WO2010061989A1 - Organometallic complex compounds for photoelectric device and photoelectric device including the same - Google Patents
Organometallic complex compounds for photoelectric device and photoelectric device including the same Download PDFInfo
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- WO2010061989A1 WO2010061989A1 PCT/KR2008/007010 KR2008007010W WO2010061989A1 WO 2010061989 A1 WO2010061989 A1 WO 2010061989A1 KR 2008007010 W KR2008007010 W KR 2008007010W WO 2010061989 A1 WO2010061989 A1 WO 2010061989A1
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- cyclic compound
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 125000002524 organometallic group Chemical group 0.000 title 1
- 239000000126 substance Substances 0.000 claims abstract description 64
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 239000010410 layer Substances 0.000 claims description 82
- -1 aliphatic cyclic compound Chemical class 0.000 claims description 32
- 150000001923 cyclic compounds Chemical group 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- 125000005842 heteroatom Chemical group 0.000 claims description 17
- 125000000129 anionic group Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000004982 aromatic amines Chemical class 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 claims description 10
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 10
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 10
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 125000005549 heteroarylene group Chemical group 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910021472 group 8 element Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 4
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 230000009878 intermolecular interaction Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 15
- 239000000872 buffer Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000001716 carbazoles Chemical class 0.000 description 6
- 230000005283 ground state Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XEPMXWGXLQIFJN-UHFFFAOYSA-K aluminum;2-carboxyquinolin-8-olate Chemical compound [Al+3].C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1.C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1.C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1 XEPMXWGXLQIFJN-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 *C1(C=*)C(*=**)=C(*=C)C2=C1****2 Chemical compound *C1(C=*)C(*=**)=C(*=C)C2=C1****2 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/08—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing alicyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
Definitions
- the present invention relates to an organic metallic complex compound for an organic photoelectric device and an organic photoelectric device including the same. More particularly, the present invention relates to an organic metallic complex compound for an organic photoelectric device having improved luminous efficiency and solubility, and an organic photoelectric device including the same.
- An organic photoelectric device has been highlighted as a next generation display device.
- the organic photoelectric device can be driven at a low voltage, and can solve various problems of a liquid crystal display (LCD), such that is difficult to make it thinner and have a wide viewing angle and rapid response speed.
- LCD liquid crystal display
- An organic photoelectric device of a middle size or less also has equivalent or better image quality to a liquid crystal display (LCD) compared to other displays, and its manufacturing process is very simple. Therefore, it is evaluated to be advantageous in terms of cost in the future.
- An organic photoelectric device includes an organic light emitting material between a rear plate including ITO transparent electrode patterns as an anode on a transparent glass substrate and an upper plate including a metal electrode as a cathode on a substrate. When a predetermined voltage is applied between the transparent electrode and the metal electrode, current flows through the organic light emitting material to emit light.
- Such an organic light emitting material for an organic photoelectric device was firstly developed by Eastman Kodak, Inc., in 1987.
- the material is a low molecular aromatic diamine and aluminum complex as an emission-layer-forming material (Applied Physics Letters. 51 , 913, 1987).
- C. W. Tang et al. firstly disclosed a practicable device as an organic photoelectric device in 1987 (Applied Physics Letters, 51 12, 913-915, 1987).
- the organic layer has a structure in which a thin film (hole transport layer (HTL)) of a diamine derivative and a thin film of tris(8-hydroxy-quinolate)aluminum (AIq 3 ) are laminated.
- HTL hole transport layer
- AIq 3 tris(8-hydroxy-quinolate)aluminum
- an organic photoelectric device is composed of an anode of a transparent electrode, an organic thin layer of a light emitting region, and a metal electrode (cathode) formed on a glass substrate, in that order.
- the organic thin layer may include an emission layer, a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (EIL). It may further include an electron blocking layer or a hole blocking layer due to the emission characteristics of the emission layer.
- HIL hole injection layer
- HTL hole transport layer
- ETL electron transport layer
- EIL electron injection layer
- the holes and electrons are injected from the anode and the cathode, respectively.
