 1 -R 11 each represent hydrogen, halogen, alkyl group, alkenyl group, amino group, alkoxy group, formyl group, nitrile group, aroyl group, alkyl) Any one of a royl group, an aryl group, an aralkyl group, and a heterocyclic group, each of which may be substituted or unsubstituted on the condition that adjacent one or two or more pairs of R 1 -R 11 may form a condensed ring; Is displayed. The organoboron compound comprises (A) reacting an aromatic ketone compound X with an aromatic ketone compound or an aromatic aldehyde compound in the presence of ammonium chloride, and (B) reacting the product in the step (A) with an aromatic boric acid compound. It can manufacture by the manufacturing method which consists of a process.
Description
본 발명은 새로운 유기붕소화합물을 사용하는 유기(전계)발광소자 및 그 소자의 제조방법에 관한 것이다. The present invention relates to an organic (electric field) light emitting device using a novel organic boron compound and a method for manufacturing the device.
일반적으로 유기발광소자는, 1쌍의 전극(양극 및 음극으로 이루어짐) 및 상기 전극사이에 배치된 형광성 유기화합물을 함유하는 막으로 이루어진다. 유기화합물층(막)에는, 정공(hole)과 전자가 양극 및 음극으로부터 각각 주입되고, 이렇게 해서 형광성 유기화합물의 여기자를 생성시킨다. 여기자가 기저상태로 돌아오면, 유기발광소자는 광을 방사시키거나 또는 발광을 일으킨다.In general, an organic light emitting element is composed of a film containing a pair of electrodes (composed of an anode and a cathode) and a fluorescent organic compound disposed between the electrodes. Holes and electrons are injected into the organic compound layer (film) from the anode and the cathode, respectively, thereby generating excitons of the fluorescent organic compound. When the excitons return to the ground state, the organic light emitting element emits light or emits light.
이스트만 코닥사의 연구("Appl. Phys. Lett.", vol.51, pp.913-(1987))에 따르면, 알루미늄퀴놀리놀 착체(전자전송 및 발광재료로서)의 층과 트리페닐아민 유도체(정공전송재료로서)의 층을 포함하는 상호 적층된 2개의 층으로 이루어진 기능분리형 유기발광층이 약 10V의 전압인가에 의해 약 1000cd/㎡의 조도(밝기)로 발광한다는 것이 보고되어 있다. 이것은 예를 들면 미국특허 제 4,539,507호, 제 4,720,432호 및 제 4,885,211호에도 보고되어 있다.According to Eastman Kodak's study ("Appl. Phys. Lett.", Vol. 51, pp. 913- (1987)), a layer of aluminum quinolinol complex (as electron transport and luminescent material) and triphenylamine derivative ( It has been reported that a functionally separated organic light emitting layer composed of two stacked layers including a layer of a hole transport material) emits light at an illuminance (brightness) of about 1000 cd / m 2 by applying a voltage of about 10V. This is also reported, for example, in US Pat. Nos. 4,539,507, 4,720,432 and 4,885,211.
또, 형광성 유기화합물의 종류를 변경시킴으로써, 자외선 영역에서부터 적외선영역까지 광범위한 파장영역에 걸쳐서 발광이 가능하다. 이에 대해서는, 최근 여러 화합물이 광범위하게 연구되어 왔다. 이러한 화합물은 예를들면 미국특허 제 5,151,629호, 제 5,409,783호, 제 5,382,477호와, 일본국 특개평(JPA) 2-247278호 공보, 동3-255190호 공보, 동 5-202356호 공보, 동 9-202878호 공보, 동 9-227576호 공보 등에 제안되어 있다.In addition, by changing the type of the fluorescent organic compound, light emission is possible over a wide range of wavelengths from the ultraviolet region to the infrared region. In recent years, various compounds have been extensively studied. Such compounds are described, for example, in US Pat. Nos. 5,151,629, 5,409,783, 5,382,477, JPA 2-247278, 3-255190, 5-202356, 9 -202878 and 9-227576.
저분자량재료를 사용하는 상기한 유기발광소자외에도, 공역계 폴리머를 사용하는 유기발광소자가 캠브리지대학의 리서치그룹("Nature", vol.347, pp.539-(1990))에 의해 보고되어 있다. 이 보고에 따르면, 습식도포공정에 의해 폴리페닐렌비닐렌(PPV)의 단일층이 형성되고, 상기 단일층으로부터의 발광이 확인되어 있다. 공역계 폴리머를 사용하는 이러한 유기발광소자는 또한 예를들면 미국특허 제5,247,190호, 제 5,514,878호, 제 5,672,678호와, 일본국 특개평 4-145192호 공보, 동 5-247460호 공보에도 제안되어 있다.In addition to the above organic light emitting devices using low molecular weight materials, organic light emitting devices using conjugated polymers have been reported by the Research Group of Cambridge University ("Nature", vol. 347, pp. 539- (1990)). . According to this report, a single layer of polyphenylenevinylene (PPV) is formed by a wet coating process, and light emission from the single layer is confirmed. Such organic light emitting devices using conjugated polymers have also been proposed in, for example, US Pat. Nos. 5,247,190, 5,514,878, 5,672,678, and Japanese Patent Laid-Open Nos. 4-145192 and 5-247460. .
상기한 바와 같이, 유기발광소자에 있어서의 최근의 발전은 주목할 만하고, 그에 의한 유기발광소자는 저전압인가하에서의 고휘도(밝기), 발광파장의 다양성, 고속응답성, 작은 두께 및 경량으로 특징지워지며, 이렇게 하여 광범위한 용도의 가능성을 시사하고 있다.As described above, recent developments in organic light emitting devices are noteworthy, whereby the organic light emitting devices are characterized by high brightness (brightness) under low voltage application, diversity of emission wavelengths, high-speed response, small thickness and light weight, This suggests a wide range of uses.
그러나, 상기한 유기 발광소자는, 현재 상태에서 여전히 고휘도의 광출력(발광) 및/또는 보다 높은 변환효율을 필요로 한다. 또 이들 유기발광소자는 장기간 사용하면 시간이 지남에 따라 특성이 변화되기 쉽거나, 또는 산소를 포함하는 분위기기체 또는 습기의 영향으로 열화하기 쉽다고 하는 내구성의 면에서 여전히 불충분하다.또, 전자주입재료로서는, 옥사디아졸유도체(일본국 특개평 2-216791호 공보, 동 4-363891호 공보 등)와 트리아진유도체(일본국 특개평 7-41759호 공보, 동 7-90260호 공보 등)가 알려져 있다. 그러나 유기발광소자에서 사용되는 경우, 이러한 전자주입재료는 안정된 층 또는 충분한 전자주입효율의 제공면에서 충분히 만족스럽지 못하다. 발광강도 또는 수명도 역시 충분하지 않다. However, the above organic light emitting device still requires high brightness light output (light emission) and / or higher conversion efficiency in the present state. In addition, these organic light emitting diodes are still insufficient in terms of durability such that their properties tend to change over time when they are used for a long time, or are easily degraded by the influence of an atmosphere gas or moisture containing oxygen. As the oxadiazole derivatives (Japanese Patent Laid-Open Publication No. 2-216791, Japanese Patent Application Laid-Open No. 4-363891, etc.) and triazine derivatives (Japanese Patent Laid-Open Publication No. Hei 7-41759, Japanese Patent Laid-Open No. 7-417260, etc.) are known. have. However, when used in an organic light emitting device, such an electron injection material is not sufficiently satisfactory in terms of providing a stable layer or sufficient electron injection efficiency. Luminous intensity or lifetime is also not enough.
삭제delete
본 발명의 일반적인 목적은 상기한 종래의 기술상태를 개선하는 것이다.It is a general object of the present invention to improve the above state of the art.
삭제delete
본 발명의 보다 구체적인 목적은, 새로운 유기붕소화합물을 사용하는, 수명이 길면서 고효율로 고휘도로 발광할 수 있는 유기발광소자 및 그의 제조방법을 제공하는 것이다.A more specific object of the present invention is to provide an organic light emitting device which can emit light with high brightness with long lifespan and high efficiency using a novel organic boron compound, and a manufacturing method thereof.
본 발명의 또 다른 목적은 발광파장에 다양성이 있고, 아주 우수한 내구성을 가지고 여러가지 발광색상을 나타낼 수 있는 유기발광소자 및 그의 제조방법을 제공하는 것이다. Still another object of the present invention is to provide an organic light emitting device having a variety of light emission wavelengths, having excellent durability, and exhibiting various light emission colors, and a method of manufacturing the same.
본 발명의 또 다른 목적은 용이하게 제조가 가능하고 상대적으로 값이 저렴한 유기발광소자를 제공하는 것이다. Another object of the present invention is to provide an organic light emitting device which can be easily manufactured and relatively inexpensive.
