EP2004774A1 - Organic electroluminescent compounds and display device using the same as an electrolu¢ minescent material - Google Patents
Organic electroluminescent compounds and display device using the same as an electrolu¢ minescent materialInfo
- Publication number
- EP2004774A1 EP2004774A1 EP07708585A EP07708585A EP2004774A1 EP 2004774 A1 EP2004774 A1 EP 2004774A1 EP 07708585 A EP07708585 A EP 07708585A EP 07708585 A EP07708585 A EP 07708585A EP 2004774 A1 EP2004774 A1 EP 2004774A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chemical formula
- mmol
- compound
- electroluminescent
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 66
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- GHGZVWOTJDLREY-UHFFFAOYSA-N 2-(1,3-benzoxazol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2O1 GHGZVWOTJDLREY-UHFFFAOYSA-N 0.000 description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 9
- DIMYTQPLZWDZFE-UHFFFAOYSA-L beryllium sulfate tetrahydrate Chemical compound [Be+2].O.O.O.O.[O-]S([O-])(=O)=O DIMYTQPLZWDZFE-UHFFFAOYSA-L 0.000 description 9
- 239000004246 zinc acetate Substances 0.000 description 9
- MVVGSPCXHRFDDR-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2S1 MVVGSPCXHRFDDR-UHFFFAOYSA-N 0.000 description 8
- PMVRBPKKJNHTLA-UHFFFAOYSA-N 2-(1-phenylbenzimidazol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2N1C1=CC=CC=C1 PMVRBPKKJNHTLA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- HPDNGBIRSIWOST-UHFFFAOYSA-N 2-pyridin-2-ylphenol Chemical compound OC1=CC=CC=C1C1=CC=CC=N1 HPDNGBIRSIWOST-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- -1 α-naphthyl Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G08—SIGNALLING
- G08G—TRAFFIC CONTROL SYSTEMS
- G08G1/00—Traffic control systems for road vehicles
- G08G1/09—Arrangements for giving variable traffic instructions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
-
- G—PHYSICS
- G08—SIGNALLING
- G08G—TRAFFIC CONTROL SYSTEMS
- G08G1/00—Traffic control systems for road vehicles
- G08G1/005—Traffic control systems for road vehicles including pedestrian guidance indicator
-
- G—PHYSICS
- G08—SIGNALLING
- G08G—TRAFFIC CONTROL SYSTEMS
- G08G1/00—Traffic control systems for road vehicles
- G08G1/07—Controlling traffic signals
- G08G1/075—Ramp control
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/186—Metal complexes of the light metals other than alkali metals and alkaline earth metals, i.e. Be, Al or Mg
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the present invention relates to an electroluminescent compound comprised of a metal complex, which shows excellent electrical conductivity and electroluminescent property with high efficiency, and an electroluminescent device comprising the same as a host material.
- iridium(i ⁇ ) complexes are widely known as phosphorescent dopants, including (acac)Ir(btp) , Ir(ppy) and Firpic, as the red, green and blue one, re- spectively.
- phosphorescent dopants including (acac)Ir(btp) , Ir(ppy) and Firpic, as the red, green and blue one, re- spectively.
- a lot of phosphorescent materials have been investigated in Japan and Europe and America, so that development of further improved phosphorescent materials is expected.
- CBP As a host material for phosphorescent light emitting material, CBP is most widely known up to the present, and OLEDs having high efficiency to which a hole blocking layer such as BCP and BAIq, etc. has been applied have been known.
- Pioneer (Japan) reported OLEDs having high efficiency using a BAIq derivative as the host.
- the materials in prior art are advantageous in view of light emitting property, they have low glass transition temperature and very poor thermal stability, so that the materials tend to be changed during high temperature vacuum- vapor-deposition process. In addition, they are not satisfactory in terms of lifetime of an OLED device, so that development of host materials having better material stability and more excellent EL performance is required.
- [10] According to the present invention, developed are metal complex materials exhibiting excellent material stability, excellent electrical conductivity and luminous property of high efficiency as compared to conventional materials.
- An aromatic ring containing a hetero atom or a side chain substituent hetero atom containing non- bonding electron pair has a property to readily coordinate to metal. Such a coordination shows very stable property in electrochemical aspect, which has been known widely.
- the present invention developed various ligands, prepared metal complexes having above-mentioned properties and applied them as host materials.
- the object of the invention is to overcome the disadvantages as described above, and to provide mixed type ligand-metal complexes as electroluminescent materials, which are very excellent in luminous and physical properties as compared to conventional organic host materials or aluminum complexes.
- Another object of the invention is to provide an electroluminescent device containing the electroluminescent compound thus prepared as a host material.
- the present invention relates to an electroluminescent compound comprised represented by Chemical Formula 1 and an electroluminescent device containing the same as a host material.
- M is a divalent metal
- X is O, S or Se
- a ring is oxazole, thiazole, imidazole, oxadiazole, thiadiazole, benzoxazole, benzothiazole, benzimidazole, pyridine or quinoline, and the pyridine or quinoline may form a fused ring with R via chemical bond, and said A ring may have additional substituent such as C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s); B ring is pyridine or quinoline, and said B ring may have additional substituent such as C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s); and R independently represents hydrogen or C1-C5 alkyl.
