WO2016060463A2 - Novel compound and organic light-emitting element comprising same - Google Patents
Novel compound and organic light-emitting element comprising same Download PDFInfo
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- WO2016060463A2 WO2016060463A2 PCT/KR2015/010829 KR2015010829W WO2016060463A2 WO 2016060463 A2 WO2016060463 A2 WO 2016060463A2 KR 2015010829 W KR2015010829 W KR 2015010829W WO 2016060463 A2 WO2016060463 A2 WO 2016060463A2
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- 0 CCC=CC(C(C)(C)[n]1c(cccc2)c2c(*)c1)=CC=CC(C)(C)Nc1ccccc1 Chemical compound CCC=CC(C(C)(C)[n]1c(cccc2)c2c(*)c1)=CC=CC(C)(C)Nc1ccccc1 0.000 description 44
- ABRWESLGGMHKEA-UHFFFAOYSA-N CC(C)(C)Nc1ccccc1 Chemical compound CC(C)(C)Nc1ccccc1 ABRWESLGGMHKEA-UHFFFAOYSA-N 0.000 description 1
- KBTVORQFWQZMNH-UHFFFAOYSA-N CC1(C)C(CCCC2)C2C(CCC(C2)N(C(CCC3)CC3C(CCC3)=CC3[n]3c(CCCC4)c4cc3)C3C4OC(CCCC5)C5C4CCC3)C2C1 Chemical compound CC1(C)C(CCCC2)C2C(CCC(C2)N(C(CCC3)CC3C(CCC3)=CC3[n]3c(CCCC4)c4cc3)C3C4OC(CCCC5)C5C4CCC3)C2C1 KBTVORQFWQZMNH-UHFFFAOYSA-N 0.000 description 1
- DXSIFZLOUITCRR-UHFFFAOYSA-N CC1(C)c2cc(C)ccc2-c2c1cccc2 Chemical compound CC1(C)c2cc(C)ccc2-c2c1cccc2 DXSIFZLOUITCRR-UHFFFAOYSA-N 0.000 description 1
- RQLWFJACLHVHMP-UHFFFAOYSA-N CC1(C)c2ccccc2C2C=CC(N(C(CC3)CC=C3c(cc3)ccc3-c([n](C3C=CCC3)c3ccccc33)c3-c3ccccc3)C3C4Oc5ccccc5C4=CCC3)=CC12 Chemical compound CC1(C)c2ccccc2C2C=CC(N(C(CC3)CC=C3c(cc3)ccc3-c([n](C3C=CCC3)c3ccccc33)c3-c3ccccc3)C3C4Oc5ccccc5C4=CCC3)=CC12 RQLWFJACLHVHMP-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N CNc1ccccc1 Chemical compound CNc1ccccc1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
Definitions
- the present invention relates to a novel compound and an organic light emitting device comprising the same, in particular, when applied to the organic light emitting device for fluorescence and phosphorescence excellent hole injection and hole transfer characteristics, at the same time excellent electron blocking characteristics, high triplet energy And a novel compound capable of realizing high Tg and having low driving voltage, low power consumption, high efficiency and long life.
- an organic light emitting device capable of low voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is the mainstream of flat panel display devices.
- LCD liquid crystal display
- the material used as the organic material layer in the organic light emitting device can be largely classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on the function.
- the light emitting material may be classified into a polymer and a low molecule according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. According to the emission color can be divided into blue, green, red light emitting material and yellow and orange light emitting material required to implement a better natural color.
- a host / dopant system may be used as a light emitting material.
- the principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light.
- the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host to be used.
- the present invention is excellent in the hole injection and hole transfer characteristics when applied to the organic light emitting device, and at the same time excellent in the electron blocking characteristics, high triplet energy and high Tg can be realized, low driving
- An object of the present invention is to provide a novel compound which can have a voltage, low power consumption, high efficiency and long life, and is particularly suitable for an organic light emitting device for blue and phosphorescence.
- the present invention also includes the novel compound, which has excellent hole injection and hole transport characteristics, and at the same time, excellent electron blocking characteristics, and at the same time, can realize high triplet energy and high Tg, and low driving voltage, low power consumption, and high efficiency. And it is an object to provide an organic light emitting device that can have a long life.
- Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substitute
- the present invention also provides an organic light emitting device including one or more organic material layers containing a compound represented by Chemical Formula 1 between a first electrode, a second electrode, and two electrodes.
- the compound of the present invention has excellent hole injection and hole transport characteristics when applied to the organic light emitting device for blue and phosphorescence, at the same time excellent in the electron blocking characteristics, high triplet energy and high Tg, low drive voltage, low consumption It can have power, high efficiency and long life.
- FIG. 1 schematically illustrates a cross section of an OLED according to an embodiment of the invention.
- the compound of the present invention is characterized by represented by the following formula (1).
- Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substitute
- the compound represented by Chemical Formula 1 may be one of the compounds represented by the following Chemical Formulas 1-1 to 1-7.
- N, p, q and r in the formulas are each independently an integer selected from 1 to 3,
- Ar 1 and Ar 2 are each independently a C 6-50 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro groups; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
- R 1 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or
- R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , Ar 1 , Ar 2 may form an adjacent group or a ring with each other.
- the compound of formula 1 according to the present invention has excellent hole injection and hole transport characteristics when applied to an organic light emitting device, and at the same time excellent in electron blocking characteristics, high triplet energy and high Tg, low driving voltage, low consumption It can have power, high efficiency and long life.
- the compounds represented by Chemical Formulas 1-1 and 1-2 may exhibit more excellent device characteristics in fluorescent and red phosphorescent organic light emitting diodes, and the compounds represented by Chemical Formula 1-7 may be further represented in green phosphorescent organic light emitting diodes It can exhibit excellent device characteristics.
- the present invention also provides an organic light emitting device comprising the compound represented by Chemical Formula 1 in an organic material layer. Specifically, it will be included as a hole injection material, a hole transport material, a light emitting auxiliary material, wherein the compound of the present invention may be used alone or in combination with a known organic light emitting compound. More specifically, the organic light emitting device is preferably a fluorescent, red phosphorescent, green phosphorescent organic light emitting device.
- the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Chemical Formula 1, and the method of manufacturing the organic light emitting device is as follows.
- the organic light emitting diode includes a hole injection layer (HIL), a hole transport layer (HTL), an emission auxiliary layer, an emission layer (EML), and an electron transport layer between a first electrode (anode) and a second electrode (cathod).
- HIL hole injection layer
- HTL hole transport layer
- EML emission auxiliary layer
- ETL electron injection layer
- EIL electron injection layer
- an anode is formed by depositing a material for an anode electrode having a high work function on the substrate.
- the substrate may be a substrate used in a conventional organic light emitting device, it is particularly preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof.
- the anode electrode material transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and the like may be used.
- the anode electrode material may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.
- the hole injection layer material may be formed on the anode electrode by a method such as vacuum deposition, spin coating, casting, and Langmuir-Blodgett (LB).
- the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the desired hole injection layer, and generally, a deposition temperature of 50-500 ° C., It can be suitably selected from a vacuum degree of 10 ⁇ 8 to 10 ⁇ 3 torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 kPa to 5 ⁇ m.
- the hole injection layer material may be a compound represented by Formula 1 of the present invention, it may be used with a known material.
- the known material is not particularly limited, and TCTA (4,4 ′, 4 ′′ -tri (N-carbazolyl) triphenyl, which is a phthalocyanine compound or starburst amine derivatives such as copper phthalocyanine disclosed in US Pat. No.
- the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, or the like.
- the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.
- the hole transport material may be a compound represented by the formula (1) of the present invention, it may be used with a known material.
- the known material is not particularly limited, and may be arbitrarily selected and used from conventional known materials used in the hole transport layer.
- the hole transport layer material is carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine ( ⁇ -NPD) Derivatives and the like can be used.
- an auxiliary layer may be further included on the hole transport layer.
- the auxiliary layer may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, cast, LB, or the like.
- the auxiliary layer may be a compound represented by the formula (1) of the present invention, in this case, the hole transport layer is preferably used a compound represented by the formula (2).
- Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
- R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuter
- the light emitting layer material may be formed on the hole transport layer or the auxiliary layer by a method such as vacuum deposition, spin coating, cast, LB, or the like.
- a method such as vacuum deposition, spin coating, cast, LB, or the like.
- the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer.
- the light emitting layer material may use a known compound as a host or dopant.
- a fluorescent dopant may be IDE102 or IDE105 available from Idemitsu, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethycrylicene- 6,12-diamine) can be used as green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate), a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped).
- Ir ppy
- F2Irpic iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate
- the hole suppressing material when used with a phosphorescent dopant in the light emitting layer, to prevent the triplet exciton or hole from being diffused into the electron transport layer, the hole suppressing material (HBL) may be further laminated by vacuum deposition or spin coating.
- the hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used.
- an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited.
- Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound e.g., BCP (vasocuproin) from UDC
- BCP vasocuproin
- An electron transport layer is formed on the light emitting layer formed as described above, wherein the electron transport layer may be formed by a vacuum deposition method, a spin coating method, a casting method, or the like.
- the electron transport layer material functions to stably transport electrons injected from the electron injection electrode, and the type thereof is not particularly limited, and examples thereof include quinoline derivatives, especially tris (8-quinolinolato) aluminum (Alq 3). ), Or ET4 (6,6 '-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl) di-2,2'-bipyridine).
- an electron injection layer (EIL) which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and the electron injection layer material may be LiF, NaCl, CsF, Li 2 O, BaO, or the like. The substance of can be used.
- the deposition conditions of the electron transport layer is different depending on the compound used, but can be generally selected in the same condition range as the formation of the hole injection layer.
- an electron injection layer material may be formed on the electron transport layer, wherein the electron transport layer is formed of a conventional electron injection layer material by a vacuum deposition method, a spin coating method, a casting method, and the like. It is good to form.
- a cathode forming metal is formed on the electron injection layer by a method such as vacuum deposition or sputtering and used as a cathode.
- the cathode forming metal may be a metal having low work function, an alloy, an electrically conductive compound, and a mixture thereof. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. There is this.
- a transmissive cathode using ITO or IZO may be used to obtain the front light emitting device.
- the organic light emitting device of the present invention is capable of not only an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device having a cathode structure, but also an organic light emitting device having various structures, and emits light as necessary. It is also possible to form one or two intermediate layers such as an auxiliary layer.
- each organic material layer formed according to the present invention as described above can be adjusted according to the required degree, specifically 1 to 1,000 nm, more preferably 5 to 200 nm. Within this range, the effect of high efficiency, long life and high color purity is more excellent.
- the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.
- the organic light emitting device of the present invention includes the compound represented by Chemical Formula 1, and has excellent hole injection and hole transport characteristics, and at the same time, excellent electron blocking characteristics, high triplet energy and high Tg, and low driving voltage. It has low power consumption, high efficiency and long life.
- An organic light emitting device was manufactured according to the structure of FIG. 1.
- the organic light emitting element is formed from the bottom of the anode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transfer layer 15 / cathode (electron injection electrode 16) It is laminated in order.
- the substrate 10 may be a transparent glass substrate or a flexible plastic substrate when the organic light emitting diode is manufactured.
- the hole injection electrode 11 is used as an anode for hole injection of the organic light emitting device.
- a material having a low work function may be used to inject holes, and may be formed of a transparent material such as indium tin oxide (ITO), indium zinc oxide (IZO), and graphene.
- the hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of Examples and Comparative Examples used the following materials.
- the cathode 16 for electron injection is formed on the electron injection layer 15.
- Various metals may be used as the cathode. Specific examples include materials such as aluminum, gold, and silver.
- a glass substrate coated with an indium tin oxide (ITO) 1500 ⁇ thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes using an oxygen plasma. Using an evaporator, a film was deposited with a hole injection layer HT01 600 ⁇ and a compound transport 1 with 250 ⁇ as the hole transport layer. Next, the light emitting layer was doped with BH01: BD01 5% to form 250 ⁇ . Next, ET01: Liq (1: 1) 300 ⁇ was formed into an electron transport layer, followed by LiF 10 ⁇ and aluminum (Al) 1000 ⁇ , which were encapsulated in a glove box to produce an organic light emitting device.