본 발명에 따르면, 양극과 음극으로 이루어진 1쌍의 전극, 상기 전극사이에 배치된 발광층, 상기 발광층과 음극사이에 배치된 유기화합물층을 구비해서 이루어진 유기발광소자에 있어서, 상기 유기화합물층은 하기 일반식(1):According to the present invention, an organic light emitting device comprising a pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the electrodes, and an organic compound layer disposed between the light emitting layer and the cathode, wherein the organic compound layer is represented by the following general formula: (One):
(식중, Ar1은 치환 또는 무치환의 아릴기 또는 복소환기(heterocyclic group)이고; R1-R11은 각각 수소, 할로겐, 알킬기, 알케닐기, 아미노기, 알콕시기, 포르밀기, 니트릴기, 아로일기, 알킬로일기, 아릴기, 아랄킬기 또는 복소환기중 어느 하나를 나타내고, 이들 각각은 R1-R11의 인접한 하나 또는 2 이상의 쌍이 축합고리를 형성할 수 있다는 조건으로 치환되어 있어도 무치환이라도 됨)로 표시되는 유기붕소화합물로 이루어진 것을 특징으로 하는 유기발광소자가 제공된다.Wherein Ar 1 is a substituted or unsubstituted aryl group or heterocyclic group; R 1 -R 11 are each hydrogen, halogen, alkyl group, alkenyl group, amino group, alkoxy group, formyl group, nitrile group, aro Any one of a diary, an alkyloyl group, an aryl group, an aralkyl group, or a heterocyclic group, each of which is unsubstituted even if substituted on the condition that adjacent one or two or more pairs of R 1 -R 11 may form a condensed ring. Provided is an organic light emitting device, characterized in that the organic boron compound represented by).
본 발명에 따르면, 양극과, 발광층과, 상기 일반식(1)의 유기붕소화합물로 이루어진 유기화합물층과, 음극이 이 순서로 배치된, 상기 유기발광소자의 제조방법에 있어서, 상기 유기화합물층은,According to the present invention, in the method of manufacturing the organic light emitting device, the organic compound layer comprising an anode, a light emitting layer, an organic compound layer composed of the organic boron compound of the general formula (1), and a cathode in this order,
(A) 염화암모늄의 존재하에 케톤화합물 X를 케톤화합물 Y 또는 알데히드화합물과 반응시키는 공정; 및(A) reacting ketone compound X with ketone compound Y or an aldehyde compound in the presence of ammonium chloride; And
(B) 상기 공정(A)에서의 생성물을 유기붕산화합물과 반응시키는 공정을 행함으로써 형성하는 것을 특징으로 하는 유기발광소자의 제조방법이 제공된다.(B) A method for producing an organic light emitting device is provided by performing a step of reacting a product in step (A) with an organic boric acid compound.
삭제delete
본 발명의 유기붕소화합물은 강한 형광특성을 나타내고, 발광소자의 발광재료로서 유용하다.The organoboron compound of the present invention exhibits strong fluorescence and is useful as a light emitting material of a light emitting device.
본 발명의 방법에 의하면, 유기붕소화합물을 용이하게 제조할 수 있다. According to the method of this invention, an organoboron compound can be manufactured easily.
본 발명의 유기붕소화합물은 전자전송층 또는/및 발광층을 구성하는 데에 유용하고, 전자주입층을 구성하는 데에도 유용하다.The organoboron compound of the present invention is useful for forming an electron transport layer and / or a light emitting layer, and is also useful for constructing an electron injection layer.
본 발명에 의한 유기발광소자는, 저전압의 인가하에 상당히 높은 휘도의 발광능력, 우수한 내구성에 의해 특징지워지며, 또한 다양한 색상의 발광이 가능하다. 예를들면, 상기 유기발광소자는 원색인 적, 청, 녹색의 발광이 가능하고, 따라서 표시장치로서 유망하다. 또, 상기 소자는 일반적으로 진공증착 또는 주조에 의해 제조할 수 있어서, 비교적 저렴하게 대면적의 소자를 용이하게 제조할 수 있다.The organic light emitting device according to the present invention is characterized by the light emitting ability of a considerably high luminance and excellent durability under the application of low voltage, and also it is possible to emit light of various colors. For example, the organic light emitting device can emit light of primary colors red, blue, and green, and thus is promising as a display device. In addition, the device can generally be manufactured by vacuum deposition or casting, so that a large-area device can be easily manufactured at a relatively low cost.
본 발명의 이들 및 다른 목적, 특징 및 이점 등은 첨부도면과 관련하여 취한 이하의 본 발명의 바람직한 실시예의 설명을 고려하면 더욱 명백해질 것이다.These and other objects, features and advantages of the present invention will become more apparent upon consideration of the following description of the preferred embodiments of the present invention taken in conjunction with the accompanying drawings.
본 발명에 이용되는 새로운 유기붕소화합물은, 하기 일반식(1)로 표시된다:The new organoboron compound used in the present invention is represented by the following general formula (1):
. .
일반식(1)에 있어서, Ar1은 치환 또는 무치환의 아릴기 또는 복소환기를 나타낸다. 아릴기의 예로서는, 페닐기, 톨릴기, 아미노페닐기, 니트로페닐기, 할로겐치환페닐기 등의 단환기; 비페닐기, 테르페닐기, 나프틸기, 안트라닐기 등의 다환 방향족기를 들 수 있다.In General formula (1), Ar <1> represents a substituted or unsubstituted aryl group or heterocyclic group. As an example of an aryl group, Monocyclic groups, such as a phenyl group, a tolyl group, an aminophenyl group, a nitrophenyl group, and a halogen substituted phenyl group; Polycyclic aromatic groups, such as a biphenyl group, a terphenyl group, a naphthyl group, and anthranyl group, are mentioned.
복소환기의 예로서는, 피리딜기외에, 피롤릴기, 티에닐기, 이미다졸릴기, 피라졸릴기와 같은 5원고리 기 등의 단환성 복소환기; 퀴놀릴기, 아크리디닐기와 같은 6,6-축합복소환기 및 인돌리닐기와 같은 6,5-축합복소환기 등의 축합복소환기를 들 수 있다.As an example of a heterocyclic group, In addition to a pyridyl group, Monocyclic heterocyclic groups, such as 5-membered ring groups, such as a pyrrolyl group, a thienyl group, an imidazolyl group, a pyrazolyl group; And condensed heterocyclic groups such as 6,6-condensed heterocyclic groups such as quinolyl groups and acridinyl groups and 6,5-condensed heterocyclic groups such as indolinyl groups.
또, 아릴기 또는 복소환기에 임의로 소유되는 치환기로서는, 할로겐, 알킬기, 알콕시기, 아미노기, 이미노기, 아세틸기, 포르밀기, 니트로기, 실릴(silyl)기, 아릴기, 복소환기 및 니트릴기를 들 수 있다. 더 구체적으로는, 할로겐치환기로서는 클로로, 브로모, 플루오로 및 요오도를 들 수 있고, 알킬치환기로서는 메틸기, 에틸기 및 프로필기와 같은 직쇄알킬기와, 이소부틸기 및 이소프로필기와 같은 분기알킬과, 벤질기와 같은 아랄킬기를 포함하는 치환된 알킬기를 들 수 있다. 또, 아미노알콕시치환기로서는 메톡시기와 에톡시기를 들 수 있고, 아미노치환기로서는 2급아미노기와 3급아미노기를 들 수 있고, 실릴치환기로서는 디메틸실릴기, 디페닐실릴기 및 t-부틸디페닐실릴기를 들 수 있다. 또, 아릴치환기로서는, 페닐기와 같은 치환 또는 무치환의 단환기와, 비페닐기, 테르페닐기, 나프틸기 및 안트라닐기와 같은 치환 또는 무치환의 다환성 방향족기를 들 수 있고, 복소환기의 치환기로서는 퀴놀릴기, 피롤릴기 및 티에닐기와 같은 단환성 복소환기와, 아크리디닐기와 같은 6,6-축합복소환기와 인돌리닐기와 같은 6,5-축합복소환기를 들 수 있다.Examples of the substituent optionally possessed by an aryl group or a heterocyclic group include halogen, alkyl group, alkoxy group, amino group, imino group, acetyl group, formyl group, nitro group, silyl group, aryl group, heterocyclic group and nitrile group. Can be. More specifically, examples of the halogen substituent include chloro, bromo, fluoro and iodo, and examples of the alkyl substituent include linear alkyl groups such as methyl, ethyl and propyl, branched alkyl such as isobutyl and isopropyl and benzyl And substituted alkyl groups including aralkyl groups such as groups. Moreover, a methoxy group and an ethoxy group are mentioned as an aminoalkoxy substituent, A secondary amino group and a tertiary amino group are mentioned as an amino substituent, As a silyl substituent, a dimethyl silyl group, a diphenyl silyl group, and t-butyl diphenyl silyl group are mentioned. Can be mentioned. Moreover, as an aryl substituent, substituted or unsubstituted monocyclic groups, such as a phenyl group, and substituted or unsubstituted polycyclic aromatic groups, such as a biphenyl group, a terphenyl group, a naphthyl group, and an anthranyl group, are mentioned, As a substituent of a heterocyclic group, Monocyclic heterocyclic groups, such as a teal group, a pyrrolyl group, and a thienyl group, 6, 5- condensed heterocyclic groups, such as an acridinyl group, and 6, 5- condensed heterocyclic groups, such as an indolinyl group, are mentioned.