- the injected holes and electrons are recombined on the emission layer though the hole transport layer (HTL) and the electron transport layer (ETL) to provide light emitting excitons.
- the provided light emitting excitons emit light by transiting to the ground state.
- a light emitting colorant (dopant) may be added in an emission layer (host) in order to increase the efficiency and stability in the emission state.
- the light emitting material may be classified as a fluorescent material singlet excitons and a phosphorescent material including triplet excitons according to the light emitting mechanism.
- a phosphorescent light emitting material can be used for a light emitting material of an organic photoelectric device as well as the fluorescent light emitting material (D. F. O'Brien et al., Applied Physics Letters, 74 3, 442-444, 1999; M. A. Baldo et al., Applied Physics letters, 75 1 , 4-6, 1999).
- Such a phosphorescent material emits light by transiting the electrons from a ground state to an excited state, non-radiance transiting of a singlet exciton to a triplet exciton through intersystem crossing, and transiting a triplet exciton to a ground state to emit light.
- the triplet exciton When the triplet exciton is transited, it cannot directly transit to the ground state. Therefore, the electron spin is flipped, and then it is transited to the ground state so that it provides a characteristic of extending the lifetime (emission duration) to more than that of fluorescent emission.
- the duration of fluorescent emission is extremely short at several nanoseconds, but the duration of phosphorescent emission is relatively long such as at several microseconds.
- the singlet and the triplet are produced in a ratio of 1 :3, in which the triplet light emitting excitons are produced at three times the amount of the singlet light emitting excitons in the organic photoelectric device. Accordingly, the percentage of the singlet exited state is 25% (the triplet is 75%) in the case of a fluorescent material, so it has limits in luminous efficiency. On the other hand, in the case of a phosphorescent material, it can utilize 75% of the triplet exited state and 25% of the singlet exited state, so theoretically the internal quantum efficiency can reach up to 100%. When a phosphorescent light emitting material is used, it has advantages in an increase in luminous efficiency of around three times that of the fluorescent light emitting material.
- a phosphorescent light emitting material has a molecule structure that is appropriate for intersystem crossing.
- the molecule structure includes heavy metals such as Ir, Pt, Rh, or Pd in an organic molecule, which incurs spin-orbital coupling and thus triplets and singlets are mixed. Thereby, inhibited transition is allowed and phosphorescent light emission at room temperature can effectively occur.
- Such an organic metallic complex for phosphorescent light emission is a low molecular material that is applicable using a general dry process such as vacuum deposition.
- a polymer material it can be applied to a device using a wet process such as spin coating, InkJet printing, or casting.
- the wet process using a polymer allows ease of device manufacture compared with a dry process such as vacuum deposition, and has merits in terms of costs and scalability.
- polymer materials have problems of lower life-span, luminous efficiency, color purity, and so on compared with low molecular materials.
- An exemplary embodiment of the present invention provides an organic metallic complex compound for an organic photoelectric device having improved luminous efficiency and solubility.
- Another embodiment of the present invention provides the organic photoelectric device including the organic metallic complex compound for an organic photoelectric device.
- an organic metallic complex compound for an organic photoelectric device represented by the following Chemical Formula 1 is provided. [Chemical Formula 1]
- n is an integer ranging from 1 to 3
- a and b are independently integers of 0 or 1
- a cyclic compound group including Ci and Xi to X 5 a cyclic compound group including C 2 , Y-i, and Xe to Xg
- a cyclic compound group including C 3 and X 10 to Xi 4 are independently selected from the group consisting of an aliphatic cyclic compound, a hetero aliphatic cyclic compound, an aromatic cyclic compound, and a hetero aromatic cyclic compound,
- M is a metal to form an octahedral complex
- L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp 2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms
- Ci to C 3 are -C(Ri7) h -, where h is an integer of 0 or 1 ,
- Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp 2 carbon and a heteroatom
- Xi to Xi4 are independently C(Ri)j(R 2 )j, N(R 3 ) k , Si(R 4 ) 0 (R5)p, O, or S 1 where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
- Ri to R 5 and R 17 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, R 16 , OR 16 , N(R 16 J 2 , P(Rie) 2 , P(OR 16 ) 2) POR 16 , PO 2 R 16 , PO 3 R 16 , SR 16 , Si(R 16 )S, Si(CH 3 ) 2 Ri 6 , Si(Ph) 2 R 16 , B(R 16 ) 2 , B(OR 16 ) 2 , C(O)R 16 , C(O)OR 16 , C(O)N(R 16 ) 2 , CN, NO 2 , SOR 16 , SO 2 R 16 , and SO 3 R 16 ,
- R 1 to R 5 are present as independent substituents, or are fused together to form a cycle bound to the X 1 to X 14 , at least one of Ri to R 5 is selected from the group consisting of a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, and a substituted or unsubstituted biarylphenyl,
- R 16 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted
- R 1S is selected from the group consisting of a halogen, a nitro, a substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C2 to C30 heteroaryl, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C2 to C20 acyl, an amino, and a substituted or unsubstituted C1 to C20 alkoxy.