- ITO indium tin oxide
- a device was manufactured in the same manner as in Example 1, except that Compound 1 was used as the NPB as the hole transport layer.
- a device was manufactured in the same manner as in Example 1, except that Compound 1 was used as Ref. 1 as the hole transport layer.
- a device was manufactured in the same manner as in Example 1, except that Compound 1 was used as Ref. 2 as the hole transport layer.
- Example 1 4.441 10 5.85 4.79 0.141 0.120 22
- Example 2 4.352 10 5.85 4.71 0.141 0.117 27
- Example 3 4.343 10 5.88 4.76 0.142 0.115 30
- Example 4 4.221 10 5.97 4.94 0.139 0.112 32
- Example 5 4.212 10 6.00 4.92 0.138 0.113 35
- Example 6 4.203 10 6.04 4.94 0.140 0.113 35
- Example 7 4.295 10 6.07 4.99 0.140 0.113 37
- Example 8 4.157 10 6.70 5.69 0.140 0.111 50
- Example 9 4.130 10 6.63 5.64 0.139 0.112 47
- Example 10 4.104 10 6.70 5.64 0.141 0.112 49
- Example 11 4.100 10 6.59 5.67 0.142 0.112 49
- Example 12 4.110 10 6.60 5.69 0.141 0.113 48
- Example 13 4.109 10 6.63 5.65 0.142 0.113 50
- Example 14 4.241 10 6.11 4.97 0.141 0.114 32
- Example 15 4.214 10 6.19 4.80 0.141 0.113 35
- Example 16 4.4
- the Examples evaluated by the hole transport layer of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Examples 1 to 3.
- the structure in which the aryl group is substituted at the position of indole 3 as shown in Chemical Formulas 1-1 and 1-2 has better planarity of molecules than simultaneous substitution of indole 2 and indole 2,3, and excellent mobility of molecules in the thin film. It can be seen that the efficiency and device life are significantly improved due to the excellent increase and chemical stability.
- the linking group of Formula 1-6, indole, and arylamine is a phenyl moiety
- the planarity of the fluorene groups improves the arrangement of the thin films, increases mobility, and significantly improves efficiency and lifetime. Able to know.
- a glass substrate coated with an indium tin oxide (ITO) 1500 ⁇ thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes using an oxygen plasma.
- 600 cc of the hole injection layer HT01 and 400 cc of the compound 31 were formed into a first hole transport layer using an evaporator.
- 150 ⁇ of the compound 8 was formed as an auxiliary layer, and then 250 ⁇ was formed by doping with 5% of BH01: BD01.
- An organic light-emitting device was manufactured in the same manner as in Example 26, using Compound 32 as an auxiliary layer and Compound 8 as an auxiliary layer.
- Example 26 In the same manner as in Example 26, an organic light emitting device was manufactured by using the compound 33 as an auxiliary layer and the compound 8 as a hole transport layer.
- Example 26 In the same manner as in Example 26, an organic light emitting device was manufactured by using the compound 34 as a hole transport layer and the compound 8 as an auxiliary layer.
- An organic light-emitting device was manufactured in the same manner as in Example 26, using Compound 35 as an auxiliary layer and Compound 8 as an auxiliary layer.
- Example 26 In the same manner as in Example 26, an organic light emitting diode was manufactured by using Compound 36 as an auxiliary layer and Compound 8 as an auxiliary layer.
- Example 26 In the same manner as in Example 26, an organic light emitting device was manufactured by using the compound 37 as a hole transport layer and the compound 8 as an auxiliary layer.
- An organic light-emitting device was manufactured in the same manner as in Example 26, using Compound 38 as an auxiliary layer and Compound 8 as an auxiliary layer.
- a device was manufactured in the same manner as in Example 26, except that Compound 24 was used as the NPB as the hole transport layer.
- a device was manufactured in the same manner as in Example 26, except that Compound 24 was used as Ref. 3 as the hole transport layer.
- a device was manufactured in the same manner as in Example 26, except that Compound 24 was used as Ref. 4 as the hole transport layer.
- the embodiments of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Examples 4 to 6.
- the driving voltage was significantly lowered, and the efficiency and lifespan were increased.
- It can have easy homo and fast hole mobility in the hole transport layer in accordance with the 2,3 arylamine substitution of indole, and in the case of indole N substitution, it can form a deep homogeneous easily in the auxiliary layer. It can be seen that greatly improved.
- a glass substrate coated with an indium tin oxide (ITO) 1500 ⁇ thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes using an oxygen plasma.
- a film injection layer HT01 600 ⁇ a hole transport layer to the film 37 to 400 ⁇ was formed into a film.
- 250 ⁇ of Compound 8 was formed as an auxiliary layer, and then 300 ⁇ was formed by doping with 10% CzT: Ir (ppy) 3 .
- An organic light-emitting device was manufactured in the same manner as in Example 34, using the auxiliary layer as a compound 26 to form a film.
- Example 34 In the same manner as in Example 34, an organic light emitting device was manufactured by using the auxiliary layer as a compound 27.
- Example 34 In the same manner as in Example 34, an organic light-emitting device was manufactured by using the auxiliary layer as a compound 28.
- Example 34 In the same manner as in Example 34, an organic light-emitting device was manufactured by using the auxiliary layer as a compound 29.
- An organic light-emitting device was manufactured in the same manner as in Example 34, using the auxiliary layer as a compound 30.
- an organic light emitting diode was manufactured by using the hole transport layer as an NPB and the auxiliary layer as a compound 30.
- a device was fabricated in the same manner as in Example 34, except that Ref. 1 was used as the hole transport layer and NPB.
- a device was fabricated in the same manner as in Example 34, except that the hole transport layer was NPB, and the auxiliary layer was Ref.2.
- the embodiments of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Example 7 and Comparative Example 8.
- the compound in which the linking group between indole N and arylamine is substituted with phenyl moiety and meta, ortho as an auxiliary layer of the phosphor it may have a wide band gap capable of forming a deep homo with short conjugation length. It can be seen that the triplet energy is easy to block excitons from phosphorescent light emission, thereby improving efficiency and improving lifespan.
- the compound of the present invention has excellent hole injection and hole transport characteristics when applied to the organic light emitting device for blue and phosphorescence, at the same time excellent in the electron blocking characteristics, high triplet energy and high Tg, low drive voltage, low consumption It can have power, high efficiency and long life.
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Abstract
The present invention relates to a novel compound, and in particular, when applied to a fluorescent and phosphorescent organic light-emitting element, the novel compound has superb hole injection and hole transmission characteristics as well as an excellent electron blocking characteristic, can exhibit high triplet energy and Tg, and can impart a low driving voltage, low energy consumption, superb efficiency and a long lifespan.
Description
본 발명은 신규한 화합물 및 이를 포함하는 유기발광소자에 관한 것으로, 특히 형광 및 인광용 유기발광소자에 적용시 정공주입 및 정공전달 특성이 우수하고, 동시에 전자차단 특성이 우수하며, 높은 삼중항 에너지 및 높은 Tg를 구현할 수 있으며, 낮은 구동전압, 저소비전력, 고효율 및 장수명을 가지게 할 수 있는 신규한 화합물에 관한 것이다.The present invention relates to a novel compound and an organic light emitting device comprising the same, in particular, when applied to the organic light emitting device for fluorescence and phosphorescence excellent hole injection and hole transfer characteristics, at the same time excellent electron blocking characteristics, high triplet energy And a novel compound capable of realizing high Tg and having low driving voltage, low power consumption, high efficiency and long life.
최근, 자체 발광형으로 저전압 구동이 가능한 유기발광소자는, 평판 표시소자의 주류인 액정디스플레이(LCD, liquid crystal display)에 비해, 시야각, 대조비 등이 우수하고 백라이트가 불필요하여 경량 및 박형이 가능하며 소비전력 측면에서도 유리하고 색 재현 범위가 넓어, 차세대 표시소자로서 주목을 받고 있다.Recently, an organic light emitting device capable of low voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is the mainstream of flat panel display devices. In terms of power consumption and wide color reproduction range, it is attracting attention as a next-generation display device.
유기발광소자에서 유기물 층으로 사용되는 재료는 크게 기능에 따라, 발광 재료, 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. 상기 발광 재료는 분자량에 따라 고분자과 저분자로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와 전자의 삼중항 여기상태로부터 유래되는 인광 재료로 분류될 수 있으며, 발광 재료는 발광 색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 물질로서 호스트/도판트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도판트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트와 호스트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다. The material used as the organic material layer in the organic light emitting device can be largely classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on the function. The light emitting material may be classified into a polymer and a low molecule according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. According to the emission color can be divided into blue, green, red light emitting material and yellow and orange light emitting material required to implement a better natural color. In addition, in order to increase luminous efficiency through an increase in color purity and energy transfer, a host / dopant system may be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host to be used.
특히 현재까지 이러한 유기발광소자에 사용되는 정공주입 및 정공수송 재료에는 카바졸 골격을 가지는 아민 유도체가 많이 연구되었으나 보다 높은 구동전압, 낮은 효율 및 짧은 수명으로 인해 실용화하는 데에 많은 어려움이 있었다. 따라서 우수한 특성을 갖는 물질을 이용하여 저전압 구동, 고휘도 및 장수명을 갖는 유기발광소자를 개발하려는 노력이 지속되어 왔다. In particular, many amine derivatives having a carbazole skeleton have been studied in the hole injection and hole transport materials used in the organic light emitting device, but there are many difficulties in practical use due to the higher driving voltage, lower efficiency and shorter lifetime. Therefore, efforts have been made to develop organic light emitting diodes having low voltage driving, high brightness and long life using materials having excellent characteristics.
상기와 같은 문제점을 해결하기 위해, 본 발명은 유기발광소자에 적용시 정공주입 및 정공전달 특성이 우수하고, 동시에 전자차단 특성이 우수하며, 높은 삼중항 에너지 및 높은 Tg를 구현할 수 있으며, 낮은 구동전압, 저소비전력, 고효율 및 장수명을 가지게 할 수 있으며, 특히 청색 및 인광용 유기발광소자에 적합한 신규한 화합물을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention is excellent in the hole injection and hole transfer characteristics when applied to the organic light emitting device, and at the same time excellent in the electron blocking characteristics, high triplet energy and high Tg can be realized, low driving An object of the present invention is to provide a novel compound which can have a voltage, low power consumption, high efficiency and long life, and is particularly suitable for an organic light emitting device for blue and phosphorescence.
본 발명은 또한 상기 신규한 화합물을 포함하여 정공주입 및 정공수송 특성이 우수하고, 동시에 전자차단 특성이 우수하며, 동시에 높은 삼중항 에너지 및 높은 Tg를 구현할 수 있으며, 낮은 구동전압, 저소비전력, 고효율 및 장수명을 가지게 할 수 있는 유기발광소자를 제공하는 것을 목적으로 한다.The present invention also includes the novel compound, which has excellent hole injection and hole transport characteristics, and at the same time, excellent electron blocking characteristics, and at the same time, can realize high triplet energy and high Tg, and low driving voltage, low power consumption, and high efficiency. And it is an object to provide an organic light emitting device that can have a long life.
상기 목적을 달성하기 위해 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:In order to achieve the above object, the present invention provides a compound represented by the following Chemical Formula 1:
[화학식 1][Formula 1]
상기 식에서,Where
l, m, n, o는 각각 독립적으로 1 내지 3으로부터 선택되는 정수이며, Ar은 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,l, m, n, o are each independently an integer selected from 1 to 3, Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R1, R2, R3, R4, R5, 및 R6은 각각 독립적으로 수소; 중수소; 할로겐; 아미노기; 니트릴기; 니트로기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
또한, 본 발명은 제1전극, 제2전극 및 두 전극 사이에 상기 화학식 1로 표시되는 화합물을 함유하는 1층 이상의 유기물층을 포함하는 유기발광소자를 제공한다.The present invention also provides an organic light emitting device including one or more organic material layers containing a compound represented by Chemical Formula 1 between a first electrode, a second electrode, and two electrodes.
본 발명의 화합물은 청색 및 인광용 유기발광소자에 적용시 정공주입 및 정공전달 특성이 우수하고, 동시에 전자차단 특성이 우수하며, 높은 삼중항 에너지 및 높은 Tg를 구현할 수 있으며, 낮은 구동전압, 저소비전력, 고효율 및 장수명을 가지게 할 수 있다.The compound of the present invention has excellent hole injection and hole transport characteristics when applied to the organic light emitting device for blue and phosphorescence, at the same time excellent in the electron blocking characteristics, high triplet energy and high Tg, low drive voltage, low consumption It can have power, high efficiency and long life.