반면에, 치환기 R1-R11은 각각 독립적으로 수소, 할로겐, 알킬기, 알케닐기, 아미노기, 알콕시기, 포르밀기, 니트릴기, 아로일기, 알킬로일기, 아릴기, 아랄킬기 또는 복소환기 중 어느 하나를 나타내고, R1-R11의 하나 또는 2이상의 쌍, 즉 1쌍의 R1 및 R2, R2 및 R3, R3 및 R4, R4 및 R5, R5 및 R6, R6 및 R7, R8 및 R9, R9 및 R10, R10 및 R11 또는 R11 및 R1이 축합환을 형성할 수 있다는 조건으로 치환되어 있어도 무치환되어 있어도 된다.On the other hand, substituents R 1 -R 11 are each independently hydrogen, halogen, alkyl group, alkenyl group, amino group, alkoxy group, formyl group, nitrile group, aroyl group, alkyloyl group, aryl group, aralkyl group or heterocyclic group One, one or two or more pairs of R 1 -R 11 , that is, one pair of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , Unsubstituted even if R 5 and R 6 , R 6 and R 7 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 or R 11 and R 1 may be substituted on the condition that they may form a condensed ring; You may be.
치환기 R1-R11의 특정예를 아래에 열거한다.Specific examples of the substituents R 1 -R 11 are listed below.
할로겐의 예로서는 클로로, 브로모, 플루오로 및 요오도를 들 수 있다.Examples of halogen include chloro, bromo, fluoro and iodo.
알킬기의 예로서는, 1∼20의 탄소원자수를 가지는 직쇄 또는 분기알킬기를 포함하며, 이와 같은 알킬기로서는 메틸기, 에틸기, n-프로필기, n-옥틸기 및 n-데실기와 같은 직쇄알킬기와; 이소프로필기 및 t-부틸기와 같은 분기알킬기를 들 수 있다.알케닐기의 예로서는 비닐기를 들 수 있다.Examples of the alkyl group include a straight chain or branched alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group include straight chain alkyl groups such as methyl group, ethyl group, n-propyl group, n-octyl group and n-decyl group; Branched alkyl groups, such as an isopropyl group and t-butyl group, are mentioned. As an example of an alkenyl group, a vinyl group is mentioned.
아미노기의 예로서는, 무치환 아미노기; 하나의 알킬기, 아랄킬기 또는 아릴기로 치환된 1치환아미노기; 및 알킬기, 아랄킬기 또는 아릴기가 2개 치환된 2치환 아미노기를 들 수 있다. 치환알킬기의 예로서는, 메틸기, 에틸기, n-프로필기, n-옥틸기 및 n-데실기와 같은 직쇄 알킬기와, 이소프로필기 및 t-부틸기와 같은 분기알킬기를 들 수 있다.As an example of an amino group, Unsubstituted amino group; A monosubstituted amino group substituted with one alkyl group, aralkyl group or aryl group; And a bisubstituted amino group in which two alkyl groups, aralkyl groups or aryl groups are substituted. Examples of the substituted alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-octyl group and n-decyl group, and branched alkyl groups such as isopropyl group and t-butyl group.
삭제delete
알콕시기의 예로서는, 메톡시기, 에톡시기와 같은 알킬옥시기; 페닐옥시기와 같은 방향족 옥시기를 들 수 있다.Examples of the alkoxy group include alkyloxy groups such as methoxy group and ethoxy group; Aromatic oxy groups, such as a phenyloxy group, are mentioned.
아로일기의 예로서는, 벤조일기, 나프토일기 및 안트로일기를 들 수 있다.As an example of an aroyl group, a benzoyl group, a naphthoyl group, and an anthroyl group are mentioned.
알킬로일기의 예로서는, 아세틸기, n-프로피오닐기, 이소부티로일기와 같은 직쇄 또는 분기의 지방족 카르보닐기와; 시클로헥실카르보닐기와 같은 환상 지방족 카르보닐기를 들 수 있다.Examples of the alkyloyl group include linear or branched aliphatic carbonyl groups such as acetyl group, n-propionyl group and isobutyroyl group; Cyclic aliphatic carbonyl groups, such as a cyclohexylcarbonyl group, are mentioned.
아릴기의 예로서는, 페닐기와 같은 단환성 방향족기와; 나프틸기, 안트라닐기와 같은 방향족 축합고리기를 들 수 있다.Examples of the aryl group include monocyclic aromatic groups such as phenyl group; Aromatic condensed ring groups, such as a naphthyl group and anthranyl group, are mentioned.
아랄킬기의 예로서는, 벤질기, 피리딜메틸기, 나프토메틸기를 들 수 있다.As an example of an aralkyl group, a benzyl group, a pyridylmethyl group, a naphthomethyl group is mentioned.
복소환기의 예로서는, 푸릴기, 티에닐기, 피롤릴기, 이미다졸릴기, 피리딜기와 같은 단환성 복소환기와; 인돌릴기, 아미디닐기와 같은 축합복소환기를 들 수 있다.Examples of the heterocyclic group include monocyclic heterocyclic groups such as furyl group, thienyl group, pyrrolyl group, imidazolyl group and pyridyl group; Condensed heterocyclic groups, such as an indolyl group and an amidinyl group, are mentioned.
이들 치환기는 더욱 치환되어 있어도 된다. 치환의 경우에 있어서는, 치환기의 예로서는, 할로겐, 알킬기, 아미노기, 알콕시기, 포르밀기, 니트릴기, 니트로기, 아로일기, 알킬로일기, 치환 또는 무치환의 아릴기, 치환 또는 무치환의 아랄킬기 및 치환 또는 무치환의 복소환기를 포함하며, 치환 또는 무치환의 아릴기, 아랄킬기 및 복소환기의 치환기로서는 할로겐기, 알릴기, 아미노기, 알콕시기, 포르밀기, 니트릴기, 아로일기, 알킬로닐기, 치환 또는 무치환의 아릴기, 치환 또는 무치환의 아랄킬기, 치환 또는 무치환의 복소환기를 포함하는 것을 특징으로 하지만, 이들에 한정되는 것은 아니다. 그 특정예는 아래에 열거한 것들을 포함한다.These substituents may further be substituted. In the case of substitution, as an example of a substituent, a halogen, an alkyl group, an amino group, an alkoxy group, a formyl group, a nitrile group, a nitro group, an aroyl group, an alkyloyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group And a substituted or unsubstituted heterocyclic group, and examples of the substituted or unsubstituted aryl group, aralkyl group and heterocyclic group substituent include halogen group, allyl group, amino group, alkoxy group, formyl group, nitrile group, aroyl group and alkyl group. It includes, but is not limited to, a silyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and a substituted or unsubstituted heterocyclic group. Specific examples include those listed below.
또, R1∼R11 중 상기한 인접한 하나 또는 그 이상의 쌍의 조합에 의해 형성할 수 있는 축합고리의 예로서는, 벤조기, 안트로기, 피리도기, 피라지노기, 이미다조기, 티에노기, 피라졸로기, 카르바졸로기 등의 단환구조 또는 축합고리구조를 들 수 있다.Moreover, as an example of the condensed ring which can be formed by the combination of said adjacent one or more pair among R <1> -R <11> , A benzo group, anthro group, a pyrido group, a pyrazino group, an imidazo group, a thieno group, Monocyclic structures or condensed ring structures such as pyrazolo groups and carbazole groups.
일반식(1)로 표시되는 유기붕소화합물의 대표적인 예시 화합물을 구조식으로서 이하에 열거하나, 이들로 한정되는 것은 아니다. 다음의 구조식에 있어서 치환기를 나타내기 위하여 몇몇 기호, 즉 메틸기에 대해서는 Me, 페닐기에 대해서는 Ph, 삼차부틸기에 대해서는 t-Bu가 사용된다.Representative exemplary compounds of the organoboron compound represented by the general formula (1) are listed below as structural formulas, but are not limited thereto. In the following structural formulae, some symbols, Me for methyl group, Ph for phenyl group, t-Bu for tertiary butyl group are used.
본 발명의 프로세스에 따르면, 상기한 일반식(1)의 유기붕소화합물은, 방향족 케톤화합물, 바람직하게는 벤조일케톤화합물을 방향족 케톤화합물, 바람직하게는 벤조일케톤화합물, 또는 방향족 알데히드화합물, 바람직하게는 벤즈알데히드화합물과 아세트산 암모늄이 존재하는 데에서 반응시키는 공정과, 상기 공정의 반응생성물을 유기붕산화합물, 바람직하게는 방향족 붕산화합물과 반응시키는 공정에 의해서 제조할 수 있다.According to the process of the present invention, the organoboron compound of formula (1) is an aromatic ketone compound, preferably a benzoyl ketone compound, an aromatic ketone compound, preferably a benzoyl ketone compound, or an aromatic aldehyde compound, preferably It can be produced by the step of reacting in the presence of a benzaldehyde compound and ammonium acetate and the step of reacting the reaction product of the step with an organic boric acid compound, preferably an aromatic boric acid compound.