- the ligands L and L are different each other, and may be selected from those represented by one of the following structural formulas:
- M is divalent metal
- X is O, S or Se
- Y is O, S or N-R 4
- Z is CH or N
- R 2 and R independently represent hydrogen, phenyl or naphthyl with or without substituent(s); and R 4 is C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s).
- M is preferably selected from Be, Zn, Mg, Cu and Ni, and
- the ligands L and L are preferably selected from those represented by one of the following structural formulas:
- electroluminescent compounds of Chemical Formula 1 according to the present invention may be exemplified as the compounds represented by one of the Chemical Formulas 1-1 through 1-18:
- Example 1 [72] Fig. 2 Luminance-applied voltage characteristic of the OLED device prepared according to Comparative Example 1 [73] Fig. 3 Luminous efficiency-luminance characteristic of the OLED device prepared according to Comparative Example 1 [74] Fig. 4 Luminance-applied voltage characteristic of the OLED device prepared according to Example 1 [75] Fig. 5 Luminous efficiency-luminance characteristic of the OLED device prepared according to Example 1 [76] [77]
- OLED devices having the structure employing the host materials according to the present invention were manufactured.
- a transparent electrode ITO thin film (15 ⁇ /D) obtained from a glass for OLED was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, subsequently, and stored in isopronanol before use.
- an ITO substrate was equipped in a substrate folder of vacuum vapor-deposit device, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) represented by following structural formula was placed in a cell of the vacuum vapor- deposit device, which was then ventilated up to 10 " torr of vacuum in the chamber. Electric current was applied to the cell to evaporate 2-TNATA to vapor-deposit a hole injection layer having 40 nm of thickness on the ITO substrate.
- 2-TNATA 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine
- NPB N,N'-bis( ⁇ -naphthyl)-N,N'-diphenyl-4,4'-diamine
- an electroluminescent layer was vapor-deposited thereon as follows.
- a compound selected from Compounds 1-1 through 1-18 which was purified via sublimation in vacuo under 10 " torr, as a host material, and in another cell, charged was (NPy) Ir(acac).
- the two materials were evaporated at different rates to give doping of 4-10 mol%, to vapor-deposit light emitting layer having 30 nm of thickness on the hole transport layer.
- FIG. 1 an EL spectrum of Comparative Example 1 wherein (NPy) Ir(acac) compound (emitting orange-red light) was used as an electroluminescent material and BAIq as a host material, shows maximum EL peak at about 624 nm. From Fig. 2 showing luminance-applied voltage characteristic of Comparative Example 1, it is confirmed that driving voltage of the device of Comparative Example 1 is about 5 V, and the driving voltage at 1,000 cd/m (standard of Table 1) was 7.49 V. From Fig.
- Fig. 4 which shows luminance-applied voltage characteristic of the OLED device prepared according to Example 14, the device of Example 14 employing the electroluminescent compound according to the present invention showed driving voltage of about 3 V, and luminance of about 1,000 cd/m at about 4.86 V; the result shows decrease of driving voltage by at least 2.6 V as compared to the device of Comparative Example 1.
- Fig. 5 which shows luminous efficiency-luminance characteristic of the device according to Example 14, it showed luminous efficiency of about 6.67 cd/A at 1,000 cd/m of luminance; which shows higher luminous efficiency by about 0.5 cd/A as compared to the device of Comparative Example 1 at the same luminance.
- the device employing an electroluminescent compound according to the present invention as the host material lowers the driving voltage to induce increase of power efficiency by 0.5 ⁇ 2.0 lm/W, thereby improving the power consumption.
- the electroluminescent compounds according to the present invention are employed in OLED devices as a host material, driving voltage is noticeably lowered and power efficiency is considerably increased.
- the compounds in the present invention are suitable for an OLED material in next generation, and expected to greatly contribute for the development of large size display adopted OLED.
Abstract
The present invention relates to an organic electroluminescent compound represented by Chemical Formula 1 and an electroluminescent device containing the same as an electroluminescent material. The electroluminescent compound according to the present invention is advantageous in that it prominently lowers the driving voltage and considerably enhances the power efficiency when being used as a host material for an OLED device.
Description
Description
ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE
USING THE SAME
Technical Field
[1] The present invention relates to an electroluminescent compound comprised of a metal complex, which shows excellent electrical conductivity and electroluminescent property with high efficiency, and an electroluminescent device comprising the same as a host material.
[2]
Background Art [3] The most important factor to determine luminous efficiency in an OLED is the electroluminescent characteristics of electroluminescent material. Though a fluorescent material has been widely used as an electroluminescent material up to the present, a development of phosphorescent material is one of the best solutions to improve luminous efficiency theoretically up to four times in view of electroluminescent mechanism.
[4] Up to now, iridium(iπ) complexes are widely known as phosphorescent dopants, including (acac)Ir(btp) , Ir(ppy) and Firpic, as the red, green and blue one, re- spectively. In particular, a lot of phosphorescent materials have been investigated in Japan and Europe and America, so that development of further improved phosphorescent materials is expected.