도 1은 본 발명의 일 실시예에 따른 OLED의 단면을 개략적으로 도시한 것이다.1 schematically illustrates a cross section of an OLED according to an embodiment of the invention.
도면의 부호Sign of drawing
10 : 기판10: substrate
11 : 양극11: anode
12 : 정공주입층12: hole injection layer
13 : 정공전달층13: hole transport layer
14 : 발광층14: light emitting layer
15 : 전자전달층15: electron transport layer
16: 음극16: cathode
본 발명의 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다.The compound of the present invention is characterized by represented by the following formula (1).
[화학식 1][Formula 1]
상기 식에서,Where
l, m, n, o는 각각 독립적으로 1 내지 3으로부터 선택되는 정수이며, Ar은 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,l, m, n, o are each independently an integer selected from 1 to 3, Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R1, R2, R3, R4, R5, 및 R6은 각각 독립적으로 수소; 중수소; 할로겐; 아미노기; 니트릴기; 니트로기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
구체적으로 상기 화학식 1로 표시되는 화합물은 하기 화학식 1-1 내지 1-7으로 표시되는 화합물 중 하나인 것이 좋다.Specifically, the compound represented by Chemical Formula 1 may be one of the compounds represented by the following Chemical Formulas 1-1 to 1-7.
[화학식 1-1] [Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
[화학식 1-4][Formula 1-4]
[화학식 1-5][Formula 1-5]
[화학식 1-6][Formula 1-6]
[화학식 1-7][Formula 1-7]
상기 화학식들에서 n, p, q 및 r은 각각 독립적으로 1 내지 3으로부터 선택되는 정수이며, N, p, q and r in the formulas are each independently an integer selected from 1 to 3,
Ar1 및 Ar2는 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,Ar 1 and Ar 2 are each independently a C 6-50 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro groups; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R1, R5, R6, R7, R8, R9, R10, R11, R12, 및 R13은 각각 독립적으로 수소; 중수소; 할로겐; 아미노기; 니트릴기; 니트로기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며, R 1 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R5, R6, R7, R8, R9, R10, Ar1, Ar2는 인접한 기 또는 서로 고리를 형성할 수 있다.R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , Ar 1 , Ar 2 may form an adjacent group or a ring with each other.
본 발명에 있어서, 상기 화학식 1로 표시되는 화합물의 바람직한 구체적인 예는 다음과 같다:In the present invention, preferred specific examples of the compound represented by Formula 1 are as follows:
본 발명에 따른 화학식 1의 화합물은 유기발광소자에 적용시 정공주입 및 정공전달 특성이 우수하고, 동시에 전자차단 특성이 우수하며, 높은 삼중항 에너지 및 높은 Tg를 구현할 수 있으며, 낮은 구동전압, 저소비전력, 고효율 및 장수명을 가지게 할 수 있다. The compound of formula 1 according to the present invention has excellent hole injection and hole transport characteristics when applied to an organic light emitting device, and at the same time excellent in electron blocking characteristics, high triplet energy and high Tg, low driving voltage, low consumption It can have power, high efficiency and long life.
특히, 상기 화학식 1-1 및 1-2로 표시되는 화합물은 형광 및 적색 인광 유기발광소자에서 더욱 우수한 소자 특성을 나타낼 수 있으며, 상기 화학식 1-7로 표시되는 화합물은 녹색 인광 유기발광소자에서 더욱 우수한 소자 특성을 나타낼 수 있다.In particular, the compounds represented by Chemical Formulas 1-1 and 1-2 may exhibit more excellent device characteristics in fluorescent and red phosphorescent organic light emitting diodes, and the compounds represented by Chemical Formula 1-7 may be further represented in green phosphorescent organic light emitting diodes It can exhibit excellent device characteristics.
또한 본 발명의 화합물은 하기 반응식 1을 통하여 제조될 수 있다:Compounds of the invention can also be prepared via Scheme 1 below:
[반응식 1]Scheme 1
상기 반응식 1에서 l, m, n, o, Ar, R1, R2, R3, R4, R5, 및 R6은 화학식 1에서 정의한 바와 같다.In Scheme 1, l, m, n, o, Ar, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are as defined in Formula 1.
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 유기물층에 포함하는 유기발광소자를 제공한다. 구체적으로 정공주입물질, 정공수송물질, 발광보조물질로 포함하는 것이며, 이때, 본 발명의 화합물은 단독으로 사용되거나 공지의 유기발광 화합물과 함께 사용될 수 있다. 더욱 구체적으로는 상기 유기발광소자는 형광, 적색인광, 녹색인광 유기발광소자인 것이 좋다. The present invention also provides an organic light emitting device comprising the compound represented by Chemical Formula 1 in an organic material layer. Specifically, it will be included as a hole injection material, a hole transport material, a light emitting auxiliary material, wherein the compound of the present invention may be used alone or in combination with a known organic light emitting compound. More specifically, the organic light emitting device is preferably a fluorescent, red phosphorescent, green phosphorescent organic light emitting device.
또한 본 발명의 유기발광소자는 상기 화학식 1로 표시되는 화합물을 포함하는 1층 이상의 유기물층을 포함하는 바, 상기 유기발광소자의 제조방법을 설명하면 다음과 같다.In addition, the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Chemical Formula 1, and the method of manufacturing the organic light emitting device is as follows.
상기 유기발광소자는 제1전극(애노드(anode))과 제2전극(캐소드(cathod)) 사이에 정공주입층(HIL), 정공수송층(HTL), 발광보조층, 발광층(EML), 전자수송층(ETL), 전자주입층(EIL) 등의 유기물층을 1 개 이상 포함할 수 있다.The organic light emitting diode includes a hole injection layer (HIL), a hole transport layer (HTL), an emission auxiliary layer, an emission layer (EML), and an electron transport layer between a first electrode (anode) and a second electrode (cathod). One or more organic material layers, such as (ETL) and an electron injection layer (EIL), may be included.
먼저, 기판 상부에 높은 일함수를 갖는 애노드 전극용 물질을 증착시켜 애노드를 형성한다. 이때, 상기 기판은 통상의 유기발광소자에서 사용되는 기판을 사용할 수 있으며, 특히 기계적 강도, 열적 안정성, 투명성, 표면평활성, 취급용이성, 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판을 사용하는 것이 좋다. 또한, 애노드 전극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등을 사용할 수 있다. 상기 애노드 전극용 물질은 통상의 애노드 형성방법에 의해 증착할 수 있으며, 구체적으로 증착법 또는 스퍼터링법에 의해 증착할 수 있다.First, an anode is formed by depositing a material for an anode electrode having a high work function on the substrate. In this case, the substrate may be a substrate used in a conventional organic light emitting device, it is particularly preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproof. In addition, as the anode electrode material, transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and the like may be used. The anode electrode material may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.
그 다음, 상기 애노드 전극 상부에 정공주입층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB(Langmuir-Blodgett)법 등과 같은 방법에 의해 형성할 수 있다. 상기 진공증착법에 의해 정공주입층을 형성하는 경우 그 증착조건은 정공주입층의 재료로서 사용하는 화합물, 목적하는 정공주입층의 구조 및 열적특성 등에 따라 다르지만, 일반적으로 50-500 ℃의 증착온도, 10-8 내지 10-3 torr의 진공도, 0.01 내지 100 Å/sec의 증착속도, 10 Å 내지 5 ㎛의 층 두께 범위에서 적절히 선택할 수 있다.Subsequently, the hole injection layer material may be formed on the anode electrode by a method such as vacuum deposition, spin coating, casting, and Langmuir-Blodgett (LB). When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the desired hole injection layer, and generally, a deposition temperature of 50-500 ° C., It can be suitably selected from a vacuum degree of 10 −8 to 10 −3 torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 kPa to 5 μm.
상기 정공주입층 물질은 본 발명의 화학식 1로 표시되는 화합물을 사용할 수 있으며, 공지의 물질과 함께 사용할 수도 있다. 상기 공지의 물질은 특별히 제한되지 않으며, 미국특허 제4,356,429호에 개시된 구리 프탈로시아닌 등의 프탈로시아닌 화합물 또는 스타버스트형 아민 유도체류인 TCTA(4,4',4"-트리(N-카바졸릴)트리페닐아민), m-MTDATA(4,4',4"-트리스(3-메틸페닐아미노)트리페닐아민), m-MTDAPB(4,4',4"-트리스(3-메틸페닐아미노)페녹시벤젠), HI-406(N1,N1'-(비페닐-4,4'-디일)비스(N1-(나프탈렌-1-일)-N4,N4-디페닐벤젠-1,4-디아민) 등을 정공주입층 물질로 사용할 수 있다.The hole injection layer material may be a compound represented by Formula 1 of the present invention, it may be used with a known material. The known material is not particularly limited, and TCTA (4,4 ′, 4 ″ -tri (N-carbazolyl) triphenyl, which is a phthalocyanine compound or starburst amine derivatives such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 Amine), m-MTDATA (4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine), m-MTDAPB (4,4', 4" -tris (3-methylphenylamino) phenoxybenzene) , HI-406 (N1, N1 '-(biphenyl-4,4'-diyl) bis (N1- (naphthalen-1-yl) -N4, N4-diphenylbenzene-1,4-diamine) It can be used as injection layer material.
다음으로 상기 정공주입층 상부에 정공수송층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있다. 상기 진공증착법에 의해 정공수송층을 형성하는 경우 그 증착조건은 사용하는 화합물에 따라 다르지만 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다.Next, the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, or the like. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.
또한, 상기 정공수송층 물질은 본 발명의 화학식 1로 표시되는 화합물을 사용할 수 있으며, 공지의 물질과 함께 사용할 수도 있다. 상기 공지의 물질은 특별히 제한되지는 않으며, 정공수송층에 사용되고 있는 통상의 공지 물질 중에서 임의로 선택하여 사용할 수 있다. 구체적으로, 상기 정공수송층 물질은 N-페닐카바졸, 폴리비닐카바졸 등의 카바졸 유도체, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD), N.N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등의 방향족 축합환을 가지는 통상의 아민 유도체 등이 사용될 수 있다.In addition, the hole transport material may be a compound represented by the formula (1) of the present invention, it may be used with a known material. The known material is not particularly limited, and may be arbitrarily selected and used from conventional known materials used in the hole transport layer. Specifically, the hole transport layer material is carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD) Derivatives and the like can be used.
또한 상기 정공수송층 상부에 보조층을 더욱 포함할 수 있다. 상기 보조층은 정공수송층 상부에 보조층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있다. 상기 보조층은 본 발명의 화학식 1로 표시되는 화합물을 사용할 수 있으며, 이 경우 정공수송층은 하기 화학식 2로 표시되는 화합물을 사용하는 것이 좋다.In addition, an auxiliary layer may be further included on the hole transport layer. The auxiliary layer may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, cast, LB, or the like. The auxiliary layer may be a compound represented by the formula (1) of the present invention, in this case, the hole transport layer is preferably used a compound represented by the formula (2).
[화학식 2][Formula 2]
상기 화학식에서,In the above formula,
l, m, n, o는 각각 독립적으로 1 내지 3으로부터 선택되는 정수이며, Ar은 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,l, m, n, o are each independently an integer selected from 1 to 3, Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,
R1, R2, R3, R4, 및 R5는 각각 독립적으로 수소; 중수소; 할로겐; 아미노기; 니트릴기; 니트로기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
상기 화학식 2로 표시되는 화합물의 구체적인 예는 다음과 같다:Specific examples of the compound represented by Formula 2 are as follows:
상기와 같은 경우, 효율 상승 및 수명 개선 효과가 현저히 개선될 수 있다. In such a case, the effect of increasing the efficiency and improving the life may be remarkably improved.