더 구체적인 실시예에 따르면, 케톤화합물 X와 케톤화합물 Y에 아세트산 암모늄과 함께 고리부가반응을 실시하여 피리딘화합물을 형성하고, 이 피리딘화합물을 붕산화합물과 반응시켜 부가반응을 야기하도록 함으로써, 일반식(1)의 유기붕소화합물을 합성할 수 있다.According to a more specific embodiment, the ketone compound X and the ketone compound Y are subjected to a ring addition reaction with ammonium acetate to form a pyridine compound, and the pyridine compound is reacted with a boric acid compound to cause an addition reaction. The organoboron compound of 1) can be synthesized.
더욱 구체적으로는, 하기 일반식(2):More specifically, the following general formula (2):
(식중, R12-R15는 일반식(1)의 R1-R11로 나타낸 것들과 동일한 치환기를 나타냄)의 케톤화합물 X는, 아세트산 암모늄과 함께 하기 일반식(3):(Wherein R 12 -R 15 represents the same substituents as those represented by R 1 -R 11 in formula (1)), the ketone compound X is represented by the following general formula (3) together with ammonium acetate:
삭제delete
(식중, R16-R20은 일반식(1)의 R1-R11로 나타낸 것과 동일한 치환기를 나타냄)의 케톤화합물 Y와 반응하여, 하기 일반식(4):Wherein R 16 -R 20 represent the same substituents as those represented by R 1 -R 11 of General Formula (1), and react with ketone compound Y of General Formula (4):
(식중, R12-R20은 상기한 것과 동일함)의 피리딘화합물을 형성한다.Wherein R 12 -R 20 are the same as described above.
상기 일반식(4)의 피리딘화합물은 다음의 공정에 의해서도 합성할 수 있다.The pyridine compound of the general formula (4) can also be synthesized by the following process.
하기 일반식(5):General formula (5) below:
(여기에서, R21-R24는 일반식(1)의 R1-R11로 나타낸 것과 동일한 치환기임)의 케톤화합물 X는, 아세트산 암모늄과 함께 하기 일반식(6):Here, the ketone compound X of R 21 -R 24 is the same substituent as represented by R 1 -R 11 in formula (1), together with ammonium acetate, has the following formula (6):
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(식중, R25-R29는, 일반식(1)의 R1-R11로 나타낸 것들과 동일한 치환기임)의 알데히드화합물과 반응하여, 하기 일반식(7):Wherein R 25 -R 29 are the same substituents as those represented by R 1 -R 11 in General Formula (1), and react with an aldehyde compound of the following General Formula (7):
삭제delete
로 표시되는 화합물을 형성한다. 일반식(7)의 화합물은 산성 조건하에서 가수분해되어, 하기 일반식(8)(상기 일반식(4)에 의해서도 표시될 수 있음):To form a compound represented by. The compound of formula (7) is hydrolyzed under acidic conditions to give the following formula (8), which may also be represented by formula (4) above:
(식중, R21-R29는 상기와 동일함)의 화합물을 형성한다.In which R 21 -R 29 are the same as defined above.
상기 일반식(4) 및 일반식(8)의 화합물은 하기 일반식(9):Compounds of the general formulas (4) and (8) are represented by the following general formula (9):
(식중, Ar2는 일반식(1)의 Ar1으로 나타낸 것과 동일한 치환기임)의 붕산화합물과 반응하여, 하기 일반식(10) 또는 일반식(11)의 화합물을 형성한다:Wherein Ar 2 is the same substituent as represented by Ar 1 in formula (1) to form a compound of formula (10) or formula (11):
. .
일반식(10) 또는 일반식(11)의 화합물은 일반식(1)로 표시되는 것과 실질적으로 동일하다.The compound of general formula (10) or general formula (11) is substantially the same as that represented by general formula (1).
상기한 반응구조에서, 일반식(2)의 화합물과 일반식(3)의 화합물은 2:5 내지 5:2의 몰비로 반응하는 것이 바람직하다. 아세트산 암모늄은 몰비의 견지에서 일반식(2)의 화합물보다 적어도 10배의 양을 사용하는 것이 바람직하다. 반응은 70-100℃에서 3-20시간 동안 아세트산과 같은 용매중에서 이루어지는 것이 바람직하다.In the above reaction structure, the compound of formula (2) and the compound of formula (3) are preferably reacted in a molar ratio of 2: 5 to 5: 2. Ammonium acetate is preferably used in an amount of at least 10 times greater than the compound of the general formula (2) in terms of molar ratio. The reaction is preferably carried out in a solvent such as acetic acid at 70-100 ° C. for 3-20 hours.
또, 일반식(5)의 화합물과 일반식(6)의 화합물은 1:1 내지 4:1의 몰비로 반응하는 것이 바람직하다. 아세트산 암모늄은 몰비의 견지에서 일반식(5)의 화합물의 적어도 10배의 양을 사용하는 것이 바람직하다. 반응은 70-100℃에서 3-20시간 동안 아세트산과 같은 용매중에서 이루어지는 것이 바람직하다.Moreover, it is preferable that the compound of General formula (5) and the compound of General formula (6) react with the molar ratio of 1: 1-4: 1. Ammonium acetate is preferably used in an amount of at least 10 times the compound of the formula (5) in terms of molar ratio. The reaction is preferably carried out in a solvent such as acetic acid at 70-100 ° C. for 3-20 hours.
일반식(7)의 화합물의 가수분해는 70-100℃에서 3-10시간 동안 브롬화 수소산(hydrobromic acid)과 같은 산을 사용해서 행하는 것이 바람직하다.Hydrolysis of the compound of the general formula (7) is preferably carried out using an acid such as hydrobromic acid at 70-100 ° C. for 3-10 hours.
일반식(4) 또는 일반식(8)의 화합물과 일반식(9)의 화합물은 1:1 내지 4:1의 몰비로 반응하는 것이 바람직하다. 반응은 20-100℃에서 1-10시간 동안 아세트산과 같은 용매중에서 이루어지는 것이 바람직하다.It is preferable that the compound of the formula (4) or (8) and the compound of the formula (9) react in a molar ratio of 1: 1 to 4: 1. The reaction is preferably carried out in a solvent such as acetic acid at 20-100 ° C. for 1-10 hours.
본 발명에 의한 유기붕소화합물은 강한 형광방출특성을 나타내고, 따라서 다음에 기술하는 유기발광소자에서 적합하게 사용될 뿐만 아니라 예를 들면 붕산 등의 정량분석용 시약으로서도 유용하다.The organoboron compound according to the present invention exhibits strong fluorescence emission characteristics, and therefore is not only suitably used in the organic light emitting device described below, but also as a reagent for quantitative analysis such as, for example, boric acid.
본 발명의 일양상에 따르면, 1쌍의 전극과 이 1쌍의 전극사이에 배치된 일반식(1)의 유기붕소화합물로 이루어진 층을 구비한 유기발광소자를 제공하는 것이다.According to one aspect of the present invention, there is provided an organic light emitting device having a pair of electrodes and a layer made of an organoboron compound of the general formula (1) disposed between the pair of electrodes.
본 발명의 유기발광소자에 있어서는, 상기한 일반식(1)의 유기붕소화합물로 이루어진 유기화합물층이 진공증착 또는 습식도포처리에 의해 상기 1쌍의 전극을 이루는 양극과 음극사이에 형성된다. 유기화합물층은 10㎛이하의 두께로 형성하는 것이 바람직하며, 더 바람직하게는 0.5㎛이하, 더욱 바람직하게는 0.01-0.5㎛이하로 형성하는 것이 바람직하다.In the organic light emitting device of the present invention, an organic compound layer made of the organoboron compound of the general formula (1) is formed between the anode and the cathode which form the pair of electrodes by vacuum deposition or wet coating. The organic compound layer is preferably formed to a thickness of 10 μm or less, more preferably 0.5 μm or less, and more preferably 0.01 to 0.5 μm or less.
또, 1쌍의 전극사이에 상기한 일반식(1)의 유기붕소화합물로 이루어진 적어도 한개의 층을 포함하는 복수의 층을 배치함으로써 본 발명의 발광소자를 제공할 수 있다. 본 발명에 따르면, 일반식(1)로 표시되는 화합물의 범위로부터 유기붕소화합물을 적당히 선택함으로써 소망의 발광색을 발광하는 발광소자를 제공할 수 있다.Further, the light emitting device of the present invention can be provided by disposing a plurality of layers including at least one layer of the organoboron compound of the general formula (1) described above between a pair of electrodes. According to the present invention, it is possible to provide a light emitting device that emits a desired emission color by appropriately selecting an organoboron compound from the range of the compound represented by the general formula (1).
즉, 도면을 참조하면, 본 발명의 유기발광소자를 구성하는 유기화합물층은 도 1에 도시한 바와 같은 단층구조 또는 도 2 및 3에 도시한 바와 같은 2이상의 층의 적층구조를 가진다.That is, referring to the drawings, the organic compound layer constituting the organic light emitting device of the present invention has a single layer structure as shown in Fig. 1 or a lamination structure of two or more layers as shown in Figs.