- an organic photoelectric device is provided that includes an organic thin layer disposed between a pair of electrodes.
- the organic thin layer includes the above organic metallic complex compound.
- the organic metallic complex compound for an organic photoelectric device suppresses molecular interaction and thus improves luminous efficiency and solubility.
- the organic metallic complex compound can be applicable to a wet process such as spin coating, InkJet printing, casting, and so on due to excellent solubility during fabrication of an organic photoelectric device, resulting in a fabrication cost reduction of an organic photoelectric device.
- FIG. 1 is an exploded perspective view showing an organic photoelectric device according to one embodiment of the present invention.
- organic photoelectric device 10 substrate 20: first electrode 30: second electrode 100: organic thin layer 110: first buffer layer 120: emission layer 130: second buffer layer
- an organic metallic complex compound for an organic photoelectric device represented by the following Chemical Formula 1 is provided.
- n is an integer ranging from 1 to 3
- a and b are independently integers of 0 or 1
- a cyclic compound group including Ci and Xi to X 5 a cyclic compound group including C2, Y-i, and X 6 to X 9
- a cyclic compound group including C 3 and X10 to Xi4 are independently selected from the group consisting of an aliphatic cyclic compound, an hetero aliphatic cyclic compound, an aromatic cyclic compound, and a hetero aromatic cyclic compound,
- M is a metal to form an octahedral complex
- L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp 2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms,
- Ci to C 3 are -C(Ri 7 )h-, where h is an integer of 0 or 1 ,
- Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp 2 carbon and a heteroatom
- Xi to Xi4 are independently C(Ri)i(R 2 )j, N(R 3 )k, Si(R 4 ) 0 (R5)p, O, or S, where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
- Ri to R 5 , and Ri 7 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, R 16 , OR 16 , N(R 16 ) 2 , P(R 16 )2, P(OR 16 ) 2 , POR 16 , PO 2 R 16 , PO 3 R 16 , SR 16 , Si(R 16 ) 3 , Si(CHs) 2 R 16 , Si(Ph) 2 R 16 , B(R 16 ) 2 , B(OR 16 ) 2 , C(O)R 16 , C(O)OR 16 , C(O)N(R 16 ) 2 , CN, NO 2 , SOR 16 , SO 2 R 16 , and SO 3 R 16 , Ri to R 5 are present as
- R 16 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and
- Ri 5 is selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene.
- heteroatom refers to an atom selected from the group consisting of nitrogen (N), oxygen (O), sulfur (S), and phosphorus (P).
- hetero aliphatic cyclic compound refers to an aliphatic cyclic compound, an aromatic cyclic compound, an alkyl, and an aryl including 1 to 3 heteroatoms selected from the group consisting of nitrogen (N), oxygen (O), sulfur (S), and phosphorus (P), and the remainder being carbon.
- substituted refers to one substituted with at least a substituent selected from the group consisting of a halogen, a cyano, a hydroxy, an amino, a substituted or unsubstituted C6 to C30 aryl, and a substituted or unsubstituted C2 to C30 heteroaryl instead of hydrogen.