그 후, 상기 정공수송층 또는 보조층 상부에 발광층 물질을 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법에 의해 형성할 수 있다. 상기 진공증착법에 의해 발광층을 형성하는 경우 그 증착조건은 사용하는 화합물에 따라 다르지만 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택하는 것이 좋다. 또한, 상기 발광층 재료는 공지의 화합물을 호스트 또는 도펀트로 사용할 수 있다.Thereafter, the light emitting layer material may be formed on the hole transport layer or the auxiliary layer by a method such as vacuum deposition, spin coating, cast, LB, or the like. In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer. In addition, the light emitting layer material may use a known compound as a host or dopant.
일예로 형광 도펀트로는 이데미츠사(Idemitsu사)에서 구입 가능한 IDE102 또는 IDE105, 또는 BD142(N6,N12-비스(3,4-디메틸페닐)-N6,N12-디메시틸크리센-6,12-디아민)를 사용할 수 있으며, 인광 도펀트로는 녹색 인광 도펀트 Ir(ppy)3(트리스(2-페닐피리딘) 이리듐), 청색 인광 도펀트인 F2Irpic(이리듐(Ⅲ) 비스[4,6-다이플루오로페닐)-피리디나토-N,C2'] 피콜린산염), UDC사의 적색 인광 도펀트 RD61 등이 공동 진공증착(도핑)될 수 있다.For example, a fluorescent dopant may be IDE102 or IDE105 available from Idemitsu, or BD142 (N 6 , N 12 -bis (3,4-dimethylphenyl) -N 6 , N 12 -dimethycrylicene- 6,12-diamine) can be used as green phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate), a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped).
또한, 발광층에 인광 도펀트와 함께 사용할 경우에는 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지하기 위하여 정공억제재료(HBL)를 추가로 진공증착법 또는 스핀코팅법에 의해 적층할 수 있다. 이때 사용할 수 있는 정공억제물질은 특별히 제한되지는 않으나, 정공억제재료로 사용되고 있는 공지의 것에서 임의의 것을 선택해서 이용할 수 있다. 예를 들면, 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, 또는 일본특개평 11-329734(A1)에 기재되어 있는 정공억제재료 등을 들 수 있으며, 대표적으로 Balq(비스(8-하이드록시-2-메틸퀴놀리놀나토)-알루미늄 비페녹사이드), 페난트롤린(phenanthrolines)계 화합물(예: UDC사 BCP(바쏘쿠프로인)) 등을 사용할 수 있다.In addition, when used with a phosphorescent dopant in the light emitting layer, to prevent the triplet exciton or hole from being diffused into the electron transport layer, the hole suppressing material (HBL) may be further laminated by vacuum deposition or spin coating. The hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited. Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound (e.g., BCP (vasocuproin) from UDC) can be used.
상기와 같이 형성된 발광층 상부에는 전자수송층이 형성되는데, 이때 상기 전자수송층은 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성될 수 있다.An electron transport layer is formed on the light emitting layer formed as described above, wherein the electron transport layer may be formed by a vacuum deposition method, a spin coating method, a casting method, or the like.
상기 전자수송층 재료는 전자주입전극으로부터 주입된 전자를 안정하게 수송하는 기능을 하는 것으로서 그 종류가 특별히 제한되지는 않으며, 예를 들어 퀴놀린 유도체, 특히 트리스(8-퀴놀리놀라토)알루미늄(Alq3), 또는 ET4(6,6'-(3,4-디메시틸-1,1-디메틸-1H-실올-2,5-디일)디-2,2'-비피리딘)을 사용할 수 있다. 또한, 전자수송층 상부에 캐소드로부터 전자의 주입을 용이하게 하는 기능을 가지는 물질인 전자주입층(EIL)이 적층될 수 있으며, 전자주입층 물질로는 LiF, NaCl, CsF, Li2O, BaO 등의 물질을 이용할 수 있다.The electron transport layer material functions to stably transport electrons injected from the electron injection electrode, and the type thereof is not particularly limited, and examples thereof include quinoline derivatives, especially tris (8-quinolinolato) aluminum (Alq 3). ), Or ET4 (6,6 '-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl) di-2,2'-bipyridine). In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and the electron injection layer material may be LiF, NaCl, CsF, Li 2 O, BaO, or the like. The substance of can be used.
또한, 상기 전자수송층의 증착조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건 범위에서 선택할 수 있다.In addition, the deposition conditions of the electron transport layer is different depending on the compound used, but can be generally selected in the same condition range as the formation of the hole injection layer.
그 뒤, 상기 전자수송층 상부에 전자주입층 물질을 형성할 수 있으며, 이때 상기 전자수송층은 통상의 전자주입층 물질을 진공증착법, 스핀코팅법, 캐스트법 등의 방법으로 형성되며, 특히 진공증착법에 의해 형성하는 것이 좋다.Subsequently, an electron injection layer material may be formed on the electron transport layer, wherein the electron transport layer is formed of a conventional electron injection layer material by a vacuum deposition method, a spin coating method, a casting method, and the like. It is good to form.
마지막으로 전자주입층 상부에 캐소드 형성용 금속을 진공증착법이나 스퍼터링법 등의 방법에 의해 형성하고 캐소드로 사용한다. 여기서 캐소드 형성용 금속으로는 낮은 일함수를 가지는 금속, 합금, 전기전도성 화합물, 및 이들의 혼합물을 사용할 수 있다. 구체적인 예로는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등이 있다. 또한, 전면 발광소자를 얻기 위하여 ITO, IZO를 사용한 투과형 캐소드를 사용할 수도 있다.Finally, a cathode forming metal is formed on the electron injection layer by a method such as vacuum deposition or sputtering and used as a cathode. The cathode forming metal may be a metal having low work function, an alloy, an electrically conductive compound, and a mixture thereof. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. There is this. In addition, a transmissive cathode using ITO or IZO may be used to obtain the front light emitting device.
본 발명의 유기발광소자는 애노드, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 캐소드 구조의 유기발광소자 뿐만 아니라, 다양한 구조의 유기발광소자의 구조가 가능하며, 필요에 따라 발광보조층과 같은 1층 또는 2층의 중간층을 더 형성하는 것도 가능하다.The organic light emitting device of the present invention is capable of not only an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device having a cathode structure, but also an organic light emitting device having various structures, and emits light as necessary. It is also possible to form one or two intermediate layers such as an auxiliary layer.
상기와 같이 본 발명에 따라 형성되는 각 유기물층의 두께는 요구되는 정도에 따라 조절할 수 있으며, 구체적으로는 1 내지 1,000 ㎚이며, 더욱 구체적으로는 5 내지 200 ㎚인 것이 좋다. 이 범위 내에서 고효율, 장수명, 고색순도의 효과가 더욱 우수하다.The thickness of each organic material layer formed according to the present invention as described above can be adjusted according to the required degree, specifically 1 to 1,000 nm, more preferably 5 to 200 nm. Within this range, the effect of high efficiency, long life and high color purity is more excellent.
또한 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 유기물층의 두께를 분자 단위로 조절할 수 있기 때문에 표면이 균일하며, 형태안정성이 뛰어난 장점이 있다.In addition, the present invention has an advantage that the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.
본 발명의 유기발광소자는 상기 화학식 1로 표시되는 화합물을 포함하여 정공주입 및 정공전달 특성이 우수하고, 동시에 전자차단 특성이 우수하며, 높은 삼중항 에너지 및 높은 Tg를 구현하여, 낮은 구동전압, 저소비전력, 고효율 및 장수명을 가진다.The organic light emitting device of the present invention includes the compound represented by Chemical Formula 1, and has excellent hole injection and hole transport characteristics, and at the same time, excellent electron blocking characteristics, high triplet energy and high Tg, and low driving voltage. It has low power consumption, high efficiency and long life.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
OP의 합성OP synthesis
목적 화합물 합성을 위해 OP의 준비는 상기 단계를 거쳐 합성하였다.Preparation of OP for synthesis of the desired compound was carried out via the above steps.
하기 OP1의 합성법은 다음과 같다.Synthesis of OP1 below is as follows.
둥근바닥플라스크에 N-phenylnaphthalen-1-amine 10 g, 1-bromo-4-iodobenzene 18.0 g, t-BuONa 6.5 g, Pd2(dba)3 1.7 g,(t-Bu)3P 2.6 ml를 톨루엔 100 ml에 녹인 후 50 ℃로 교반하였다. TLC로 반응을 확인하고 물을 첨가 후 반응을 종결하였다. 유기층을 EA로 추출하고 감압여과한 후 컬럼정제하여 중간체 OP1 7.6 g (수율 45%)를 얻었다.Toluene was added 10 g of N-phenylnaphthalen-1-amine, 18.0 g of 1-bromo-4-iodobenzene, 6.5 g of t-BuONa, 1.7 g of Pd 2 (dba) 3 and 2.6 ml of (t-Bu) 3 P in a round bottom flask. After dissolving in 100 ml and stirred at 50 ℃. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 7.6 g (yield 45%) of intermediate OP1.
상기 OP1과 대등한 방법으로 출발물질을 달리하여 하기 OP2 내지 OP19를 합성하였다.The following OP2 to OP19 were synthesized by varying the starting material in the same manner as the OP1.
화학식 1의 합성예Synthesis Example of Formula 1
화합물 1의 합성Synthesis of Compound 1
둥근바닥플라스크에 1H-indole 3.0 g, OP1 10.54 g, t-BuONa 3.7 g, Pd2(dba)3 0.95 g,(t-Bu)3P 1.1 ml를 톨루엔 95 ml에 녹인 후 환류 교반하였다. TLC로 반응을 확인하고 물을 첨가 후 반응을 종결하였다. 유기층을 EA로 추출하고 감압여과한 후 컬럼정제하여 화합물1 3.63 g (수율 50%)를 얻었다.In a round bottom flask, 3.0 g of 1H-indole, 10.54 g of OP1, 3.7 g of t-BuONa, 0.95 g of Pd 2 (dba) 3 , and 1.1 ml of (t-Bu) 3 P were dissolved in 95 ml of toluene, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 3.63 g (50% yield) of compound 1.