더 구체적으로는, 도 1은 본 발명의 유기발광소자의 실시예를 예시한 개략적 단면도이다. 도 1을 참조하면, 유기발광소자는, 기판(1)상에 차례대로 양극(2), 발광층(3) 및 음극을 배치해서 적층구조를 형성하고 있다. 발광층(3)은 정공전송기능, 전자전송기능 및 발광기능을 각각 나타내는 복수의 화합물을 조합 또는 혼합하여 상기 기능들을 나타내는 단일종류의 발광재료로 이루어진다. 발광층(3)은 5nm~1㎛, 바람직하게는 10-500nm의 두께를 가진다.More specifically, Figure 1 is a schematic cross-sectional view illustrating an embodiment of the organic light emitting device of the present invention. Referring to FIG. 1, in the organic light emitting device, an anode 2, a light emitting layer 3, and a cathode are sequentially arranged on a substrate 1 to form a stacked structure. The light emitting layer 3 is composed of a single kind of light emitting material showing the above functions by combining or mixing a plurality of compounds each showing a hole transport function, an electron transport function and a light emission function. The light emitting layer 3 has a thickness of 5 nm to 1 mu m, preferably 10 to 500 nm.
도 2는 유기발광소자의 다른 실시예의 적층구조를 나타내는 단면도이다. 도 2를 참조하면, 유기발광소자는 적층구조를 형성하기 위하여 기판(1)상에 양극(2), 정공전송층(5), 전자전송층(6) 및 음극(4)이 순서대로 연속적으로 배치되고, 정공전송층(5)과 전자전송층(6)의 어느 하나 또는 양쪽은, 조합해서 발광층(3)을 구성하기 위해, 정공전송기능 및/또는 전자전송기능을 역시 각각 가지는 발광재료를 포함해도 된다. 상기 층(6)과 (5)중의 하나는 발광기능은 가지지 않으나, 양호한 전자전송기능 또는 정공전송기능을 가지는 재료를 포함해도 된다. 정공전송층(5)과 전자전송층(6)의 각각은 5nm~1㎛, 바람직하게는 10-500nm의 두께를 가진다.2 is a cross-sectional view showing a laminated structure of another embodiment of an organic light emitting device. Referring to FIG. 2, in the organic light emitting diode, an anode 2, a hole transport layer 5, an electron transport layer 6, and a cathode 4 are sequentially disposed on a substrate 1 to form a stacked structure. One or both of the hole transport layer 5 and the electron transport layer 6 are disposed so as to combine the light emitting material with the hole transport function and / or the electron transport function, respectively, to form the light emitting layer 3 in combination. You may include it. One of the layers 6 and 5 does not have a light emitting function but may include a material having a good electron transfer function or a hole transfer function. Each of the hole transport layer 5 and the electron transport layer 6 has a thickness of 5 nm to 1 탆, preferably 10-500 nm.
도 3은 본 발명의 유기발광소자의 또 다른 실시예를 나타내는 단면도이다. 도 3을 참조하면, 유기발광소자는 적층구조를 형성하기 위해 기판(1)상에 양극(2), 정공전송층(5), 전자전송층(6) 및 음극(4)이 순서대로 연속적으로 배치되어 있다. 이 실시예에 있어서는, 유기화합물층의 캐리어전송기능과 발광기능은 각 층에 분리되어 있다. 정공전송층(5), 발광층(3) 및 전자전송층(6)의 각각은 소망의 성능을 나타내기 위하여 기대되는 기능을 각각 가지는 단일종류 또는 복수종류의 화합물을 포함한다. 더 구체적으로는, 복수종의 화합물을 조합해서 사용하는 경우에는 각 층에 대한 재료를 선택하는데 있어서 자유도가 증가하고, 다른 발광파장을 가진 여러 종류의 화합물을 사용할 수 있기 때문에 발광색상을 다양하게 할 수 있다.3 is a cross-sectional view showing still another embodiment of the organic light emitting device of the present invention. Referring to FIG. 3, in the organic light emitting diode, an anode 2, a hole transport layer 5, an electron transport layer 6, and a cathode 4 are sequentially disposed on a substrate 1 to form a stacked structure. It is arranged. In this embodiment, the carrier transfer function and the light emission function of the organic compound layer are separated in each layer. Each of the hole transport layer 5, the light emitting layer 3, and the electron transport layer 6 contains a single kind or a plurality of kinds of compounds each having a function expected to exhibit a desired performance. More specifically, when a combination of plural kinds of compounds is used, the degree of freedom in selecting materials for each layer is increased, and various kinds of compounds having different emission wavelengths can be used. Can be.
또, 캐리어와 여기자는 중앙의 발광층(3)에서 효율적으로 가두어지기 때문에 발광효율을 증가시킬 수 있다.In addition, since the carrier and the exciton are efficiently confined in the central light emitting layer 3, the light emission efficiency can be increased.
도 3의 실시예에 있어서, 정공전송층(5), 발광층(3) 및 전자전송층(6)의 각각은 5nm~1㎛, 바람직하게는 10-500nm의 두께를 가진다.In the embodiment of Fig. 3, each of the hole transport layer 5, the light emitting layer 3 and the electron transport layer 6 has a thickness of 5nm to 1㎛, preferably 10-500nm.
그러나, 상기한 도 1 ~ 도 3은 단순히 본 발명에 따른 유기발광소자의 기본적인 구성을 나타낸 것으로 이해되어야 하며, 여러 가지 변형이 가능하다. 예를 들면, 하나 또는 복수의 유기화합물층과 전극들(양극 및 음극)사이에, 전자주입층(음극쪽 위에), 정공주입층(양극쪽 위에), 절연층, 접착층 또는 간섭층을 배치하는 것도 가능하다. 또, 정공전송층(5)은 이온화전위가 다른 2개의 층으로 분리할 수 있다.However, it should be understood that FIG. 1 to FIG. 3 merely show the basic configuration of the organic light emitting device according to the present invention, and various modifications are possible. For example, an electron injection layer (on the cathode side), a hole injection layer (on the anode side), an insulating layer, an adhesive layer, or an interference layer may be disposed between one or a plurality of organic compound layers and the electrodes (anode and cathode). It is possible. In addition, the hole transport layer 5 can be separated into two layers having different ionization potentials.
일반식(1)의 유기붕소화합물로 이루어진 층을 정공주입 및 전송층, 전자전송층 및 발광층의 어느 것을 구성하기 위하여 사용할 수 있다. 그러나, 일반식(1)의 유기붕소화합물은 이러한 기능층을 형성하기 위하여, 그 예가 이후에 열거되는 공지의 정공전송화합물, 전자전송화합물 또는 발광화합물과 조합하여 필요에 따라서 사용할 수 있다.The layer made of the organoboron compound of the formula (1) can be used to form any of a hole injection and transport layer, an electron transport layer and a light emitting layer. However, the organoboron compound of the general formula (1) may be used if necessary in combination with a known hole transport compound, electron transport compound or light emitting compound, examples of which are listed hereinafter, in order to form such a functional layer.
정공전송화합물Hole transport compound
정공전송화합물Hole transport compound
정공전송화합물Hole transport compound
정공전송화합물Hole transport compound
정공전송화합물Hole transport compound
전자전송화합물Electron transport compound
전자전송화합물Electron transport compound
전자전송화합물Electron transport compound
전자전송화합물Electron transport compound
발광재료(도펀트)Emitting Material (Dopant)
상기한 바와 같이, 일반식(1)의 유기붕소화합물 또는 다른 유기화합물층을 포함하는 유기화합물층은 진공증착 또는 적당한 용매에서 관련 화합물의 용액의 도포에 의해서 형성된다. 용액도포의 경우에 있어서, 유기화합물을 적당한 바인더수지와 혼합하여 막을 형성하는 것도 가능하다. 이 경우, 일반식(1)의 유기붕소화합물을 포함하는 유기화합물을 예를 들면 바인더수지 1중량부당 0.01~20중량부, 바람직하게는 0.1~10중량부 사용한다.As described above, the organic compound layer comprising the organoboron compound or other organic compound layer of formula (1) is formed by vacuum deposition or application of a solution of the related compound in a suitable solvent. In the case of solution coating, it is also possible to form a film by mixing an organic compound with a suitable binder resin. In this case, the organic compound containing the organoboron compound of the general formula (1) is used, for example, 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 1 part by weight of the binder resin.
상기 목적을 위해 사용되는 바인더수지는 광범위한 범위로부터 선택된다. 그 예로서는, 폴리비닐카르바졸수지, 폴리카보네이트수지, 폴리에스테르수지, 폴리아릴레이트수지, 폴리스티렌수지, 아크릴수지, 메타크릴수지, 부티랄수지, 폴리비닐아세탈수지, 디알릴프탈레이트수지, 페놀수지, 에폭시수지, 실리콘수지, 폴리술폰수지 및 요소수지를 포함한다. 이들 수지는 단독으로, 또는 2종 이상 조합해서, 또는 공중합체의 형태로 사용해도 된다.The binder resin used for this purpose is selected from a wide range. Examples thereof include polyvinylcarbazole resin, polycarbonate resin, polyester resin, polyarylate resin, polystyrene resin, acrylic resin, methacryl resin, butyral resin, polyvinyl acetal resin, diallyl phthalate resin, phenol resin, epoxy Resins, silicone resins, polysulfone resins and urea resins. You may use these resin individually or in combination of 2 or more types, or in the form of a copolymer.