[5]
(acac)lr(btp);. !r(PPy)3 Firpic
[6] As a host material for phosphorescent light emitting material, CBP is most widely known up to the present, and OLEDs having high efficiency to which a hole blocking layer such as BCP and BAIq, etc. has been applied have been known. Pioneer (Japan) reported OLEDs having high efficiency using a BAIq derivative as the host.
CBP BCP
[8]
BAIq BAIq DERIVATIVE
[9] Though the materials in prior art are advantageous in view of light emitting property, they have low glass transition temperature and very poor thermal stability, so that the materials tend to be changed during high temperature vacuum- vapor-deposition process. In addition, they are not satisfactory in terms of lifetime of an OLED device, so that development of host materials having better material stability and more excellent EL performance is required.
[10] According to the present invention, developed are metal complex materials exhibiting excellent material stability, excellent electrical conductivity and luminous property of high efficiency as compared to conventional materials. An aromatic ring containing a hetero atom or a side chain substituent hetero atom containing non- bonding electron pair has a property to readily coordinate to metal. Such a coordination shows very stable property in electrochemical aspect, which has been known widely. The present invention developed various ligands, prepared metal complexes having above-mentioned properties and applied them as host materials.
[H] A number of conventional complexes of such type have been researched since the middle of 1990's. However, those materials have been applied merely as an electroluminescent material, but rarely as a host material.
[12]
Disclosure of Invention Technical Problem
[13] The object of the invention is to overcome the disadvantages as described above, and to provide mixed type ligand-metal complexes as electroluminescent materials, which are very excellent in luminous and physical properties as compared to conventional organic host materials or aluminum complexes. Another object of the
invention is to provide an electroluminescent device containing the electroluminescent compound thus prepared as a host material. [14]
Technical Solution
[15] The present invention relates to an electroluminescent compound comprised represented by Chemical Formula 1 and an electroluminescent device containing the same as a host material.
[16]
[17] [Chemical Formula 1 ]
[18] L1L2M
1 9
[19] In the formula, L and L are different each other, and selected from those represented by one of the following structural formulas: [20]
[21] wherein M is a divalent metal; X is O, S or Se; A ring is oxazole, thiazole, imidazole, oxadiazole, thiadiazole, benzoxazole, benzothiazole, benzimidazole, pyridine or quinoline, and the pyridine or quinoline may form a fused ring with R via chemical bond, and said A ring may have additional substituent such as C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s); B ring is pyridine or quinoline, and said B ring may have additional substituent such as C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s); and R independently represents hydrogen or C1-C5 alkyl.
[22]
1 9
[23] In the Chemical Formula 1 as described above, the ligands L and L are different each other, and may be selected from those represented by one of the following structural formulas:
[24]
[25] wherein, M is divalent metal; X is O, S or Se; Y is O, S or N-R 4 , Z is CH or N; R 2 and R independently represent hydrogen, phenyl or naphthyl with or without substituent(s); and R 4 is C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s).
[26] In Chemical Formula 1, M is preferably selected from Be, Zn, Mg, Cu and Ni, and
1 9 the ligands L and L are preferably selected from those represented by one of the following structural formulas:
[27]
[28] wherein, X is O, S or Se. [29] The ligands L and L of the electroluminescent compounds according to the present invention are exemplified as follows:
[30]
[31] wherein, X is O or S.
[32] Specifically, the electroluminescent compounds of Chemical Formula 1 according to the present invention may be exemplified as the compounds represented by one of the Chemical Formulas 1-1 through 1-18:
[33] [Chemical Formula 1-1] [34]
[35] [Chemical Formula 1-2] [36]
[37] [Chemical Formula 1-3] [38]
[39] [Chemical Formula 1-4] [40]
[41] [Chemical Formula 1-5] [42]
[43] [Chemical Formula 1-6] [44]
[45] [Chemical Formula 1-7] [46]
[47] [Chemical Formula 1-8] [48]
[49] [Chemical Formula 1-9]
[50]
[51] [Chemical Formula 1-10] [52]
[53] [Chemical Formula 1-11] [54]
[55] [Chemical Formula 1-12] [56]
[57] [Chemical Formula 1-13]
[59] [Chemical Formula 1-14] [60]
[61] [Chemical Formula 1-15] [62]
[63] [Chemical Formula 1-16] [64]
[65] [Chemical Formula 1-17] [66]
[67] [Chemical Formula 1-18]
[68]
[69]
Brief Description of the Drawings
[70]
[71] Fig. 1 EL spectrum of the OLED device prepared according to Comparative
Example 1 [72] Fig. 2 Luminance-applied voltage characteristic of the OLED device prepared according to Comparative Example 1 [73] Fig. 3 Luminous efficiency-luminance characteristic of the OLED device prepared according to Comparative Example 1 [74] Fig. 4 Luminance-applied voltage characteristic of the OLED device prepared according to Example 1 [75] Fig. 5 Luminous efficiency-luminance characteristic of the OLED device prepared according to Example 1 [76] [77] Other and further objects, features and advantages of the invention will appear more fully from the following description. [78] [79]
Mode for the Invention [80] The present invention is further described with respect to the electroluminescent compounds according to the present invention, a process for preparing the same and
the electroluminescent properties of the device employing the same, by referring to representative compounds according to the present invention, which are provided for illustration only and are not intended to be limiting in any way. [81] [Preparation Example 1] Compound of Chemical Formula 1-1
[82] In 50 mL of methanol, 2-pyridin-2-yl-phenol (1.0 g, 5.84 mmol) was dissolved, and
10 mL of aqueous IM sodium hydroxide solution was added thereto. To the mixed solution, a solution of beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol) in 10 mL of aqueous methanol (methanol 7 mL: water 3 mL) was added dropwise, and the resultant mixture was stirred at ambient temperature for 2 hours. After completing the stirring, 2-hydroxy-phenyl benzoxazole (1.54 g, 7.30 mmol) dissolved in 50 mL of methanol was slowly added. The reaction solution was then stirred at ambient temperature for 2 hours. The temperature of the solution was raised to 50°C, and the solution was stirred for 10 hours.