m/z: 486.21 (100.0%), 487.21 (39.7%), 488.22 (7.5%)m / z: 486.21 (100.0%), 487.21 (39.7%), 488.22 (7.5%)
화합물 2의 합성Synthesis of Compound 2
화합물 1과 같은 방법으로 OP1 대신 OP2를 사용하여 화합물 2를 합성하였다. (수율53%)Compound 2 was synthesized using OP2 instead of OP1 in the same manner as compound 1. (Yield 53%)
m/z: 512.23 (100.0%), 513.23 (41.4%), 514.23 (8.7%), 515.24 (1.1%)m / z: 512.23 (100.0%), 513.23 (41.4%), 514.23 (8.7%), 515.24 (1.1%)
화합물 3의 합성Synthesis of Compound 3
화합물 1과 같은 방법으로 OP1 대신 OP3을 사용하여 화합물 3를 합성하였다. (수율48%)Compound 3 was synthesized using OP3 instead of OP1 in the same manner as compound 1. (Yield 48%)
m/z: 552.26 (100.0%), 553.26 (44.7%), 554.26 (9.9%), 555.27 (1.4%)m / z: 552.26 (100.0%), 553.26 (44.7%), 554.26 (9.9%), 555.27 (1.4%)
화합물 4의 합성Synthesis of Compound 4
화합물 1과 같은 방법으로 OP1 대신 OP4를 사용하여 화합물 4를 합성하였다. (수율55%)Compound 4 was synthesized using OP4 instead of OP1 in the same manner as compound 1. (Yield 55%)
m/z: 588.26 (100.0%), 589.26 (48.0%), 590.26 (11.4%), 591.27 (1.7%)m / z: 588.26 (100.0%), 589.26 (48.0%), 590.26 (11.4%), 591.27 (1.7%)
화합물 5의 합성Synthesis of Compound 5
화합물 1과 같은 방법으로 OP1 대신 OP5를 사용하여 화합물 5를 합성하였다. (수율48%)Compound 5 was synthesized using OP5 instead of OP1 in the same manner as compound 1. (Yield 48%)
m/z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)m / z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)
화합물 6의 합성Synthesis of Compound 6
화합물 1과 같은 방법으로 OP1 대신 OP6을 사용하여 화합물 6을 합성하였다. (수율49%)Compound 6 was synthesized using OP6 instead of OP1 in the same manner as compound 1. (Yield 49%)
m/z: 588.26 (100.0%), 589.26 (48.0%), 590.26 (11.4%), 591.27 (1.7%)m / z: 588.26 (100.0%), 589.26 (48.0%), 590.26 (11.4%), 591.27 (1.7%)
화합물 7의 합성Synthesis of Compound 7
화합물 1과 같은 방법으로 OP1 대신 OP7을 사용하여 화합물 7을 합성하였다. (수율48%)Compound 7 was synthesized using OP7 instead of OP1 in the same manner as compound 1. (Yield 48%)
m/z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)m / z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)
화합물 8의 합성Synthesis of Compound 8
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP4를 사용하여 화합물 8을 합성하였다. (수율52%)Compound 8 was synthesized using the same method as Compound 1 using 3-phenyl-1H-indole instead of 1H-indole and OP4 instead of OP1. (Yield 52%)
m/z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)
화합물 9의 합성Synthesis of Compound 9
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP5를 사용하여 화합물 9을 합성하였다. (수율48%)Compound 9 was synthesized in the same manner as in compound 1, using OP5 instead of OP1 as 3-phenyl-1H-indole instead of 1H-indole. (Yield 48%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 10의 합성Synthesis of Compound 10
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP6을 사용하여 화합물 10을 합성하였다. (수율50%) Compound 10 was synthesized using the same method as Compound 1 using 3-phenyl-1H-indole instead of 1H-indole and OP6 instead of OP1. (50% yield)
m/z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)
화합물 11의 합성Synthesis of Compound 11
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP7을 사용하여 화합물 11을 합성하였다. (수율49%) Compound 11 was synthesized using the same method as Compound 1 using 3-phenyl-1H-indole instead of 1H-indole and OP7 instead of OP1. (Yield 49%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 12의 합성Synthesis of Compound 12
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP8을 사용하여 화합물 12을 합성하였다. (수율44%) Compound 12 was synthesized using the same method as Compound 1 using 3-phenyl-1H-indole instead of 1H-indole and OP8 instead of OP1. (Yield 44%)
m/z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)
화합물 13의 합성Synthesis of Compound 13
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP9를 사용하여 화합물 13을 합성하였다. (수율38%) Compound 13 was synthesized in the same manner as in compound 1, using OP9 instead of OP1 as 3-phenyl-1H-indole instead of 1H-indole. (Yield 38%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 14의 합성Synthesis of Compound 14
화합물 1과 같은 방법으로 1H-indole 대신 2-phenyl-1H-indole로 OP1 대신 OP4를 사용하여 화합물 14를 합성하였다. (수율55%) Compound 14 was synthesized using the same method as Compound 1 using 2-phenyl-1H-indole instead of 1H-indole and OP4 instead of OP1. (Yield 55%)
m/z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)
화합물 15의 합성Synthesis of Compound 15
화합물 1과 같은 방법으로 1H-indole 대신 2-phenyl-1H-indole로 OP1 대신 OP5를 사용하여 화합물 15를 합성하였다. (수율48%) Compound 15 was synthesized in the same manner as in compound 1, using OP5 instead of OP1 as 2-phenyl-1H-indole instead of 1H-indole. (Yield 48%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 16의 합성Synthesis of Compound 16
화합물 1과 같은 방법으로 1H-indole 대신 2-phenyl-1H-indole로 OP1 대신 OP6을 사용하여 화합물 16을 합성하였다. (수율49%)Compound 16 was synthesized in the same manner as in compound 1, using OP6 instead of OP1 as 2-phenyl-1H-indole instead of 1H-indole. (Yield 49%)
m/z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)
화합물 17의 합성Synthesis of Compound 17
화합물 1과 같은 방법으로 1H-indole 대신 2-phenyl-1H-indole로 OP1 대신 OP7을 사용하여 화합물 17을 합성하였다. (수율45%)Compound 17 was synthesized in the same manner as in compound 1, using OP7 instead of OP1 with 2-phenyl-1H-indole instead of 1H-indole. (Yield 45%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 18의 합성Synthesis of Compound 18
화합물 1과 같은 방법으로 1H-indole 대신 2-phenyl-1H-indole로 OP1 대신 OP8을 사용하여 화합물 18을 합성하였다. (수율49%)Compound 18 was synthesized using the same method as Compound 1 using 2-phenyl-1H-indole instead of 1H-indole and OP8 instead of OP1. (Yield 49%)
m/z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)
화합물 19의 합성Synthesis of Compound 19
화합물 1과 같은 방법으로 1H-indole 대신 2-phenyl-1H-indole로 OP1 대신 OP9를 사용하여 화합물 19를 합성하였다. (수율40%)Compound 19 was synthesized using the same method as Compound 1 using 2-phenyl-1H-indole instead of 1H-indole and OP9 instead of OP1. (Yield 40%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 20의 합성Synthesis of Compound 20
화합물 1과 같은 방법으로 1H-indole 대신 2,3-diphenyl-1H-indole로 OP1 대신 OP4를 사용하여 화합물 20을 합성하였다. (수율42%)Compound 20 was synthesized by using OP4 instead of OP1 with 2,3-diphenyl-1H-indole instead of 1H-indole in the same manner as compound 1. (Yield 42%)
m/z: 740.32 (100.0%), 741.32 (61.3%), 742.33 (18.3%), 743.33 (3.6%)m / z: 740.32 (100.0%), 741.32 (61.3%), 742.33 (18.3%), 743.33 (3.6%)
화합물 21의 합성Synthesis of Compound 21
화합물 1과 같은 방법으로 1H-indole 대신 2,3-diphenyl-1H-indole로 OP1 대신 OP5를 사용하여 화합물 21을 합성하였다. (수율42%)Compound 21 was synthesized in the same manner as in compound 1, using OP5 instead of OP1 as 2,3-diphenyl-1H-indole instead of 1H-indole. (Yield 42%)
m/z: 780.35 (100.0%), 781.35 (64.6%), 782.36 (20.3%), 783.36 (4.2%)m / z: 780.35 (100.0%), 781.35 (64.6%), 782.36 (20.3%), 783.36 (4.2%)
화합물 22의 합성Synthesis of Compound 22
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP10을 사용하여 화합물 22를 합성하였다. (수율44%)Compound 22 was synthesized in the same manner as in compound 1, using OP10 instead of OP1 as 3-phenyl-1H-indole instead of 1H-indole. (Yield 44%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 23의 합성Synthesis of Compound 23
화합물 1과 같은 방법으로 1H-indole 대신 3-phenyl-1H-indole로 OP1 대신 OP11을 사용하여 화합물 23을 합성하였다. (수율43%)Compound 23 was synthesized in the same manner as in compound 1, using OP11 instead of OP1 as 3-phenyl-1H-indole instead of 1H-indole. (Yield 43%)
m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)m / z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)
화합물 24의 합성Synthesis of Compound 24
화합물 1과 같은 방법으로 OP1 대신 OP13을 사용하여 화합물 24를 합성하였다. (수율55%)Compound 24 was synthesized using OP13 instead of OP1 in the same manner as in compound 1. (Yield 55%)
m/z: 592.29 (100.0%), 593.29 (48.0%), 594.29 (11.4%), 595.30 (1.7%)m / z: 592.29 (100.0%), 593.29 (48.0%), 594.29 (11.4%), 595.30 (1.7%)
화합물 25의 합성Synthesis of Compound 25
화합물 1과 같은 방법으로 OP1 대신 OP14를 사용하여 화합물 25를 합성하였다. (수율52%)Compound 25 was synthesized using OP14 instead of OP1 in the same manner as Compound 1. (Yield 52%)
m/z: 716.32 (100.0%), 717.32 (59.1%), 718.33 (17.0%), 719.33 (3.2%)m / z: 716.32 (100.0%), 717.32 (59.1%), 718.33 (17.0%), 719.33 (3.2%)
화합물 26의 합성Synthesis of Compound 26
화합물 1과 같은 방법으로 OP1 대신 OP15을 사용하여 화합물 26를 합성하였다. (수율50%)Compound 26 was synthesized using OP15 instead of OP1 in the same manner as in compound 1. (50% yield)
m/z: 592.29 (100.0%), 593.29 (48.0%), 594.29 (11.4%), 595.30 (1.7%)m / z: 592.29 (100.0%), 593.29 (48.0%), 594.29 (11.4%), 595.30 (1.7%)
화합물 27의 합성Synthesis of Compound 27
화합물 1과 같은 방법으로 OP1 대신 OP16을 사용하여 화합물 27를 합성하였다. (수율51%)Compound 27 was synthesized using OP16 instead of OP1 in the same manner as in compound 1. (Yield 51%)
m/z: 716.32 (100.0%), 717.32 (59.1%), 718.33 (17.0%), 719.33 (3.2%)m / z: 716.32 (100.0%), 717.32 (59.1%), 718.33 (17.0%), 719.33 (3.2%)
화합물 28의 합성Synthesis of Compound 28
화합물 1과 같은 방법으로 OP1 대신 OP17을 사용하여 화합물 28을 합성하였다. (수율45%)Compound 28 was synthesized using OP17 instead of OP1 in the same manner as in compound 1. (Yield 45%)
m/z: 592.29 (100.0%), 593.29 (48.0%), 594.29 (11.4%), 595.30 (1.7%)m / z: 592.29 (100.0%), 593.29 (48.0%), 594.29 (11.4%), 595.30 (1.7%)
화합물 29의 합성Synthesis of Compound 29
화합물 1과 같은 방법으로 OP1 대신 OP18을 사용하여 화합물 29를 합성하였다. (수율47%)Compound 29 was synthesized using OP18 instead of OP1 in the same manner as Compound 1. (Yield 47%)
m/z: 716.32 (100.0%), 717.32 (59.1%), 718.33 (17.0%), 719.33 (3.2%)m / z: 716.32 (100.0%), 717.32 (59.1%), 718.33 (17.0%), 719.33 (3.2%)
화합물 30의 합성Synthesis of Compound 30
화합물 1과 같은 방법으로 OP1 대신 OP19을 사용하여 화합물 30을 합성하였다. (수율47%)Compound 30 was synthesized using OP19 instead of OP1 in the same manner as in compound 1. (Yield 47%)
m/z: 714.30 (100.0%), 715.31 (58.8%), 716.31 (17.0%), 717.31 (3.3%)m / z: 714.30 (100.0%), 715.31 (58.8%), 716.31 (17.0%), 717.31 (3.3%)
화학식 2의 합성예Synthesis Example of Formula 2
화합물 31의 합성Synthesis of Compound 31
둥근바닥플라스크에 (1-phenyl-1H-indol-2-yl)boronic acid 2.2 g, OP3 4.0 g 1,4-dioxan 70 ml에 녹이고 K2CO3(2M) 12 ml와 Pd(PPh3)4 0.3 g을 넣은 후 환류 교반하였다. TLC로 반응을 확인하고 물을 첨가 후 반응을 종결시켰다. 유기층을 MC로 추출하고 감압여과한 후 컬럼정제 후 재결정하여 화합물 31 2.73 g (수율 56%)를 얻었다.In a round bottom flask, dissolve in 2.2 g of (1-phenyl-1H-indol-2-yl) boronic acid and 70 ml of OP3 4.0 g 1,4-dioxan, 12 ml of K 2 CO 3 (2M) and Pd (PPh 3 ) 4 0.3 g was added thereto, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure, and then recrystallized after column purification to obtain 2.73 g (56% yield) of compound 31.