양극(도 1 ~ 도 3에 도시한 (2))의 재료로서는, 가능한 한 큰 일함수를 가지는 것을 사용하는 것이 바람직하며; 그 예로서는 금, 백금, 니켈, 팔라듐, 코발트, 바나듐과 같은 금속류 및 이들의 합금; 산화주석, 산화아연, 산화주석인듐(ITO), 산화아연인듐과 같은 금속산화물; 및 폴리아닐린, 폴리피롤, 폴리티오펜, 황화폴리페닐렌과 같은 도전성 폴리머를 포함한다. 이들 화합물은 단독으로 또는 2종 이상 조합해서 사용해도 된다.As a material of the anode ((2) shown in Figs. 1 to 3), it is preferable to use one having a work function as large as possible; Examples thereof include metals such as gold, platinum, nickel, palladium, cobalt and vanadium and alloys thereof; Metal oxides such as tin oxide, zinc oxide, tin indium oxide (ITO), and zinc indium oxide; And conductive polymers such as polyaniline, polypyrrole, polythiophene, polyphenylene sulfide. You may use these compounds individually or in combination of 2 or more types.
한편, 도 1 ~ 도 3에 도시한 음극(4)의 재료로서는, 작은 일함수를 가진 것을 사용하는 것이 바람직하고, 그 예로서는, 리튬, 나트륨, 칼륨, 칼슘, 마그네슘, 알루미늄, 인듐, 은, 납, 주석 및 크롬과 같은 금속류 및 이들의 합금을 포함한다. 산화주석인듐(ITO)과 같은 금속산화물을 사용하는 것도 가능하다. 음극은 1층 또는 복수층의 적층체로 형성해도 된다.On the other hand, as the material of the negative electrode 4 shown in Figs. 1 to 3, those having a small work function are preferably used. Examples thereof include lithium, sodium, potassium, calcium, magnesium, aluminum, indium, silver, and lead. Metals such as tin and chromium and alloys thereof. It is also possible to use metal oxides such as tin indium oxide (ITO). The cathode may be formed of a laminate of one layer or a plurality of layers.
본 발명의 유기발광소자용의 도 1 ~ 도 3에 도시한 기판(1)으로서는, 금속, 세라믹스 등과 같은 불투명성 기판이나, 유리, 석영, 플라스틱 등과 같은 투명성 기판을 이용한다. 또, 컬러필터막, 형광색변환막, 유전체반사막 등을 가진 기판을 형성해서 발색광을 제어하는 일도 가능하다.As the substrate 1 shown in Figs. 1 to 3 for the organic light emitting device of the present invention, an opaque substrate such as metal, ceramics, or the like, or a transparent substrate such as glass, quartz, or plastic is used. In addition, it is also possible to form a substrate having a color filter film, a fluorescent color conversion film, a dielectric reflector film and the like to control the emitted light.
산소 및/또는 수분과의 접촉을 피하기 위하여, 본 발명의 유기발광소자는 또 보호층 또는 봉지층을 포함한다. 보호층의 예로서는, 다이아몬드, 금속산화물, 금속질화물 등의 무기재료막; 불소함유수지, 폴리파라크실렌, 폴리에틸렌, 실리콘수지, 폴리스티렌 등의 폴리머막 및 광경화성 수지막을 포함한다. 또, 유리, 기체불투과성 막, 금속 등으로 유기발광소자를 커버하고 봉지수지로 유기발광소자 자체를 패키지하는 것도 가능하다.In order to avoid contact with oxygen and / or moisture, the organic light emitting element of the present invention also includes a protective layer or an encapsulation layer. Examples of the protective layer include inorganic material films such as diamond, metal oxides and metal nitrides; Polymer films such as fluorine-containing resins, polyparaxylene, polyethylene, silicone resins, polystyrene, and photocurable resin films. It is also possible to cover the organic light emitting element with glass, a gas impermeable film, a metal and the like and to package the organic light emitting element itself with a sealing resin.
이하 실시예에 의거해서 본 발명을 더욱 구체적으로 설명한다.The present invention will be described in more detail with reference to the following Examples.
실시예 1Example 1
상기한 예시 화합물 No.37을 다음과 같은 방법으로 합성하였다(반응식은 마지막에 요약되어 있음).4-[비스(4'-메틸페닐)-아미노]벤즈알데히드 3.01ｇ(10 mmol), o-메톡시아세토페논 3.00ｇ(20 mmol) 및 아세트산 암모늄 14ｇ을 아세트산 50㎖에 첨가하고, 그 혼합물을 가열하에 12시간 환류를 행하였다. 실온으로 냉각 후, 반응생성물을 200㎖의 물에 쏟아붓고, 각 100㎖의 클로로포름으로 2회 추출하였다. 얻어진 클로로포름층을 감압하에 응축하고, 그 응축물을 벤젠/헥산(=1/1)의 용제혼합물로부터 재결정해서, 2,6-비스(2'-메톡시페닐)-4-[4"-비스(4"'-메틸페닐)아미노]페닐피리딘을 1.30ｇ 얻었다. 또, 재결정 후의 여과액에, 벤젠을 용리액으로 해서 실리카겔 칼럼 크로마토그라피(column chromatography)를 행하여, 마찬가지의 화합물을 0.79ｇ 회수하였다. 수율: 37.2%.Example compound No. 37 described above was synthesized in the following manner (the scheme is summarized last): 4- [bis (4'-methylphenyl) -amino] benzaldehyde 3.01 g (10 mmol), o-methoxy 3.00 g (20 mmol) of acetophenone and 14 g of ammonium acetate were added to 50 ml of acetic acid, and the mixture was refluxed for 12 hours under heating. After cooling to room temperature, the reaction product was poured into 200 ml of water and extracted twice with 100 ml of chloroform each. The obtained chloroform layer was condensed under reduced pressure, and the condensate was recrystallized from a solvent mixture of benzene / hexane (= 1/1) to give 2,6-bis (2'-methoxyphenyl) -4- [4 "-bis 1.30g of (4 "'-methylphenyl) amino] phenylpyridine was obtained. The filtrate after recrystallization was subjected to silica gel column chromatography using benzene as an eluent to recover 0.79 g of the same compound. Yield: 37.2%.
그 후, 2,6-비스(2'-메톡시페닐)-4-[4"-(4"'-메틸페닐)아미노]-페닐피리딘 1.12ｇ(2 mmol)을 30㎖의 47%-브롬화수소산에 첨가하고, 이어서 6시간동안 가열하에 환류를 행하였다. 실온으로 냉각시킨 후, 반응액을 100㎖의 물에 쏟아붓고, 200㎖의 클로로포름으로 추출하였다. 얻어진 클로로포름층을 먼저 10%-탄산나트륨수용액으로 세정하고, 이어서 물로 세정하였다. 그 후 클로로포름을 감압하에서 증류해서 제거하고, 잔류물(residue)에 클로로포름을 용리액으로 해서 실리카겔 칼럼 크로마토그라피를 행하여, 2,6-비스(o-하이드록시페닐)-4-[4"-비스(4"'-메틸페닐)아미노]페닐피리딘을 0.46ｇ(수율: 42%) 얻였다.Subsequently, 1.12 g (2 mmol) of 2,6-bis (2'-methoxyphenyl) -4- [4 "-(4" '-methylphenyl) amino] -phenylpyridine was added to 30 ml of 47% hydrobromic acid. It was added to and then refluxed under heating for 6 hours. After cooling to room temperature, the reaction solution was poured into 100 ml of water and extracted with 200 ml of chloroform. The resulting chloroform layer was first washed with 10% aqueous sodium carbonate solution and then with water. The chloroform was then distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography using chloroform as an eluent to give 2,6-bis (o-hydroxyphenyl) -4- [4 "-bis ( 0.46 g (yield: 42%) of 4 "'-methylphenyl) amino] phenylpyridine was obtained.