[83] After completion of the stirring, the precipitate produced was filtered, washed with water (50 mL) and acetone (50 mL), and dried to obtain the title compound, Compound (1-1) (0.80 g, 2.04 mmol, yield: 34%). [84] MS/FAB : 391 (found), 391.43 (calculated)
[85] EA: C 73.55%, H 4.59%, N 7.05%, O 12.41%
[86] [Preparation Example 2] Compound of Chemical Formula 1-2
[87] In 50 mL of methanol, 2-pyridin-2-yl-phenol (1.0 g, 5.84 mmol) was dissolved, and
10 mL of aqueous IM sodium hydroxide solution was added thereto. To the mixed solution, zinc acetate (0.95 g, 5.18 mmol) dissolved in methanol (10 mL) was added dropwise, and the resultant mixture was stirred at ambient temperature for 2 hours. After completing the stirring, 2-hydroxy-phenyl benzoxazole (1.50 g, 7.10 mmol) dissolved in 50 mL of methanol was slowly added. The reaction mixture was then stirred at ambient temperature for 10 hours.
[88] After completion of the stirring, the precipitate produced was filtered, washed with water (50 mL) and acetone (50 mL), and dried to obtain the title compound, Compound (1-2) (0.72 g, 1.61 mmol, yield: 27%). [89] MS/FAB: 447(found), 447.79(calculated)
[90] EA: C 64.22%, H 4.01%, N 6.05%, O 10.95%
[91] [Preparation Example 3] Compound of Chemical Formula 1-3
[92] The same procedure as Preparation Example 1 was carried out by using
2-hydroxy-phenyl benzoxazole (1.23 g, 5.82 mmol), 10-hydroxybenzo[/ϊ]quinoline (1.48 g, 7.58 mmol) and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-3) (0.35 g, 0.84 mmol, yield: 14%). [93] MS/FAB: 415(found), 415.46(calculated)
[94] EA: C 75.02%, H 4.27%, N 6.64%, O 11.65%
[95] [Preparation Example 4] Compound of Chemical Formula 1-4
[96] The same procedure as Preparation Example 2 was carried out by using
2-hydroxy-phenyl benzoxazole (1.23 g, 5.82 mmol), 10-hydroxybenzo[/ϊ]quinoline (1.48 g, 7.58 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-4) (0.52 g, 1.10 mmol, yield: 19%). [97] MS/FAB : 471 (found), 471.81 (calculated)
[98] EA: C 66.08%, H 3.79%, N 5.84%, O 10.30%
[99] [Preparation Example 5] Compound of Chemical Formula 1-5
[100] The same procedure as Preparation Example 1 was carried out by using
2-hydroxy-phenyl benzoxazole (1.23 g, 5.82 mmol), 2-hydroxy-phenyl benzothiazole (1.72 g, 7.57 mmol) and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-5) (0.96 g, 2.15 mmol, yield: 37%). [101] MS/FAB: 447(found), 447.52(calculated)
[102] EA: C 69.68%, H 4.01%, N 6.16%, O 10.85% S 7.05%
[103] [Preparation Example 6] Compound of Chemical Formula 1-6
[104] The same procedure as Preparation Example 2 was carried out by using
2-hydroxy-phenyl benzoxazole (1.23 g, 5.82 mmol), 2-hydroxy-phenyl benzothiazole (1.72 g, 7.57 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-6) (1.36 g, 2.70 mmol, yield: 46%). [105] MS/FAB: 503(found), 503.88(calculated)
[106] EA: C 61.88%, H 3.54%, N 5.46%, O 9.73%, S 6.26%
[107] [Preparation Example 7] Compound of Chemical Formula 1-7
[108] The same procedure as Preparation Example 1 was carried out by using
2-hydroxy-phenyl benzothiazole (1.32 g, 5.80 mmol), 2-pyridine-2-yl-phenol (1.30 g, 7.59 mmol) and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-7) (0.59 g, 1.45 mmol, yield: 25%). [109] MS/FAB: 407(found), 407.50(calculated)
[110] EA: C 70.64%, H 4.35%, N 6.76%, O 7.96%, S 7.75%
[111] [Preparation Example 8] Compound of Chemical Formula 1-8
[112] The same procedure as Preparation Example 2 was carried out by using
2-hydroxy-phenyl benzothiazole (1.32 g, 5.80 mmol), 2-pyridine-2-yl-phenol (1.30 g, 7.59 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-8) (0.83 g, 1.79 mmol, yield: 31%). [113] MS/FAB: 463(found), 463.86(calculated)
[114] EA: C 62.04%, H 3.82%, N 5.98%, O 7.02%, S 6.83%
[115] [Preparation Example 9] Compound of Chemical Formula 1-9
[116] The same procedure as Preparation Example 1 was carried out by using
2-hydroxy-phenyl benzothiazole (1.32 g, 5.80 mmol), 10-hydroxybenzo[/ϊ]quinoline
(1.48 g, 7.58 mmol) instead of 2-hydroxy-phenyl benzoxazole, and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-9) (0.98 g, 2.27 mmol, yield: 39%).