m/z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)m / z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)
화합물 32의 합성Synthesis of Compound 32
화합물 31과 같은 방법으로 OP3 대신 OP5를 사용하여 화합물 32를 합성하였다. (수율48%)Compound 32 was synthesized using OP5 instead of OP3 in the same manner as compound 31. (Yield 48%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 33의 합성Synthesis of Compound 33
화합물 31과 같은 방법으로 OP3 대신 OP12를 사용하여 화합물 33을 합성하였다. (수율52%)Compound 33 was synthesized using OP12 instead of OP3 in the same manner as compound 31. (Yield 52%)
m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)m / z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)
화합물 34의 합성Synthesis of Compound 34
화합물 31과 같은 방법으로 (1-phenyl-1H-indol-2-yl)boronic acid 대신 (1-phenyl-1H-indol-3-yl)boronic acid로 OP1 대신 OP5를 사용하여 화합물 34를 합성하였다. (수율55%)Compound 34 was synthesized in the same manner as compound 31, using OP5 instead of OP1 as (1-phenyl-1H-indol-3-yl) boronic acid instead of (1-phenyl-1H-indol-2-yl) boronic acid. (Yield 55%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 35의 합성Synthesis of Compound 35
화합물 31과 같은 방법으로 (1-phenyl-1H-indol-2-yl)boronic acid 대신 (1-phenyl-1H-indol-3-yl)boronic acid로 OP1 대신 OP7을 사용하여 화합물 35를 합성하였다. (수율55%)Compound 35 was synthesized by using OP7 instead of OP1 as (1-phenyl-1H-indol-3-yl) boronic acid instead of (1-phenyl-1H-indol-2-yl) boronic acid in the same manner as Compound 31. (Yield 55%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 36의 합성Synthesis of Compound 36
화합물 35와 같은 방법으로 (1-phenyl-1H-indol-2-yl)boronic acid 대신 (1,2-diphenyl-1H-indol-3-yl)boronic acid 로 OP1 대신 OP5를 사용하여 화합물 36을 합성하였다. (수율52%)Compound 36 was synthesized using OP5 instead of OP1 with (1,2-diphenyl-1H-indol-3-yl) boronic acid instead of (1-phenyl-1H-indol-2-yl) boronic acid in the same manner as compound 35 It was. (Yield 52%)
m/z: 780.35 (100.0%), 781.35 (64.6%), 782.36 (20.3%), 783.36 (4.2%)m / z: 780.35 (100.0%), 781.35 (64.6%), 782.36 (20.3%), 783.36 (4.2%)
화합물 37의 합성Synthesis of Compound 37
화합물 31과 같은 (1-phenyl-1H-indol-2-yl)boronic acid 대신 (1-phenyl-1H-indol-3-yl)boronic acid로 OP1 대신 OP10을 사용하여 화합물 37을 합성하였다. (수율59%)Compound 37 was synthesized by using OP10 instead of OP1 as (1-phenyl-1H-indol-3-yl) boronic acid instead of (1-phenyl-1H-indol-2-yl) boronic acid as Compound 31. (Yield 59%)
m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)m / z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)
화합물 38의 합성Synthesis of Compound 38
화합물 31과 같은 방법으로 (1-phenyl-1H-indol-2-yl)boronic acid 대신 (1,2-diphenyl-1H-indol-3-yl)boronic acid 로 OP1 대신 OP10을 사용하여 화합물 38을 합성하였다. (수율49%)Compound 38 was synthesized by using OP10 instead of OP1 as (1,2-diphenyl-1H-indol-3-yl) boronic acid instead of (1-phenyl-1H-indol-2-yl) boronic acid in the same manner as Compound 31 It was. (Yield 49%)
m/z: 780.35 (100.0%), 781.35 (64.6%), 782.36 (20.3%), 783.36 (4.2%)m / z: 780.35 (100.0%), 781.35 (64.6%), 782.36 (20.3%), 783.36 (4.2%)
유기발광소자의 제조Fabrication of Organic Light Emitting Diode
도 1에 기재된 구조에 따라 유기발광소자를 제조하였다. 유기발광소자는 아래로부터 양극(정공주입전극(11))/정공주입층(12)/정공수송층(13)/발광층(14)/전자전달층(15)/음극(전자주입전극(16)) 순으로 적층되어 있다.An organic light emitting device was manufactured according to the structure of FIG. 1. The organic light emitting element is formed from the bottom of the anode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transfer layer 15 / cathode (electron injection electrode 16) It is laminated in order.
도 1에서 기판(10)은 유기발광소자 제작시 투명한 유리 기판 또는 플렉시블이 가능한 플라스틱 기판일 수 있다.In FIG. 1, the substrate 10 may be a transparent glass substrate or a flexible plastic substrate when the organic light emitting diode is manufactured.
정공 주입 전극(11)은 유기발광소자의 정공 주입을 위한 양극으로 사용된다. 정공의 주입이 가능하도록 낮은 일함수를 갖는 물질을 이용하며, 인듐틴옥사이드(ITO), 인듐징크옥사이드(IZO), 그래핀(grapheme)과 같은 투명한 재질로 형성 될 수 있다.The hole injection electrode 11 is used as an anode for hole injection of the organic light emitting device. A material having a low work function may be used to inject holes, and may be formed of a transparent material such as indium tin oxide (ITO), indium zinc oxide (IZO), and graphene.
실시예 및 비교예의 정공주입층(12), 정공전달층(13), 발광층(14), 전자전달층(15)은 아래와 같은 물질을 사용하였다.The hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of Examples and Comparative Examples used the following materials.
전자주입층(15) 위에 전자 주입을 위한 음극(16)을 형성한다. 음극으로는 다양한 금속이 사용 될 수 있다. 구체적인 예로 알루미늄, 금, 은 등의 물질이 있다.The cathode 16 for electron injection is formed on the electron injection layer 15. Various metals may be used as the cathode. Specific examples include materials such as aluminum, gold, and silver.
실시예 1Example 1
인듐틴옥사이드(ITO)가 1500 Å 두께가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공주입층 HT01 600 Å, 정공수송층으로 화합물 1로 250 Å를 제막하였다. 다음으로 상기 발광층으로 BH01:BD01 5%로 도핑하여 250 Å 제막하였다. 다음으로 전자전달층으로 ET01:Liq(1:1) 300 Å 제막한 후 LiF 10 Å, 알루미늄(Al) 1000 Å 제막하고, 이 소자를 글로브 박스에서 밀봉(Encapsulation)함으로써 유기발광소자를 제작하였다.A glass substrate coated with an indium tin oxide (ITO) 1500 Å thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes using an oxygen plasma. Using an evaporator, a film was deposited with a hole injection layer HT01 600 Å and a compound transport 1 with 250 Å as the hole transport layer. Next, the light emitting layer was doped with BH01: BD01 5% to form 250 Å. Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막, which were encapsulated in a glove box to produce an organic light emitting device.
실시예 2 내지 실시예 25Examples 2-25
실시예 1과 같은 방법으로 정공수송층을 각각 화합물 2 내지 25를 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 1, an organic light emitting diode was manufactured in which the hole transport layer was formed by using compounds 2 to 25, respectively.
비교예 1 Comparative Example 1
상기 실시예 1의 정공수송층으로 화합물 1을 NPB로 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was manufactured in the same manner as in Example 1, except that Compound 1 was used as the NPB as the hole transport layer.
비교예 2Comparative Example 2
상기 실시예 1의 정공수송층으로 화합물 1을 Ref.1로 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was manufactured in the same manner as in Example 1, except that Compound 1 was used as Ref. 1 as the hole transport layer.
비교예 3Comparative Example 3
상기 실시예 1의 정공수송층으로 화합물 1을 Ref.2로 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was manufactured in the same manner as in Example 1, except that Compound 1 was used as Ref. 2 as the hole transport layer.
유기발광소자의 성능평가Performance Evaluation of Organic Light Emitting Diode
키슬리 2400 소스 메져먼트 유닛(Kiethley 2400 source measurement unit) 으로 전압을 인가하여 전자 및 정공을 주입하고 코니카 미놀타(Konica Minolta) 분광복사계(CS-2000)를 이용하여 빛이 방출될 때의 휘도를 측정함으로써, 실시예 및 비교예의 유기발광소자의 성능을 인가전압에 대한 전류 밀도 및 휘도를 대기압 조건하에 측정하여 평가하였으며, 그 결과를 표 1에 나타내었다.Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using the Konica Minolta Spectroradiometer (CS-2000) Thus, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 1.
표 1
Table 1
Op. V | mA/cm2 | Cd/A | lm/w | CIEx | CIEy | LT95 | |
실시예1 | 4.441 | 10 | 5.85 | 4.79 | 0.141 | 0.120 | 22 |
실시예2 | 4.352 | 10 | 5.85 | 4.71 | 0.141 | 0.117 | 27 |
실시예3 | 4.343 | 10 | 5.88 | 4.76 | 0.142 | 0.115 | 30 |
실시예4 | 4.221 | 10 | 5.97 | 4.94 | 0.139 | 0.112 | 32 |
실시예5 | 4.212 | 10 | 6.00 | 4.92 | 0.138 | 0.113 | 35 |
실시예6 | 4.203 | 10 | 6.04 | 4.94 | 0.140 | 0.113 | 35 |
실시예7 | 4.295 | 10 | 6.07 | 4.99 | 0.140 | 0.113 | 37 |
실시예8 | 4.157 | 10 | 6.70 | 5.69 | 0.140 | 0.111 | 50 |
실시예9 | 4.130 | 10 | 6.63 | 5.64 | 0.139 | 0.112 | 47 |
실시예10 | 4.104 | 10 | 6.70 | 5.64 | 0.141 | 0.112 | 49 |
실시예11 | 4.100 | 10 | 6.59 | 5.67 | 0.142 | 0.112 | 49 |
실시예12 | 4.110 | 10 | 6.60 | 5.69 | 0.141 | 0.113 | 48 |
실시예13 | 4.109 | 10 | 6.63 | 5.65 | 0.142 | 0.113 | 50 |
실시예14 | 4.241 | 10 | 6.11 | 4.97 | 0.141 | 0.114 | 32 |
실시예15 | 4.214 | 10 | 6.19 | 4.80 | 0.141 | 0.113 | 35 |
실시예16 | 4.244 | 10 | 6.11 | 4.90 | 0.141 | 0.113 | 32 |
실시예17 | 4.253 | 10 | 6.13 | 4.91 | 0.140 | 0.114 | 34 |
실시예18 | 4.265 | 10 | 6.11 | 4.87 | 0.140 | 0.115 | 35 |
실시예19 | 4.255 | 10 | 6.19 | 4.85 | 0.140 | 0.114 | 32 |
실시예20 | 4.245 | 10 | 6.11 | 4.91 | 0.138 | 0.115 | 31 |
실시예21 | 4.247 | 10 | 6.09 | 4.79 | 0.139 | 0.115 | 33 |
실시예22 | 4.151 | 10 | 6.65 | 5.68 | 0.140 | 0.113 | 47 |
실시예23 | 4.109 | 10 | 6.69 | 5.60 | 0.141 | 0.112 | 48 |
실시예24 | 4.009 | 10 | 6.63 | 5.59 | 0.140 | 0.111 | 45 |
실시예25 | 4.151 | 10 | 6.70 | 5.63 | 0.140 | 0.110 | 47 |
비교예1 | 4.932 | 10 | 4.97 | 3.86 | 0.143 | 0.118 | 10 |
비교예2 | 4.657 | 10 | 5.30 | 4.24 | 0.141 | 0.115 | 19 |
비교예3 | 4.650 | 10 | 5.45 | 4.50 | 0.142 | 0.115 | 18 |
Op. V | mA / cm 2 | Cd / A | lm / w | CIEx | CIEy | LT95 | |
Example 1 | 4.441 | 10 | 5.85 | 4.79 | 0.141 | 0.120 | 22 |
Example 2 | 4.352 | 10 | 5.85 | 4.71 | 0.141 | 0.117 | 27 |
Example 3 | 4.343 | 10 | 5.88 | 4.76 | 0.142 | 0.115 | 30 |
Example 4 | 4.221 | 10 | 5.97 | 4.94 | 0.139 | 0.112 | 32 |
Example 5 | 4.212 | 10 | 6.00 | 4.92 | 0.138 | 0.113 | 35 |
Example 6 | 4.203 | 10 | 6.04 | 4.94 | 0.140 | 0.113 | 35 |
Example 7 | 4.295 | 10 | 6.07 | 4.99 | 0.140 | 0.113 | 37 |
Example 8 | 4.157 | 10 | 6.70 | 5.69 | 0.140 | 0.111 | 50 |
Example 9 | 4.130 | 10 | 6.63 | 5.64 | 0.139 | 0.112 | 47 |
Example 10 | 4.104 | 10 | 6.70 | 5.64 | 0.141 | 0.112 | 49 |
Example 11 | 4.100 | 10 | 6.59 | 5.67 | 0.142 | 0.112 | 49 |
Example 12 | 4.110 | 10 | 6.60 | 5.69 | 0.141 | 0.113 | 48 |
Example 13 | 4.109 | 10 | 6.63 | 5.65 | 0.142 | 0.113 | 50 |
Example 14 | 4.241 | 10 | 6.11 | 4.97 | 0.141 | 0.114 | 32 |
Example 15 | 4.214 | 10 | 6.19 | 4.80 | 0.141 | 0.113 | 35 |
Example 16 | 4.244 | 10 | 6.11 | 4.90 | 0.141 | 0.113 | 32 |
Example 17 | 4.253 | 10 | 6.13 | 4.91 | 0.140 | 0.114 | 34 |
Example 18 | 4.265 | 10 | 6.11 | 4.87 | 0.140 | 0.115 | 35 |
Example 19 | 4.255 | 10 | 6.19 | 4.85 | 0.140 | 0.114 | 32 |
Example 20 | 4.245 | 10 | 6.11 | 4.91 | 0.138 | 0.115 | 31 |
Example 21 | 4.247 | 10 | 6.09 | 4.79 | 0.139 | 0.115 | 33 |
Example 22 | 4.151 | 10 | 6.65 | 5.68 | 0.140 | 0.113 | 47 |
Example 23 | 4.109 | 10 | 6.69 | 5.60 | 0.141 | 0.112 | 48 |
Example 24 | 4.009 | 10 | 6.63 | 5.59 | 0.140 | 0.111 | 45 |
Example 25 | 4.151 | 10 | 6.70 | 5.63 | 0.140 | 0.110 | 47 |
Comparative Example 1 | 4.932 | 10 | 4.97 | 3.86 | 0.143 | 0.118 | 10 |
Comparative Example 2 | 4.657 | 10 | 5.30 | 4.24 | 0.141 | 0.115 | 19 |
Comparative Example 3 | 4.650 | 10 | 5.45 | 4.50 | 0.142 | 0.115 | 18 |
상기 표 1에 나타나는 바와 같이 본 발명의 정공수송층으로 평가한 실시예들은 비교예 1 내지 비교예 3에 비하여 모든 면에서 물성이 우수함을 확인할 수 있다. 특히 화학식 1-1, 화학식 1-2와 같이 인돌 3번 위치로 아릴기가 치환된 구조는 인돌 2번 및 인돌 2,3번 동시 치환보다 분자의 평면성이 뛰어나고, 박막내 분자배열이 우수하여 전하 모빌리티 증가와 화학적 안정성이 뛰어나 효율 및 소자 수명이 현저히 개선됨을 알 수 있다. 또한 화학식 1-6과 인돌과 아릴아민의 연결기가 페닐부이며, 플루오렌기가 2개 이상 치환된 경우 플루오렌기의 평면성으로 박막이 배열이 우수해지고 모빌리티가 증가해 효율 및 수명이 현저히 향상되는 것을 알 수 있다.As shown in Table 1, the Examples evaluated by the hole transport layer of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Examples 1 to 3. In particular, the structure in which the aryl group is substituted at the position of indole 3 as shown in Chemical Formulas 1-1 and 1-2 has better planarity of molecules than simultaneous substitution of indole 2 and indole 2,3, and excellent mobility of molecules in the thin film. It can be seen that the efficiency and device life are significantly improved due to the excellent increase and chemical stability. In addition, when the linking group of Formula 1-6, indole, and arylamine is a phenyl moiety, and when two or more fluorene groups are substituted, the planarity of the fluorene groups improves the arrangement of the thin films, increases mobility, and significantly improves efficiency and lifetime. Able to know.