- Xi to XH are independently C(Ri)(R 2 ), N(R 3 ),
- Si(R 5 )(Re), O, or S, and Ci to C 3 are C(Ri 7 ).
- h, i, j, k, o, and p are 1.
- Xi to Xu are independently C(Ri), N(R 3 ),
- Si(R 5 )(R 6 ), O, or S, and Ci to C 3 are C.
- h, j, k, 0, and p are O, and I is 1.
- X 1 to X 14 are independently C(ROi(R 2 )J, N(R 3 ) k , Si(R 4 ) 0 (R5)p, O, or S, i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2.
- C 1 and Xi to X 4 form a pentacyclic compound if a is 0 in the above Chemical Formula 1
- Ci and X-i to X 4 are a hexacyclic compound if a is 1 in the above Chemical Formula 1.
- C 2 , Y 1 , and X 7 to Xg form a pentacyclic compound if b is 0, and C 2 , Y 1 , and X 7 to Xg form a hexacyclic compound if b is 1.
- the cyclic compound group including Ci and Xi to X 5 , the cyclic compound group including C 2 , Yi, and X 6 to Xg, and the cyclic compound group including C 3 and Xi 0 to Xu are independently selected from the group consisting of an aromatic cyclic compound and a hetero aromatic cyclic compound.
- Ri to R5 are preferably selected from the group consisting of substituents represented by the following Chemical Formulae 2 to 6.
- X21 to X 28 , X31 to X 38 , and X 51 to X 66 are independently selected from the group consisting of CRi 8 and N,
- Ris and R" are independently selected from the group consisting of hydrogen, a halogen, R 16 , ORi 6 , N(Ri 6 ) 2 , P(Rie) 2l P(ORi 6 ) 2 , PORi 6 , PO 2 R 16 , PO 3 R 16 , SRi 6 , Si(Rie) 3 , Si(CH 3 ) 2 Ri6, Si(Ph) 2 Ri 6 , B(R i6 ) 2 , B(ORi 6 ) 2 , C(O)Ri 6 , C(O)OR 16 , C(O)N(R 16 ) 2 , CN, NO 2 , SOR 16 , SO 2 R 16 , and SO 3 R 16 ,
- Ri 6 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl,
- R 1 is selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene, and
- An to Ar 4 are selected from the group consisting of a substituted or unsubstituted C6 to C30 aryl and a substituted or unsubstituted C2 to C30 heteroaryl.
- the organic metallic complex compound represented by the above Chemical Formula 1 is preferably selected from the group consisting of the following Chemical Formulae 7 to 9.
- ni is an integer ranging from 1 to 3
- n 2 and n 3 are independently integers ranging from 1 to 5
- a and b are independently integers of 0 or 1
- the cyclic compound group including Ci and Xi to Xs the cyclic compound group including C 2 , Yi, and X 6 to X 9
- the cyclic compound group including C 3 and Xi 0 to Xu are independently selected from the group consisting of an aliphatic cyclic compound, a hetero aliphatic cyclic compound, an aromatic cyclic compound, and a hetero aromatic cyclic compound,
- M is a metal to form an octahedral complex
- L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp 2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms,
- Ci to C 3 are -C(Ri 7 )h-, where h is an integer of 0 or 1 ,
- Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp 2 carbon and a heteroatom
- X 1 to X 14 are independently C(ROi(R 2 )J, N(R 3 ) k , Si(R 4 ) 0 (R5)p, O, or S, where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
- X-I5 to X30 are independently selected from the group consisting of CRi 8 and N, Ri to R5, Ri7, R18 1 R". and R"" are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, Ri 6 , ORi 6 , N Ri 62 , P Ri 62 , P ORi 62 , PORi 6 , PO 2 Ri 6 , PO 3 Ri 6 , SRi 6 , Si R 1 ⁇ 3l Si CH 32 Ri 6 , Si (Ph) 2 Ri 6 , B Ri 62 , B OR i62 , C (O)R 16 , C(O)ORi 61 C(O)N Ri 62 , CN, NO 2 , SO 2 , SORi 6 ,
- Ri to R 5 are present as independent substituents, or are fused together to form a cycle bound to the Xi to Xi 4 ,
- Ri 6 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and
- R 15 , R 1 , and R'" are independently selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene.