[117] MS/FAB: 431(found), 431.52(calculated)
[118] EA: C 72.22%, H 4.10%, N 6.40%, O 7.62%, S 7.33%
[119] [Preparation Example 10] Compound of Chemical Formula 1-10
[120] The same procedure as Preparation Example 4 was carried out by using
2-hydroxy-phenyl benzothiazole (1.32 g, 5.80 mmol), 10-hydroxybenzo[/ϊ]quinoline (1.48 g, 7.58 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-10) (1.22 g, 2.50 mmol, yield: 43%). [121] MS/FAB: 487(found), 487.88(calculated)
[122] EA: C 63.93%, H 3.65%, N 5.64%, O 6.70%, S 6.44%
[123] [Preparation Example 11] Compound of Chemical Formula 1-11
[124] The same procedure as Preparation Example 1 was carried out by using
2-hydroxy-phenyl benzoxazole (1.23 g, 5.82 mmol),
2-(l-phenyl-lH-benzoimidazol-2-yl)-phenol (2.17 g, 7.58 mmol) and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-11) (0.56 g, 1.11 mmol, yield: 19%).
[125] MS/FAB: 506(found), 506.57(calculated)
[126] EA: C 75.67%, H 4.50%, N 8.20%, O 9.68%
[127] [Preparation Example 12] Compound of Chemical Formula 1-12
[128] The same procedure as Preparation Example 2 was carried out by using
2-hydroxy-phenyl benzoxazole (1.23 g, 5.82 mmol),
2-(l-phenyl-lH-benzoimidazol-2-yl)-phenol (2.17 g, 7.58 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-12) (0.72 g, 1.28 mmol, yield: 22%).
[129] MS/FAB: 562(found), 562.93(calculated)
[130] EA: C 68.16%, H 4.05%, N 7.36%, O 8.68%
[131] [Preparation Example 13] Compound of Chemical Formula 1-13
[132] The same procedure as Preparation Example 1 was carried out by using
2-(l-phenyl-lH-benzoimidazol-2-yl)phenol (1.67 g, 5.83 mmol), 2-pyridin-2-yl-phenol (1.30 g, 7.59 mmol) and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-13) (0.84 g, 1.80 mmol, yield: 31%). [133] MS/FAB : 466(found), 466.55(calculated)
[134] EA: C 77.08%, H 4.87%, N 8.90%, O 6.98%
[135] [Preparation Example 14] Compound of Chemical Formula 1-14
[136] The same procedure as Preparation Example 2 was carried out by using
2-(l-phenyl-lH-benzimidazol-2-yl)-phenol (1.67 g, 5.83 mmol),
2-pyridine-2-yl-phenol (1.30 g, 7.59 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-14) (0.88 g, 1.68 mmol, yield: 29%). [137] MS/FAB : 522(found), 522.91 (calculated)
[138] EA: C 68.81%, H 4.33%, N 7.92%, O 6.32%
[139] [Preparation Example 15] Compound of Chemical Formula 1-15
[140] The same procedure as Preparation Example 1 was carried out by using
2-(l-phenyl-lH-benzoimidazol-2-yl)-phenol (1.67 g, 5.83 mmol), 10-hydroxybenzo[/ϊ] quinoline (1.50 g, 7.68 mmol) and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-15) (0.26 g, 0.53 mmol, yield: 9%). [141] MS/FAB: 490(found), 490.57(calculated)
[142] EA: C 78.20%, H 4.68%, N 8.42%, O 6.70%
[143] [Preparation Example 16] Compound of Chemical Formula 1-16
[144] The same procedure as Preparation Example 2 was carried out by using
2-(l-phenyl-lH-benzimidazol-2-yl)-phenol (1.67 g, 5.83 mmol), 10-hydroxybenzo[/ϊ] quinoline (1.50 g, 7.68 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-16) (0.42 g, 0.77 mmol, yield: 13%). [145] MS/FAB: 546(found), 546.93(calculated)
[146] EA: C 70.13%, H 4.16%, N 7.58%, O 5.98%
[147] [Preparation Example 17] Compound of Chemical Formula 1-17
[148] The same procedure as Preparation Example 1 was carried out by using
2-hydroxy-phenyl benzothiazole (1.32 g, 5.80 mmol),
2-(l-phenyl-lH-benzoimidazol-2-yl)-phenol (2.17 g, 7.58 mmol) and beryllium sulfate tetrahydrate (1.05 g, 5.93 mmol), to obtain the title compound, Compound (1-17) (0.64 g, 1.22 mmol, yield: 21%).