유기발광소자(형광)의 보조층 평가예Example of evaluation of auxiliary layer of organic light emitting device (fluorescence)
실시예 26Example 26
인듐틴옥사이드(ITO)가 1500 Å 두께가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공주입층 HT01 600 Å, 제1정공수송층으로 화합물 31로 400 Å를 제막하였다. 다음으로 보조층으로 화합물 8로 150 Å을 제막한 후 상기 발광층으로 BH01:BD01 5%로 도핑하여 250 Å 제막하였다. 다음으로 전자전달층으로 ET01:Liq(1:1) 300 Å 제막한 후 LiF 10 Å, 알루미늄(Al) 1000 Å 제막하고, 이 소자를 글로브 박스에서 밀봉(Encapsulation)함으로써 유기발광소자를 제작하였다.A glass substrate coated with an indium tin oxide (ITO) 1500 Å thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes using an oxygen plasma. 600 cc of the hole injection layer HT01 and 400 cc of the compound 31 were formed into a first hole transport layer using an evaporator. Next, 150 Å of the compound 8 was formed as an auxiliary layer, and then 250 Å was formed by doping with 5% of BH01: BD01. Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막, which were encapsulated in a glove box to produce an organic light emitting device.
실시예 27Example 27
실시예 26과 같은 방법으로 정공수송층으로 화합물 32를 보조층으로 화합물 8을 사용하여 제막한 유기발광소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Example 26, using Compound 32 as an auxiliary layer and Compound 8 as an auxiliary layer.
실시예 28Example 28
실시예 26과 같은 방법으로 정공수송층으로 화합물 33을 보조층으로 화합물 8을 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 26, an organic light emitting device was manufactured by using the compound 33 as an auxiliary layer and the compound 8 as a hole transport layer.
실시예 29Example 29
실시예 26과 같은 방법으로 정공수송층으로 화합물 34를 보조층으로 화합물 8을 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 26, an organic light emitting device was manufactured by using the compound 34 as a hole transport layer and the compound 8 as an auxiliary layer.
실시예 30Example 30
실시예 26과 같은 방법으로 정공수송층으로 화합물 35를 보조층으로 화합물 8을 사용하여 제막한 유기발광소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Example 26, using Compound 35 as an auxiliary layer and Compound 8 as an auxiliary layer.
실시예 31Example 31
실시예 26과 같은 방법으로 정공수송층으로 화합물 36을 보조층으로 화합물 8을 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 26, an organic light emitting diode was manufactured by using Compound 36 as an auxiliary layer and Compound 8 as an auxiliary layer.
실시예 32Example 32
실시예 26과 같은 방법으로 정공수송층으로 화합물 37을 보조층으로 화합물 8을 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 26, an organic light emitting device was manufactured by using the compound 37 as a hole transport layer and the compound 8 as an auxiliary layer.
실시예 33Example 33
실시예 26과 같은 방법으로 정공수송층으로 화합물 38을 보조층으로 화합물 8을 사용하여 제막한 유기발광소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Example 26, using Compound 38 as an auxiliary layer and Compound 8 as an auxiliary layer.
비교예 4Comparative Example 4
상기 실시예 26의 정공수송층으로 화합물 24를 NPB로 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was manufactured in the same manner as in Example 26, except that Compound 24 was used as the NPB as the hole transport layer.
비교예 5Comparative Example 5
상기 실시예 26의 정공수송층으로 화합물 24를 Ref.3로 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was manufactured in the same manner as in Example 26, except that Compound 24 was used as Ref. 3 as the hole transport layer.
비교예 6Comparative Example 6
상기 실시예 26의 정공수송층으로 화합물 24를 Ref.4로 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was manufactured in the same manner as in Example 26, except that Compound 24 was used as Ref. 4 as the hole transport layer.
유기발광소자의 성능평가Performance Evaluation of Organic Light Emitting Diode
키슬리 2400 소스 메져먼트 유닛(Kiethley 2400 source measurement unit) 으로 전압을 인가하여 전자 및 정공을 주입하고 코니카 미놀타(Konica Minolta) 분광복사계(CS-2000)를 이용하여 빛이 방출될 때의 휘도를 측정함으로써, 실시예 및 비교예의 유기발광소자의 성능을 인가전압에 대한 전류 밀도 및 휘도를 대기압 조건하에 측정하여 평가하였으며, 그 결과를 표 2에 나타내었다. Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using the Konica Minolta Spectroradiometer (CS-2000) Thus, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 2.
표 2
TABLE 2
Op. V | mA/cm2 | Cd/A | lm/w | CIEx | CIEy | LT95 | |
실시예26 | 3.841 | 10 | 7.09 | 6.19 | 0.141 | 0.112 | 61 |
실시예27 | 3.852 | 10 | 7.00 | 6.11 | 0.141 | 0.111 | 60 |
실시예28 | 3.843 | 10 | 7.18 | 6.16 | 0.142 | 0.110 | 63 |
실시예29 | 3.821 | 10 | 7.05 | 6.14 | 0.139 | 0.112 | 69 |
실시예30 | 3.912 | 10 | 7.10 | 6.12 | 0.138 | 0.110 | 63 |
실시예31 | 3.903 | 10 | 7.04 | 6.24 | 0.140 | 0.113 | 61 |
실시예32 | 3.895 | 10 | 7.17 | 5.99 | 0.140 | 0.112 | 68 |
실시예33 | 3.897 | 10 | 7.10 | 6.09 | 0.140 | 0.110 | 66 |
비교예4 | 4.501 | 10 | 5.57 | 4.30 | 0.143 | 0.115 | 21 |
비교예5 | 4.272 | 10 | 5.98 | 4.90 | 0.141 | 0.115 | 31 |
비교예6 | 4.301 | 10 | 6.15 | 5.11 | 0.141 | 0.113 | 30 |
Op. V | mA / cm 2 | Cd / A | lm / w | CIEx | CIEy | LT95 | |
Example 26 | 3.841 | 10 | 7.09 | 6.19 | 0.141 | 0.112 | 61 |
Example 27 | 3.852 | 10 | 7.00 | 6.11 | 0.141 | 0.111 | 60 |
Example 28 | 3.843 | 10 | 7.18 | 6.16 | 0.142 | 0.110 | 63 |
Example 29 | 3.821 | 10 | 7.05 | 6.14 | 0.139 | 0.112 | 69 |
Example 30 | 3.912 | 10 | 7.10 | 6.12 | 0.138 | 0.110 | 63 |
Example 31 | 3.903 | 10 | 7.04 | 6.24 | 0.140 | 0.113 | 61 |
Example 32 | 3.895 | 10 | 7.17 | 5.99 | 0.140 | 0.112 | 68 |
Example 33 | 3.897 | 10 | 7.10 | 6.09 | 0.140 | 0.110 | 66 |
Comparative Example 4 | 4.501 | 10 | 5.57 | 4.30 | 0.143 | 0.115 | 21 |
Comparative Example 5 | 4.272 | 10 | 5.98 | 4.90 | 0.141 | 0.115 | 31 |
Comparative Example 6 | 4.301 | 10 | 6.15 | 5.11 | 0.141 | 0.113 | 30 |
상기 표 2에 나타나는 바와 같이 본 발명의 실시예들은 비교예 4 내지 비교예 6에 비하여 모든 면에서 물성이 우수함을 확인할 수 있다. 특히 정공수송층으로 인돌 2,3번 위치 아릴아민 치환된 화합물과 보조층으로 인돌N 치환된 아릴아민 화합물을 함께 사용할 경우 구동전압을 현저히 낮추고 효율 및 수명이 상승하는 결과를 얻었다. 이는 인돌의 2,3번 아릴아민 치환에 따라 정공수송층에 용이한 호모 및 빠른 홀 모빌리티를 가질 수 있고, 또한 인돌N 치환의 경우 보조층에 용이한 깊은 호모를 형성할 수 있어, 효율 및 수명이 크게 개선됨을 알 수 있다.As shown in Table 2, the embodiments of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Examples 4 to 6. In particular, when the indole 2-substituted arylamine-substituted compound as the hole transport layer and the indole N-substituted arylamine compound as the auxiliary layer were used together, the driving voltage was significantly lowered, and the efficiency and lifespan were increased. It can have easy homo and fast hole mobility in the hole transport layer in accordance with the 2,3 arylamine substitution of indole, and in the case of indole N substitution, it can form a deep homogeneous easily in the auxiliary layer. It can be seen that greatly improved.