- the L is preferably selected from the group consisting of ligands represented by the following Chemical Formulae 10 to 16.
- Ri to R 3 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, R 16 , ORi 6 , N(R 16 ) 2 , P(Ri ⁇ )2, P(ORi 6 )2, PORi 6 , PO 2 Ri 6 , PO 3 Ri 6 , SR 16 , Si(Rie) 3l Si(CH 3 ) 2 Ri6, Si(Ph) 2 Ri 6 , B(Ri 6 ) 2l B(ORi 6 ) 2 , C(O)R 16 , C(O)ORi 6 , C(O)N(R-Ie) 2 , CN, NO 2 , SOR 16 , SO 2 R 16 , and SO 3 R 16 , R 16 is selected from the group consisting of a
- M is preferably selected from the group consisting of a Group 8 element and a Group 10 element of the periodic table that is capable of forming an octahedral complex.
- An element selected from the group consisting of Ir, Pt, Rh, and Pd is more preferable, and Ir is still more preferable.
- an organic photoelectric device that includes an organic thin layer disposed between a pair of electrodes.
- the organic thin layer includes the above polymer.
- the organic photoelectric device may be an organic light emitting diode.
- the organic photoelectric device includes a first electrode disposed on a substrate, an organic thin layer including the organic metallic complex compound disposed on the first electrode, and a second electrode disposed on the organic thin layer.
- the first electrode may include transparent and highly conductive indium tin oxide (ITO), indium-zinc-oxide (IZO), or so on.
- ITO indium tin oxide
- IZO indium-zinc-oxide
- the substrate may be a glass substrate or a flexible substrate.
- the organic thin layer includes at least one of a first buffer layer for hole injection or transport, disposed on the first electrode, an emission layer disposed on the first buffer layer, and a second buffer layer for electron injection or transport, disposed on the emission layer.
- At least one layer of the organic thin layer includes the organic metallic complex compound according to one embodiment of the present invention.
- the first buffer layer may include at least one selected from the group consisting of a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer, and combinations thereof.
- the second buffer layer may include at least one selected from the group consisting of an electron injection layer
- EIL electron transport layer
- ETL electron blocking layer
- FIG. 1 is an exploded perspective view of an organic photoelectric device according to one embodiment of the present invention.
- the organic photoelectric device 1 includes a first electrode (anode, 20) including a transparent conductive metal oxide, an organic thin layer 100 including a light emitting region, and a second electrode (cathode, 30) that are sequentially disposed on a substrate 10.
- the substrate 10 may be a glass substrate or a flexible substrate.
- the first electrode 20 is disposed on the substrate 10.
- the first electrode 20 is made of a transparent conductive metal oxide such as ITO or IZO.
- the organic thin layer 100 is disposed on the first electrode 20.
- the organic thin layer 100 includes an emission layer 120, a first buffer layer 110, and a second buffer layer 130. At least one layer of the organic thin layer 100 includes the organic metallic complex compound according to one embodiment of the present invention.
- the first and second buffer layers 110 and 130 may include at least one selected from the group consisting of a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), and an electron injection layer (EIL), and may respectively further include an electron blocking layer or a hole blocking layer to improve light emitting characteristics of the emission layer 120.
- HIL hole injection layer
- HTL hole transport layer
- ETL electron transport layer
- EIL electron injection layer
- the second electrode 30 is disposed on the second buffer layer 130.
- the second electrode 30 may be formed using lithium (Li) 1 magnesium (Mg), calcium (Ca), aluminum (Al) 1 AI:Li, Ba:Li, or Ca:Li having a small work function.
- the holes and electrons are injected from the first electrode 20 and the second electrode 30, respectively.
- the injected holes and electrons are recombined on the emission layer of the organic thin layer 100 to provide light emitting excitons.
- the provided light emitting excitons emit light by transiting to the ground state.
- the organic metallic complex compound represented by Chemical Formula 15 was prepared according to the same method as Example 1 , except that a ligand b was used.