[149] MS/FAB: 522(found), 522.64(calculated)
[150] EA: C 73.42%, H 4.34%, N 7.97%, O 6.25%, S 6.04%
[151] [Preparation Example 18] Compound of Chemical Formula 1-18
[152] The same procedure as Preparation Example 2 was carried out by using
2-hydroxy-phenyl benzothiazole (1.32 g, 5.80 mmol),
2-(l-phenyl-lH-benzimidazol-2-yl)-phenol (2.17 g, 7.58 mmol) and zinc acetate (0.95 g, 5.18 mmol), to obtain the title compound, Compound (1-18) (0.94 g, 1.62 mmol, yield: 28%).
[153] MS/FAB: 578(found), 578.99(calculated)
[154] EA: C 66.22%, H 3.94%, N 7.16%, O 5.70%, S 5.49%
[155] [Example 1 - 18] Manufacture of OLED device by using the compounds according to the present invention
[156] OLED devices having the structure employing the host materials according to the present invention were manufactured.
[157] First, a transparent electrode ITO thin film (15 Ω/D) obtained from a glass for OLED was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, subsequently, and stored in isopronanol before use.
[158] Then, an ITO substrate was equipped in a substrate folder of vacuum vapor-deposit device, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) represented by following structural formula was placed in a cell of the vacuum vapor- deposit device, which was then ventilated up to 10" torr of vacuum in the chamber. Electric current was applied to the cell to evaporate 2-TNATA to vapor-deposit a hole injection layer having 40 nm of thickness on the ITO substrate.
[159]
2-TNATA
[160] Then, to another cell of the vacuum vapor-deposit device, charged was N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB), and electric current was applied to the cell to evaporate NPB to vapor-deposit a hole transport layer of 20 nm of thickness on the hole injection layer.
[161]
NPB
[162] [163] After forming the hole injection layer and hole transport layer, an electroluminescent layer was vapor-deposited thereon as follows. In one cell of the vacuum vapor-deposit device, charged was a compound selected from Compounds 1-1 through 1-18 which was purified via sublimation in vacuo under 10" torr, as a host material, and in another cell, charged was (NPy) Ir(acac). The two materials were evaporated at different rates to give doping of 4-10 mol%, to vapor-deposit light emitting layer having 30 nm of thickness on the hole transport layer.
[164]
(Npy)2Ir(acac)
[165] Then, tris(8-hydroxyquinoline)aluminum(III) (AIq) represented by following structural formula was vapor-deposited as an electron transport layer in a thickness of 20 nm, and lithium quinolate (Liq) represented by following structural formula was vapor-deposited as an electron injection layer in a thickness of 1 to 2 nm. Thereafter, an Al cathode was vapor-deposited in a thickness of 150 nm by using another vapor- deposit device to manufacture an OLED.
[166]
AIq Liq
[167] [Comparative Example 1] [168] An OLED device was made according to the same procedure as described in Example 1, but bis(2-methyl-8-quinolinato)(p-phenylphenolato)aluminum(III) (BAIq) was charged to another cell in the vacuum vapor-deposit device as a light emitting host material, while (NPy) Ir(acac) was charged as a light emitting material in still another cell, and the two materials were evaporated at different rates to give doping of 4-10 mol%, to vapor-deposit a light emitting layer having 30 nm of thickness on said hole transport layer.
[169]
BAIq (Npy)2lr(acac)
[170] [Example 19] [171] Confirmation of OLED properties [172] The luminous efficiency and power efficiency of each OLED device containing the electroluminescent compound according to the present invention prepared from one of Examples 1-18 and the conventional electroluminescent compound prepared from
Comparative Example 1 were measured at 1,000 cd/m , of which the results are shown in Table 1.
[173] From the Table showing the light emitting properties of the complexes developed by the present invention, it is found that the complexes developed by the present invention exhibit excellent properties in terms of performances as compared to conventional material.
[174] Table 1
[175] As can be seen from the Table, when the electroluminescent material according to the present invention is applied as a host, the EL performance is noticeably improved as a rule.
[176] Fig. 1, an EL spectrum of Comparative Example 1 wherein (NPy) Ir(acac) compound (emitting orange-red light) was used as an electroluminescent material and BAIq as a host material, shows maximum EL peak at about 624 nm. From Fig. 2 showing luminance-applied voltage characteristic of Comparative Example 1, it is confirmed that driving voltage of the device of Comparative Example 1 is about 5 V, and the driving voltage at 1,000 cd/m (standard of Table 1) was 7.49 V. From Fig. 3
which shows luminous efficiency-luminance characteristic of Comparative Example 1 and Table 1, it is confirmed that the device of Comparative Example 1 showed luminous efficiency of about 6.16 cd/A at the luminance of about 1,000 cd/m , and color coordinates of (0.677,0.321).