유기발광소자(인광)의 보조층 평가예Evaluation example of auxiliary layer of organic light emitting device (phosphorescence)
실시예 34Example 34
인듐틴옥사이드(ITO)가 1500 Å 두께가 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 이송시킨 다음 산소 플라즈마를 이용하여 상기 기판을 5분간 세정 한 후 ITO 기판 상부에 열 진공 증착기(thermal evaporator)를 이용하여 정공주입층 HT01 600 Å, 정공수송층으로 화합물 37로 400 Å를 제막하였다. 다음으로 보조층으로 화합물 8로 250 Å을 제막한 후 상기 발광층으로 CzT:Ir(ppy)3 10%로 도핑하여 300 Å 제막하였다. 다음으로 전자전달층으로 ET01:Liq(1:1) 300 Å 제막한 후 LiF 10 Å, 알루미늄(Al) 1000 Å 제막하고, 이 소자를 글로브 박스에서 밀봉(Encapsulation)함으로써 유기발광소자를 제작하였다.A glass substrate coated with an indium tin oxide (ITO) 1500 Å thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and then the substrate is cleaned for 5 minutes using an oxygen plasma. Using a evaporator, a film injection layer HT01 600 Å, a hole transport layer to the film 37 to 400 제 was formed into a film. Next, 250 Å of Compound 8 was formed as an auxiliary layer, and then 300 Å was formed by doping with 10% CzT: Ir (ppy) 3 . Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막, which were encapsulated in a glove box to produce an organic light emitting device.
실시예 35Example 35
실시예 34와 같은 방법으로 보조층을 화합물 26으로 사용하여 제막한 유기발광소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Example 34, using the auxiliary layer as a compound 26 to form a film.
실시예 36Example 36
실시예 34와 같은 방법으로 보조층을 화합물 27로 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 34, an organic light emitting device was manufactured by using the auxiliary layer as a compound 27.
실시예 37Example 37
실시예 34와 같은 방법으로 보조층을 화합물 28로 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 34, an organic light-emitting device was manufactured by using the auxiliary layer as a compound 28.
실시예 38Example 38
실시예 34와 같은 방법으로 보조층을 화합물 29로 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 34, an organic light-emitting device was manufactured by using the auxiliary layer as a compound 29.
실시예 39Example 39
실시예 34와 같은 방법으로 보조층을 화합물 30으로 사용하여 제막한 유기발광소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Example 34, using the auxiliary layer as a compound 30.
실시예 40Example 40
실시예 34와 같은 방법으로 정공수송층을 NPB로 보조층을 화합물 30으로 사용하여 제막한 유기발광소자를 제작하였다.In the same manner as in Example 34, an organic light emitting diode was manufactured by using the hole transport layer as an NPB and the auxiliary layer as a compound 30.
비교예 7 Comparative Example 7
상기 실시예 34와 같은 방법으로 정공수송층을 NPB로 보조층을 Ref.1를 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was fabricated in the same manner as in Example 34, except that Ref. 1 was used as the hole transport layer and NPB.
비교예 8Comparative Example 8
상기 실시예 34와 같은 방법으로 정공수송층을 NPB로 보조층을 Ref.2를 사용한 것을 제외하고는 동일한 방법으로 소자를 제작하였다.A device was fabricated in the same manner as in Example 34, except that the hole transport layer was NPB, and the auxiliary layer was Ref.2.
유기발광소자의 성능평가Performance Evaluation of Organic Light Emitting Diode
키슬리 2400 소스 메져먼트 유닛(Kiethley 2400 source measurement unit) 으로 전압을 인가하여 전자 및 정공을 주입하고 코니카 미놀타(Konica Minolta) 분광복사계(CS-2000)를 이용하여 빛이 방출될 때의 휘도를 측정함으로써, 실시예 및 비교예의 유기발광소자의 성능을 인가전압에 대한 전류 밀도 및 휘도를 대기압 조건하에 측정하여 평가하였으며, 그 결과를 표 3에 나타내었다.Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using the Konica Minolta Spectroradiometer (CS-2000) Thus, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 3.
표 3
TABLE 3
Op. V | mA/cm2 | Cd/A | lm/w | CIEx | CIEy | LT95 | |
실시예34 | 4.341 | 10 | 51.40 | 39.19 | 0.338 | 0.622 | 108 |
실시예35 | 4.352 | 10 | 54.40 | 40.11 | 0.336 | 0.620 | 113 |
실시예36 | 4.343 | 10 | 54.29 | 40.16 | 0.335 | 0.621 | 115 |
실시예37 | 4.321 | 10 | 55.05 | 40.14 | 0.336 | 0.620 | 118 |
실시예38 | 4.312 | 10 | 56.00 | 41.12 | 0.338 | 0.621 | 127 |
실시예39 | 4.303 | 10 | 56.04 | 41.24 | 0.335 | 0.621 | 125 |
실시예40 | 4.303 | 10 | 45.54 | 34.24 | 0.337 | 0.622 | 83 |
비교예7 | 4.731 | 10 | 38.60 | 25.30 | 0.340 | 0.623 | 43 |
비교예8 | 4.722 | 10 | 39.34 | 27.90 | 0.340 | 0.623 | 48 |
Op. V | mA / cm 2 | Cd / A | lm / w | CIEx | CIEy | LT95 | |
Example 34 | 4.341 | 10 | 51.40 | 39.19 | 0.338 | 0.622 | 108 |
Example 35 | 4.352 | 10 | 54.40 | 40.11 | 0.336 | 0.620 | 113 |
Example 36 | 4.343 | 10 | 54.29 | 40.16 | 0.335 | 0.621 | 115 |
Example 37 | 4.321 | 10 | 55.05 | 40.14 | 0.336 | 0.620 | 118 |
Example 38 | 4.312 | 10 | 56.00 | 41.12 | 0.338 | 0.621 | 127 |
Example 39 | 4.303 | 10 | 56.04 | 41.24 | 0.335 | 0.621 | 125 |
Example 40 | 4.303 | 10 | 45.54 | 34.24 | 0.337 | 0.622 | 83 |
Comparative Example 7 | 4.731 | 10 | 38.60 | 25.30 | 0.340 | 0.623 | 43 |
Comparative Example 8 | 4.722 | 10 | 39.34 | 27.90 | 0.340 | 0.623 | 48 |
상기 표 3에 나타나는 바와 같이 본 발명의 실시예들은 비교예 7 및 비교예 8에 비하여 모든 면에서 물성이 우수함을 확인할 수 있다. 특히 인광소자의 보조층으로 인돌N과 아릴아민사이 연결기가 페닐부 치환 및 meta, ortho 치환된 화합물의 실시예의 경우 짧은 공액길이로 깊은 호모를 형성할 수 있는 넓은 밴드갭을 가질 수 있고, 또한 높은 삼중항에너지로 인광발광으로부터 엑시톤 차단이 용이하여 효율 상승 및 수명 개선 효과가 현저히 개선됨을 알 수 있다.As shown in Table 3, the embodiments of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Example 7 and Comparative Example 8. In particular, in the case of the compound in which the linking group between indole N and arylamine is substituted with phenyl moiety and meta, ortho as an auxiliary layer of the phosphor, it may have a wide band gap capable of forming a deep homo with short conjugation length. It can be seen that the triplet energy is easy to block excitons from phosphorescent light emission, thereby improving efficiency and improving lifespan.
본 발명의 화합물은 청색 및 인광용 유기발광소자에 적용시 정공주입 및 정공전달 특성이 우수하고, 동시에 전자차단 특성이 우수하며, 높은 삼중항 에너지 및 높은 Tg를 구현할 수 있으며, 낮은 구동전압, 저소비전력, 고효율 및 장수명을 가지게 할 수 있다.The compound of the present invention has excellent hole injection and hole transport characteristics when applied to the organic light emitting device for blue and phosphorescence, at the same time excellent in the electron blocking characteristics, high triplet energy and high Tg, low drive voltage, low consumption It can have power, high efficiency and long life.
Claims (9)
- 하기 화학식 1로 표시되는 화합물 :Compound represented by the following formula (1):[화학식 1][Formula 1]상기 식에서,Wherel, m, n, o는 각각 독립적으로 1 내지 3으로부터 선택되는 정수이며, Ar은 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,l, m, n, o are each independently an integer selected from 1 to 3, Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,R1, R2, R3, R4, R5, 및 R6은 각각 독립적으로 수소; 중수소; 할로겐; 아미노기; 니트릴기; 니트로기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
- 제1항에 있어서,The method of claim 1,하기 화학식 1-1 내지 1-7 중 어느 하나로 표시되는 화합물Compound represented by any one of the following formula 1-1 to 1-7[화학식 1-1][Formula 1-1][화학식 1-2][Formula 1-2][화학식 1-3][Formula 1-3][화학식 1-4][Formula 1-4][화학식 1-5][Formula 1-5][화학식 1-6][Formula 1-6][화학식 1-7][Formula 1-7]상기 화학식들에서 n, p, q 및 r은 각각 독립적으로 1 내지 3으로부터 선택되는 정수이며,N, p, q and r in the formulas are each independently an integer selected from 1 to 3,Ar1 및 Ar2는 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,Ar 1 and Ar 2 are each independently a C 6-50 aryl group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro groups; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,R1, R5, R6, R7, R8, R9, R10, R11, R12, 및 R13은 각각 독립적으로 수소; 중수소; 할로겐; 아미노기; 니트릴기; 니트로기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이며, R 1 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,R5, R6, R7, R8, R9, R10, Ar1, Ar2는 인접한 기 또는 서로 고리를 형성할 수 있다.R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , Ar 1 , Ar 2 may form an adjacent group or a ring with each other.
- 제1전극, 제2전극 및 두 전극 사이에 제1항 기재의 화학식 1로 표시되는 화합물을 함유하는 1층 이상의 유기물층을 포함하는 유기발광소자.An organic light emitting device comprising at least one organic layer containing a compound represented by the formula (1) of claim 1 between the first electrode, the second electrode and the two electrodes.
- 제4항에 있어서,The method of claim 4, wherein제1전극과 제2전극 사이 적어도 발광층을 포함하는 일층 또는 복수층을 포함하는 유기 박막층이 협지되어 있는 유기발광소자이며, 제1전극과 발광층 사이에 적어도 1층이 제2항 내지 3항 중 어느 한 항에 기재된 화합물을 유기층으로 함유하는 유기발광소자.An organic light emitting device in which an organic thin film layer including at least one light emitting layer or a plurality of layers is sandwiched between a first electrode and a second electrode, and at least one layer is disposed between the first electrode and the light emitting layer. An organic light emitting device comprising the compound of claim 1 as an organic layer.
- 제5항에 있어서,The method of claim 5,제1전극과 발광층 사이에 발광층에 접해있는 1층이, 제2항 기재의 화학식 1-1, 화학식 1-2, 화학식 1-7로 기재된 화합물을 유기층으로 함유하는 유기발광소자.An organic light emitting device in which one layer, which is in contact with the light emitting layer between the first electrode and the light emitting layer, contains the compounds of Formulas 1-1, 1-2, and 1-7 as described in claim 2 as an organic layer.
- 제5항에 있어서,The method of claim 5,제1전극과 발광층 사이에 적어도 1층의 정공수송층을 구비하고, 상기 정공수송층과 발광층 사이에 화학식 1로 표시되는 화합물을 포함하는 보조층을 구비한 유기발광소자.An organic light emitting device comprising at least one hole transport layer between a first electrode and a light emitting layer, and an auxiliary layer including a compound represented by Formula 1 between the hole transport layer and the light emitting layer.
- 제7항에 있어서,The method of claim 7, wherein상기 정공수송층은 하기 화학식 2로 표시되는 화합물을 포함하는 유기발광소자.The hole transport layer is an organic light emitting device comprising a compound represented by the following formula (2).[화학식 2][Formula 2]상기 화학식에서,In the above formula,l, m, n, o는 각각 독립적으로 1 내지 3으로부터 선택되는 정수이며, Ar은 각각 독립적으로 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이고,l, m, n, o are each independently an integer selected from 1 to 3, Ar is each independently a C 6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino, nitrile, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group,R1, R2, R3, R4, 및 R5는 각각 독립적으로 수소; 중수소; 할로겐; 아미노기; 니트릴기; 니트로기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알킬기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알케닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-30의 알키닐기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C1-30의 알콕시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-30의 아릴옥시기; 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C6-50의 아릴기; 또는 중수소, 할로겐, 아미노기, 니트릴기, 니트로기로 치환되거나 치환되지 않은 C2-50의 헤테로아릴기이다.R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; C 1-30 alkyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C 2-30 alkenyl groups unsubstituted or substituted with deuterium, halogen, amino, nitrile, and nitro groups; C 2-30 alkynyl group which is unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; A C 1-30 alkoxy group unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-30 aryloxy group which is unsubstituted or substituted with deuterium, halogen, amino, nitrile or nitro group; C 6-50 aryl group which is optionally substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C 2-50 heteroaryl group unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group.
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