- the organic metallic complex compound represented by Chemical Formula 16 was prepared according to the same method as Example 1 , except that a ligand c was used.
- a first electrode was formed of ITO in a size of 20mm x 20mm x 0.7mm on a glass substrate of 15 ⁇ /cm 2 and 1200A, which was produced by the Corning Company.
- the substrate with the first electrode formed therein went through ultrasonic rinsing in isopropyl alcohol and deionized water for 5 minutes, respectively, and then went through UV ozone cleaning for 30 minutes.
- the upper part of the first electrode was spin-coated with poly(ethylenedioxy)thiophene (PEDOT).
- PEDOT poly(ethylenedioxy)thiophene
- PVK polyvinylcarbazole
- CBP 4,4'-N,N'-dicarbazolebiphenyl
- the emission layer was spin-coated to a thickness of 500A.
- a hole blocking layer was formed to a thickness of 50A on the emission layer through vacuum-deposition of bis(2-methyl-8-quinolinolate)-4-(phenylphenolate)aluminum (BAIq).
- an electron transport layer (ETL) was formed at a thickness of 200.A on the hole blocking film through vacuum-deposition of tris(8-hydroxy-quinolate)aluminum (AIq 3 ).
- An organic photoelectric device was fabricated by sequentially vacuum-depositing LiF on an electron transport layer (ETL) to a thickness of 10A to form an electron injection layer (EIL), and vacuum-depositing Al as a second electrode.
- ETL electron transport layer
- EIL electron injection layer
- initial driving voltage which is also referred to as "turn-on voltage”
- maximum luminance cd/m 2
- driving voltage V
- current efficiency cd/A
- electric power efficiency Im/W
- the organic photoelectric device was fabricated not through vacuum deposition but through spin-coating, which is a wet process
- the organic metallic complex compound used in the organic thin layer showed high efficiency of about 26cd/A in case of Example 1 , and all had maximum luminance of over 10,000cd/m 2 .
- the driving voltage ranged from 4.2 V to 4.6 V
- the driving voltage at 1000cd/m 2 ranged from 8.4 V to 10.2 V.
- the organic metallic complex compound according to an embodiment of the present invention shows an excellent solubility characteristic in an organic solvent, such as toluene, chloroform, or chlorobenzene, due to decreased Van der Waals force among molecules, which is different from lr(ppy) 3 or lr(mppy) 3 that are known to be effective among green phosphorescent light emitting organic metallic complex compounds. This proves that the use of the organic metallic complex compound makes it possible to easily fabricate an organic photoelectric device even through a wet process.
- the organic metallic complex compound of the present invention When a bulky substituent is introduced into the organic metallic complex compound of the present invention, the organic metallic complex compound can improve solubility since molecules therein become apart from one another, and crystallinity decreases.
- the organic metallic complex compound suppresses intermolecular interaction and thus improves luminous efficiency and electrical characteristics.
- organic metallic complex compound according to one embodiment of the present invention may be usefully applied to a phosphorescent light emitting material of an organic photoelectric device.
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Abstract
Disclosed are an organic metallic complex compound for an organic photoelectric device represented by the specific Chemical Formula, and an organic photoelectric device including the same. The organic metallic complex compound for an organic photoelectric device includes a bulky substituent as a ligand, and thus suppresses intermolecular interaction resulting in improvement of luminous efficiency and solubility.
Description
TITLE OF THE INVENTION
ORGANOMETALLIC COMPLEX COMPOUNDS FOR PHOTOELECTRIC DEVICE AND PHOTOELECTRIC DEVICE INCLUDING THE SAME
BACKGROUND OF THE INVENTION
(a) Field of the Invention
The present invention relates to an organic metallic complex compound for an organic photoelectric device and an organic photoelectric device including the same. More particularly, the present invention relates to an organic metallic complex compound for an organic photoelectric device having improved luminous efficiency and solubility, and an organic photoelectric device including the same.