[177] As can be seen from Fig. 4 which shows luminance-applied voltage characteristic of the OLED device prepared according to Example 14, the device of Example 14 employing the electroluminescent compound according to the present invention showed driving voltage of about 3 V, and luminance of about 1,000 cd/m at about 4.86 V; the result shows decrease of driving voltage by at least 2.6 V as compared to the device of Comparative Example 1.
[178] Further, as can be seen from Fig. 5 which shows luminous efficiency-luminance characteristic of the device according to Example 14, it showed luminous efficiency of about 6.67 cd/A at 1,000 cd/m of luminance; which shows higher luminous efficiency by about 0.5 cd/A as compared to the device of Comparative Example 1 at the same luminance.
[179] With respect to power efficiency which is considered important in a practical panel, since the term voltage is included in the denominator in Formula 1 below, the device having lowered driving voltage becomes far advantageous in terms of power consumption:
[180] Power efficiency(lm/W)=(π x luminance)/(current density x voltage) (1)
[181] As can be seen from Table 1 above, the device employing an electroluminescent compound according to the present invention as the host material lowers the driving voltage to induce increase of power efficiency by 0.5 ~ 2.0 lm/W, thereby improving the power consumption.
[182]
Industrial Applicability
[183] When the electroluminescent compounds according to the present invention are employed in OLED devices as a host material, driving voltage is noticeably lowered and power efficiency is considerably increased. Thus, the compounds in the present invention are suitable for an OLED material in next generation, and expected to greatly contribute for the development of large size display adopted OLED.
[184]
[185]
[186]
Claims
[Chemical Formula 1]
L1L2M wherein, L and L are different each other, and selected from those represented by one of the following structural formulas:
wherein, M is a divalent metal; X is O, S or Se; A ring is oxazole, thiazole, imidazole, oxadiazole, thiadiazole, benzoxazole, benzothiazole, benzimidazole, pyridine or quinoline, and the pyridine or quinoline may form a fused ring with R via chemical bond, and said A ring may have additional substituent such as C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s); B ring is pyridine or quinoline, and said B ring may have additional substituent such as C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s); and R independently represents hydrogen or C1-C5 alkyl.
[2] An electroluminescent compound according to claim 1, wherein the ligands L and L are different each other, and selected from those represented by one of the following structural formulas:
wherein, M is divalent metal; X is O, S or Se; Y is O, S or N-R 4 , Z is CH or N; R and R independently represent hydrogen, phenyl or naphthyl with or without substituent(s); and R 4 is C1-C5 alkyl, or phenyl or naphthyl with or without substituent(s).
[3] An electroluminescent compound according to claim 1, wherein M is selected from Be, Zn, Mg, Cu and Ni.
[4] An electroluminescent compound according to claim 1, wherein the ligands L and L2 are different each other and selected from those represented by one of the following structural formulas:
wherein, X is O, S or Se.
[5] An electroluminescent compound according to claim 4, wherein the ligands L and L2 are different each other, and selected from those represented by one of the following structural formulas:
wherein, X is O or S.
[6] An electroluminescent compound according to claim 5, which is selected from the compounds represented by one of Chemical Formulas 1-1 through 1-18: [Chemical Formula 1-1]
[Chemical Formula 1-2]
[Chemical Formula 1-3]
[Chemical Formula 1-4]
[Chemical Formula 1-5]
[Chemical Formula 1-6]
[Chemical Formula 1-7]
[Chemical Formula 1-8]
[Chemical Formula 1-9]
[Chemical Formula 1-10]
[Chemical Formula 1-11]
[Chemical Formula 1-12]
[Chemical Formula 1-13]
[Chemical Formula 1-14]
[Chemical Formula 1-15]
[Chemical Formula 1-16]
[Chemical Formula 1-17]
[Chemical Formula 1-18]
[7] An electroluminescent device comprising an electroluminescent compound according to any one of claims 1 to 6. [8] An electroluminescent device according to claim 7, in which the electroluminescent compound is used as a host material in an emitting layer.