그 후, 2,6-비스(o-하이드록시페닐)-4-[4"-비스(4"'-메틸페닐)아미노]-페닐피리딘 0.53ｇ(1 mmol)을 50~60℃로 가열하면서 30㎖의 아세트산에 용해시키고, 그것에 실온에서 휘저으면서 0.15ｇ(1.25mmol)의 페닐붕산을 첨가하여, 약 10분후에 누르스름한 침전물을 얻었다. 4시간 동안 휘저었으며, 침전물을 물로 세정하여, 거의 순수한 2,6-비스(o-하이드록시페닐)-4-[4"'-비스(4"'-메틸페닐)아미노]페닐피리딘의 페닐붕산에스테르(화합물 No.37)를 0.47ｇ(수율: 75%) 얻었다.Thereafter, 0.53 g (1 mmol) of 2,6-bis (o-hydroxyphenyl) -4- [4 "-bis (4" '-methylphenyl) amino] -phenylpyridine was heated to 50-60 DEG C while 30 It was dissolved in ml of acetic acid, and 0.15 g (1.25 mmol) of phenylboric acid was added thereto while stirring at room temperature, to give a yellowish precipitate after about 10 minutes. Stirred for 4 hours, the precipitate was washed with water and phenylboric acid ester of nearly pure 2,6-bis (o-hydroxyphenyl) -4- [4 "'-bis (4"'-methylphenyl) amino] phenylpyridine 0.47 g (yield: 75%) of (Compound No. 37) were obtained.
상기 반응식을 요약하면 다음과 같다.The reaction scheme is summarized as follows.
실시예 2Example 2
상기 예시 화합물 No.16을 다음과 같은 방법으로 합성하였다. The exemplary compound No. 16 was synthesized in the following manner.
2-하이드록시페나실-피리디늄 요드화물 1.63ｇ(5 mmol), 1-(2-하이드록시페닐)-3-(4-디메틸아미노페닐)-2-프로펜-1-온 0.53ｇ(2 mmol) 및 아세트산 암모늄 4ｇ을 4㎖의 아세트산에 첨가하고, 그 혼합물을 5시간 동안 가열하에 환류를 행하였다. 실온으로 냉각시킨 후, 반응혼합물을 50㎖의 물에 쏟아붓고, 각 30㎖의 클로로포름으로 2회 추출하였다. 클로로포름을 감압하에 증류하여 제거하고, 잔류물에 클로로포름을 용리액으로 해서 실리카겔 칼럼 크로마토그라피를 행하여, 2,6-비스(2-하이드록시페닐)-4-(4-디메틸아미노페닐)피리딘을 0.61ｇ(수율: 79%) 얻었다. (부수적으로, 반응잔류물을 30㎖의 에탄올로부터 재결정을 행한 바, 2,6-비스페놀피리딘 생성물이 64%의 수율로 회수되었다).1.63 g (5 mmol) of 2-hydroxyphenacyl-pyridinium iodide, 0.53 g of 1- (2-hydroxyphenyl) -3- (4-dimethylaminophenyl) -2-propen-1-one mmol) and 4 g of ammonium acetate were added to 4 ml of acetic acid and the mixture was refluxed under heating for 5 hours. After cooling to room temperature, the reaction mixture was poured into 50 ml of water and extracted twice with 30 ml of chloroform each. Chloroform was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography using chloroform as an eluent to give 0.61 g of 2,6-bis (2-hydroxyphenyl) -4- (4-dimethylaminophenyl) pyridine. (Yield 79%) was obtained. (Incidentally, the reaction residue was recrystallized from 30 ml of ethanol to recover 2,6-bisphenolpyridine product in 64% yield).
그 후, 2,6-비스(2-하이드록시페닐)-4-(4-디메틸아미노페닐)피리딘 0.38ｇ(1 mmol)을 30㎖의 아세트산에 용해하고, 거기에 페닐붕산 0.15ｇ(1.25 mmol)을 첨가한 후, 실온에서 휘저어서 약 10분 이내에 침전물을 얻었다. 4시간 동안 연속해서 휘저어서, 침전물을 여과에 의해 회수해서, 세정액이 중성이 될 때까지 물로 세정하였으며, 이에 의해 거의 순수한 2,6-비스(2-하이드록시페닐)-4-(4-디메틸아미노페닐)피리딘의 페닐붕산에스테르(예시 화합물 No.16)를 0.37ｇ(수율: 80%) 얻었다.Thereafter, 0.38 g (1 mmol) of 2,6-bis (2-hydroxyphenyl) -4- (4-dimethylaminophenyl) pyridine was dissolved in 30 ml of acetic acid, and 0.15 g (1.25 mmol) of phenylboric acid was added thereto. ) Was added and then stirred at room temperature to obtain a precipitate within about 10 minutes. Stirred continuously for 4 hours, the precipitate was recovered by filtration and washed with water until the wash was neutral, whereby nearly pure 2,6-bis (2-hydroxyphenyl) -4- (4-dimethyl 0.37 g (yield: 80%) of phenylboric acid esters (example compound No. 16) of aminophenyl) pyridine were obtained.
상기 반응식을 요약하면 다음과 같다.The reaction scheme is summarized as follows.
실시예 3Example 3
상기 예시 화합물 No.17을 다음과 같은 방법으로 합성하였다. Example compound No. 17 was synthesized according to the following method.
2,6-비스(o-하이드록시페닐)-4-(p-메틸페닐)피리딘 0.35ｇ(1 mmol)을 30㎖의 아세트산에 용해하고, 거기에 페닐붕산 0.15ｇ(1.25 mmol)을 첨가하였으며, 이어서 실온에서 휘저어 약 10분 이내에 침전물을 얻었다. 8시간 동안 연속해서 휘저었고, 침전물을 여과에 의해 회수하고, 수용액이 중성이 될 때까지 물로 세정하였으며, 이에 의해 거의 순수한 2,6-비스(o-하이드록시페닐)-4-(p-메틸페닐)피리딘의 페닐붕산에스테르를 0.32ｇ(수율: 74%) 얻었다.0.35 g (1 mmol) of 2,6-bis (o-hydroxyphenyl) -4- (p-methylphenyl) pyridine was dissolved in 30 ml of acetic acid, and 0.15 g (1.25 mmol) of phenylboric acid was added thereto. It was then stirred at room temperature to obtain a precipitate within about 10 minutes. Stirred continuously for 8 hours, the precipitate was recovered by filtration and washed with water until the aqueous solution was neutral, whereby nearly pure 2,6-bis (o-hydroxyphenyl) -4- (p-methylphenyl 0.32 g (yield: 74%) of phenylboric acid ester of pyridine was obtained.
반응식은 다음과 같이 표시된다.The reaction scheme is represented as follows.
실시예 4 Example 4
도 2에 도시한 바와 같은 구조의 유기붕소화합물을 다음과 같은 방법으로 작성하였다. 스퍼터링에 의해 형성된 ITO(산화주석인듐)의 120㎚ 두께의 막으로 도포된 1.1㎜ 두께의 유리기판을 초음파의 인가하에 아세톤과 이소프로필 알콜(IPA)로 세정하고, 그후 비등하에 IPA로 세정하고, 이어서 UV/오존(즉, 오존을 포함하는 분위기에서 자외선으로 조사)으로 세정하여 투명도전성 기판(기판(1)과 그 위에 형성된 ITO 양극(2)을 포함함)을 얻었다.An organoboron compound having a structure as shown in FIG. 2 was prepared by the following method. A 1.1 mm thick glass substrate coated with a 120 nm thick film of ITO (indium tin oxide) formed by sputtering was cleaned with acetone and isopropyl alcohol (IPA) under ultrasonic application, followed by IPA under boiling, Subsequently, the resultant was washed with UV / ozone (ie, irradiated with ultraviolet light in an atmosphere containing ozone) to obtain a transparent conductive substrate (including the substrate 1 and the ITO anode 2 formed thereon).
투명도전성 기판을 먼저 진공증착법에 의해 N,N-디페닐-N,N'-m-톨릴-4,4'-디아미노-1,1'-비페닐(이후 "TPD"라 칭함)(정공 전송재료)을 500Å의 두께로(층(5)), 그 후 상기 예시 화합물 No.2를 500Å의 두께로(층(6)), 그리고 그 후 Al을 1500Å의 두께로(음극(4)) 도포하여 발광소자를 작성하였다. 상기 소자는 9V에서 150cd/㎡의 휘도로 녹색발광하였다.The transparent conductive substrate was first subjected to vacuum deposition by N, N-diphenyl-N, N'-m-tolyl-4,4'-diamino-1,1'-biphenyl (hereinafter referred to as "TPD") (holes Transport material) to a thickness of 500 kPa (layer 5), then to the thickness of 500 kPa (layer 6) of the exemplary compound No. 2 above, and then to a thickness of 1500 kPa (cathode 4) It applied and the light emitting element was produced. The device emits green light at a luminance of 150 cd / m 2 at 9V.
실시예 5Example 5
실시예 4에서 사용한 것과 동일한 ITO도포 투명도전성 기판에 먼저 TPD를 500Å의 두께로(층(5)), 그 후 예시 화합물 No.16을 500Å의 두께로(층(6)), 그리고 그 후 Al을 1500Å의 두께로(음극(4)) 도포하여 유기광학소자를 작성하였다. 상기 소자는 5V에서 200cd/㎡, 그리고 9V에서 1500cd/㎡의 휘도로 녹색발광하였다.On the same ITO coated transparent conductive substrate as used in Example 4, TPD was first deposited to a thickness of 500 GPa (layer 5), then Exemplified Compound No. 16 to a thickness of 500 GPa (layer 6), and then Al Was applied at a thickness of 1500 kPa (cathode 4) to make an organic optical device. The device emits green light at a luminance of 200 cd / m 2 at 5V and 1500 cd / m 2 at 9V.