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| KR100850886B1 (en) * | 2007-09-07 | 2008-08-07 | (주)그라쎌 | Organometalic compounds for electroluminescence and organic electroluminescent device using the same |
| DE102007053771A1 (en) | 2007-11-12 | 2009-05-14 | Merck Patent Gmbh | Organic electroluminescent devices |
| TWI391468B (en) * | 2007-12-31 | 2013-04-01 | Gracel Display Inc | Novel red electroluminescent compounds and organic electroluminescent device using the same |
| KR100970713B1 (en) * | 2007-12-31 | 2010-07-16 | 다우어드밴스드디스플레이머티리얼 유한회사 | Electroluminescent device Green using the electroluminescent compounds |
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| CN102627963A (en) * | 2012-03-21 | 2012-08-08 | 电子科技大学 | Organic electrophosphorescent material and organic electroluminescent device |
| CN104183789A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic light emitting diode and preparation method thereof |
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| JP2002305083A (en) * | 2001-04-04 | 2002-10-18 | Mitsubishi Chemicals Corp | Organic electroluminescent element |
| JP2003252888A (en) * | 2001-12-26 | 2003-09-10 | Mitsubishi Chemicals Corp | Organic iridium complex and organic electroluminescent element using the same |
| WO2004055130A1 (en) * | 2002-12-17 | 2004-07-01 | Fuji Photo Film Co., Ltd. | Organic electroluminescent device |
| US20040124769A1 (en) * | 2002-12-17 | 2004-07-01 | Fuji Photo Film Co., Ltd. | Organic electroluminescent element |
| US20040131881A1 (en) * | 2002-12-31 | 2004-07-08 | Eastman Kodak Company | Complex fluorene-containing compounds for use in OLED devices |
| WO2004062324A1 (en) * | 2002-12-27 | 2004-07-22 | Fuji Photo Film Co., Ltd. | Organic electroluminescent device |
| WO2004073030A2 (en) * | 2003-02-06 | 2004-08-26 | Georgia Tech Research Corporation | Metal 8-hydroxyquinoline -functionalized polymers and related materials and methods of making and using the same |
| WO2005030900A1 (en) * | 2003-09-25 | 2005-04-07 | Nippon Steel Chemical Co., Ltd. | Organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003073355A (en) * | 2001-09-04 | 2003-03-12 | Toyota Central Res & Dev Lab Inc | Metal complex compound and organic electroluminescent device using the same |
| JP2003192691A (en) * | 2001-12-26 | 2003-07-09 | Mitsubishi Chemicals Corp | Organic iridium complex and organic electroluminescent element |
| JP4711617B2 (en) * | 2002-12-17 | 2011-06-29 | 富士フイルム株式会社 | Organic electroluminescence device |
| JP4524093B2 (en) * | 2002-12-17 | 2010-08-11 | 富士フイルム株式会社 | Organic electroluminescence device |
| JP2005002101A (en) * | 2003-05-16 | 2005-01-06 | Semiconductor Energy Lab Co Ltd | Organometallic complex and light-emitting device using the same |
| TWI245068B (en) * | 2003-11-18 | 2005-12-11 | Chi Mei Optoelectronics Corp | Iridium complex as light emitting material and organic light emitting diode device |
| TWI237524B (en) * | 2004-05-17 | 2005-08-01 | Au Optronics Corp | Organometallic compound and organic electroluminescent device including the same |
-
2006
- 2006-01-24 KR KR1020060007467A patent/KR100684109B1/en not_active IP Right Cessation
-
2007
- 2007-01-19 TW TW096102045A patent/TWI352110B/en active
- 2007-01-24 EP EP07708585A patent/EP2004774A4/en not_active Withdrawn
- 2007-01-24 CN CN200780007221XA patent/CN101517033B/en not_active Expired - Fee Related
- 2007-01-24 WO PCT/KR2007/000423 patent/WO2007086682A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002305083A (en) * | 2001-04-04 | 2002-10-18 | Mitsubishi Chemicals Corp | Organic electroluminescent element |
| JP2003252888A (en) * | 2001-12-26 | 2003-09-10 | Mitsubishi Chemicals Corp | Organic iridium complex and organic electroluminescent element using the same |
| WO2004055130A1 (en) * | 2002-12-17 | 2004-07-01 | Fuji Photo Film Co., Ltd. | Organic electroluminescent device |
| US20040124769A1 (en) * | 2002-12-17 | 2004-07-01 | Fuji Photo Film Co., Ltd. | Organic electroluminescent element |
| WO2004062324A1 (en) * | 2002-12-27 | 2004-07-22 | Fuji Photo Film Co., Ltd. | Organic electroluminescent device |
| US20040131881A1 (en) * | 2002-12-31 | 2004-07-08 | Eastman Kodak Company | Complex fluorene-containing compounds for use in OLED devices |
| WO2004073030A2 (en) * | 2003-02-06 | 2004-08-26 | Georgia Tech Research Corporation | Metal 8-hydroxyquinoline -functionalized polymers and related materials and methods of making and using the same |
| WO2005030900A1 (en) * | 2003-09-25 | 2005-04-07 | Nippon Steel Chemical Co., Ltd. | Organic electroluminescent device |
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| LIU YU ET AL: "High-performance blue electroluminescent devices based on hydroxyphenyl-pyridine beryllium complex" APPLIED PHYSICS LETTERS, AIP, AMERICAN INSTITUTE OF PHYSICS, MELVILLE, NY, US, vol. 78, no. 16, 16 April 2001 (2001-04-16), pages 2300-2302, XP012027756 ISSN: 0003-6951 * |
| See also references of WO2007086682A1 * |
| YASUNORI KIJIMA ET AL: "RGB Luminescence from Passive-Matrix Organic LED's" IEEE TRANSACTIONS ON ELECTRON DEVICES, IEEE SERVICE CENTER, PISACATAWAY, NJ, US, vol. 44, no. 8, 1 August 1997 (1997-08-01), XP011016213 ISSN: 0018-9383 * |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2007086682A1 (en) | 2007-08-02 |
| CN101517033A (en) | 2009-08-26 |
| JP5173836B2 (en) | 2013-04-03 |
| CN101517033B (en) | 2012-10-03 |
| JP2009524650A (en) | 2009-07-02 |
| TW200728433A (en) | 2007-08-01 |
| KR100684109B1 (en) | 2007-02-16 |
| EP2004774A4 (en) | 2009-11-25 |
| TWI352110B (en) | 2011-11-11 |
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