실시예 6Example 6
실시예 4에서 사용한 것과 동일한 ITO 도포 투명도전성 기판에 먼저 진공증착법에 의해 TPD를 500Å의 두께로, 그 후 공진공증착법(co-vaccum deposition)에 의해 예시 화합물 No.16과 이것의 1%의 쿠마린 6(도펀트로서)을 300Å의 두께로, 그 후 진공증착법에 의해 Al을 1500Å의 두께로(음극) 도포하여 유기발광소자를 작성하였다. 상기 소자는 5V에서 240cd/㎡, 그리고 9V에서 300cd/㎡의 휘도로 녹색발광을 하였다. 실시예 5의 예로부터 알 수 있는 바와 같이, 도펀트로서 쿠마린 6을 첨가함으로써 9V에서의 휘도가 현저하게 증가하였다.To the same ITO coated transparent conductive substrate as used in Example 4, TPD of 500 kPa was first deposited by vacuum deposition, followed by co-vaccum deposition. 6 (as a dopant) was applied at a thickness of 300 kPa, and Al was then applied at a thickness of 1500 kPa (cathode) by a vacuum deposition method to prepare an organic light emitting device. The device emits green light at a luminance of 240 cd / m 2 at 5V and 300 cd / m 2 at 9V. As can be seen from the example of Example 5, the addition of coumarin 6 as the dopant significantly increased the brightness at 9V.
실시예 7Example 7
ITO 도포 투명도전성 기판에 먼저 진공증착법에 의해 TPD를 500Å의 두께로, 그 후 예시 화합물 No.17을 500Å의 두께로, 그리고 그 후 Al을 1500Å의 두께로(음극) 도포하여 유기발광소자를 작성하였다. 상기 소자는 5V에서 40cd/㎡, 그리고 9V에서 500cd/㎡의 휘도로 노란색발광을 하였다.An organic light-emitting device was prepared by first applying TPD to a thickness of 500 kPa, an example compound No. 17 to a thickness of 500 kPa, and then Al to a thickness of 1500 kPa (cathode) on an ITO-coated transparent conductive substrate. It was. The device emits yellow light at a luminance of 40 cd / m 2 at 5V and 500 cd / m 2 at 9V.
실시예 8Example 8
ITO도포 투명도전성 기판에 진공증착법에 의해 먼저 TPD를 500Å의 두께로, 그 후 예시 화합물 No.17을 500Å의 두께로, 그 후 Al-Li 합금(Li 함량: 1 원자%)을 100Å의 두께로(전자주입층으로서), 그리고 그 후 Al을 1500Å의 두께로(음극) 도포하여 유기발광소자를 작성하였다. 상기 소자는 5V에서 40cd/㎡, 그리고 9V에서 500cd/㎡의 휘도로 녹색발광하였다.By vacuum deposition on an ITO-coated transparent conductive substrate, TPD was first deposited to a thickness of 500 GPa, then Example Compound No. 17 to 500 GPa, and then Al-Li alloy (Li content: 1 atomic%) to 100 GPa. (As an electron injection layer) and after that, Al was applied to a thickness of 1500 kPa (cathode) to prepare an organic light emitting device. The device emits green light at a luminance of 40 cd / m 2 at 5V and 500 cd / m 2 at 9V.
실시예 7과의 비교로부터 알 수 있는 바와 같이, Al-Li 합금의 전자전송층의 형성은 휘도에 있어서 거의 차이가 없었다. 이것은 예시 화합물 No.17(본 발명의 유기붕소화합물의 예)도 역시 우수한 전자주입기능을 나타낸다는 것을 의미한다.As can be seen from the comparison with Example 7, formation of the electron transport layer of the Al-Li alloy showed little difference in luminance. This means that exemplary compound No. 17 (example of the organoboron compound of the present invention) also exhibits excellent electron injection function.
실시예 9Example 9
ITO도포투명도전성 기판에 진공증착법에 의해 먼저 TPD를 500Å의 두께로(층(5)), 그 후 트리스(8-퀴놀리놀라토)알루미늄착체를 500Å의 두께로(도 3에 있어서의 발광층(3)), 그 후 예시 화합물 No.17을 20Å의 두께로(전자주입층(6)), 그리고 그 후 Al을 1500Å의 두께로(음극) 도포하여 유기발광소자를 작성하였다.TPD was first deposited to a thickness of 500 kPa (layer 5) on the ITO coated transparent conductive substrate by vacuum deposition, and then a tris (8-quinolinolato) aluminum complex was formed to a thickness of 500 kPa (the light emitting layer in FIG. 3). 3)) Then, Example compound No. 17 was apply | coated to the thickness of 20 kPa (electron injection layer 6), and after that, Al was applied to the thickness of 1500 kPa (cathode), and the organic light emitting element was produced.
비교예Comparative example
ITO도포투명도전성 기판에 진공증착법에 의해 먼저 TPD를 500Å(층(5))의 두께로, 트리스(8-퀴놀리놀라토)알루미늄착체를 500Å의 두께로(발광층(3) 또는 전자주입층(6)), 그리고 그 후 Al을 1500Å의 두께로(음극(4)) 도포하여 유기발광소자를 작성하였다.TPD was first deposited to a thickness of 500 kPa (layer 5) and tris (8-quinolinolato) aluminum complex was deposited to a thickness of 500 kPa (light emitting layer 3 or electron injection layer) by vacuum deposition on an ITO coated transparent conductive substrate. 6)), and then Al was applied to a thickness of 1500 kPa (cathode 4) to prepare an organic light emitting device.
실시예 9와 상기 작성된 비교예의 소자는 모두 녹색발광을 하고, 도 4에 도시한 전압-휘도특성을 나타내었으며, 이것은 예시 화합물 No.17(본 발명의 유기붕소화합물의 예)이 아주 효율적인 전자주입층을 형성한다는 것을 보여준다.The devices of Example 9 and the comparative example prepared above both emit green light and exhibit the voltage-luminance characteristics shown in FIG. 4, which shows that Example Compound No. 17 (an example of the organoboron compound of the present invention) is highly efficient. Shows that it forms a layer.
상기한 바와 같이, 본 발명에 따르면, 발광소자재료로서 유용한, 특히 전하전송특성이 우수하고, 우수한 성능을 나타내는 발광층 및/또는 전자전송층을 구성하는 데 유용한 일반식(1)의 유기붕소화합물을 제공한다.As described above, according to the present invention, an organoboron compound of the general formula (1) useful as a light emitting device material, and particularly useful for forming a light emitting layer and / or an electron transporting layer having excellent charge transfer characteristics and excellent performance, to provide.
더욱이, 상기 유기붕소화합물은 본 발명에 따른 제조방법에 의해 용이하고 비교적 저렴하게 제조할 수 있다.Moreover, the organoboron compound can be easily and relatively inexpensively prepared by the production method according to the present invention.
또, 유기붕소화합물층을 포함하는 본 발명의 유기발광소자는 저전압에서도 아주 높은 휘도를 나타내고, 따라서 우수한 내구성을 나타낸다.In addition, the organic light emitting device of the present invention including the organoboron compound layer exhibits very high luminance even at low voltage, and thus excellent durability.
본 발명의 유기붕소화합물로 이루어진 유기층은 전자전송층 및 발광층으로서 유용하고, 또한 전자주입층으로서도 유용하다.The organic layer made of the organoboron compound of the present invention is useful as an electron transport layer and a light emitting layer, and also as an electron injection layer.
상기 층은 진공증착 또는 주조에 의해 용이하게 형성할 수 있고, 따라서 대면적의 소자를 용이하고 저렴하게 제조할 수 있다. The layer can be easily formed by vacuum deposition or casting, thus making it possible to manufacture large area devices easily and inexpensively.
도 1 내지 도 3은 각각 본 발명의 실시예에 따른 유기발광소자의 기본구조를 예시하는 개략적 단면도1 to 3 are schematic cross-sectional views illustrating the basic structure of an organic light emitting diode according to an embodiment of the present invention, respectively.
도 4는 실시예 9와 비교예의 유기발광소자의 전압-휘도특성을 나타낸 그래프.4 is a graph showing voltage-luminance characteristics of organic light emitting diodes of Example 9 and Comparative Example.
<도면의 주요부분에 대한 설명><Description of main parts of drawing>
1: 기판 2: 양극1: substrate 2: anode
3: 발광층 4: 음극3: light emitting layer 4: cathode
5: 정공전송층 6: 전자전송층5: hole transport layer 6: electron transport layer
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| JP2001094971A JP3990869B2 (en) | 2000-03-31 | 2001-03-29 | ORGANIC BORON COMPOUND, PROCESS FOR PRODUCING THE ORGANIC BORON COMPOUND, AND ORGANIC LIGHT-EMITTING DEVICE USING THE ORGANIC BORON COMPOUND |
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| KR20240037220A (en) | 2022-01-12 | 2024-03-21 | 주식회사 에스켐 | Organoboron compounds and method for manufacturing the same |
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