(b) Description of the Related Art
An organic photoelectric device has been highlighted as a next generation display device. The organic photoelectric device can be driven at a low voltage, and can solve various problems of a liquid crystal display (LCD), such that is difficult to make it thinner and have a wide viewing angle and rapid response speed.
An organic photoelectric device of a middle size or less also has equivalent or better image quality to a liquid crystal display (LCD) compared to other displays, and its manufacturing process is very simple. Therefore, it is evaluated to be advantageous in terms of cost in the future. An organic photoelectric device includes an organic light emitting material between a rear plate including ITO transparent electrode patterns as an anode on a transparent
glass substrate and an upper plate including a metal electrode as a cathode on a substrate. When a predetermined voltage is applied between the transparent electrode and the metal electrode, current flows through the organic light emitting material to emit light. Such an organic light emitting material for an organic photoelectric device was firstly developed by Eastman Kodak, Inc., in 1987. The material is a low molecular aromatic diamine and aluminum complex as an emission-layer-forming material (Applied Physics Letters. 51 , 913, 1987). C. W. Tang et al. firstly disclosed a practicable device as an organic photoelectric device in 1987 (Applied Physics Letters, 51 12, 913-915, 1987).
According to the reference, the organic layer has a structure in which a thin film (hole transport layer (HTL)) of a diamine derivative and a thin film of tris(8-hydroxy-quinolate)aluminum (AIq3) are laminated.
Generally, an organic photoelectric device is composed of an anode of a transparent electrode, an organic thin layer of a light emitting region, and a metal electrode (cathode) formed on a glass substrate, in that order.
The organic thin layer may include an emission layer, a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (EIL). It may further include an electron blocking layer or a hole blocking layer due to the emission characteristics of the emission layer.
When the organic light emitting diode is applied with an electric field, the holes and electrons are injected from the anode and the cathode, respectively. The injected holes and electrons are recombined on the emission layer though the hole transport layer (HTL) and the electron transport layer (ETL) to provide
light emitting excitons. The provided light emitting excitons emit light by transiting to the ground state. A light emitting colorant (dopant) may be added in an emission layer (host) in order to increase the efficiency and stability in the emission state. In the above-mentioned organic photoelectric device, the light emitting material may be classified as a fluorescent material singlet excitons and a phosphorescent material including triplet excitons according to the light emitting mechanism. It is has become known that a phosphorescent light emitting material can be used for a light emitting material of an organic photoelectric device as well as the fluorescent light emitting material (D. F. O'Brien et al., Applied Physics Letters, 74 3, 442-444, 1999; M. A. Baldo et al., Applied Physics letters, 75 1 , 4-6, 1999).
Such a phosphorescent material emits light by transiting the electrons from a ground state to an excited state, non-radiance transiting of a singlet exciton to a triplet exciton through intersystem crossing, and transiting a triplet exciton to a ground state to emit light.
When the triplet exciton is transited, it cannot directly transit to the ground state. Therefore, the electron spin is flipped, and then it is transited to the ground state so that it provides a characteristic of extending the lifetime (emission duration) to more than that of fluorescent emission.
In other words, the duration of fluorescent emission is extremely short at several nanoseconds, but the duration of phosphorescent emission is relatively long such as at several microseconds.
In addition, evaluating quantum mechanically, when holes injected from
the anode are recombined with electrons injected from the cathode to provide light emitting excitons, the singlet and the triplet are produced in a ratio of 1 :3, in which the triplet light emitting excitons are produced at three times the amount of the singlet light emitting excitons in the organic photoelectric device. Accordingly, the percentage of the singlet exited state is 25% (the triplet is 75%) in the case of a fluorescent material, so it has limits in luminous efficiency. On the other hand, in the case of a phosphorescent material, it can utilize 75% of the triplet exited state and 25% of the singlet exited state, so theoretically the internal quantum efficiency can reach up to 100%. When a phosphorescent light emitting material is used, it has advantages in an increase in luminous efficiency of around three times that of the fluorescent light emitting material.
A phosphorescent light emitting material has a molecule structure that is appropriate for intersystem crossing. The molecule structure includes heavy metals such as Ir, Pt, Rh, or Pd in an organic molecule, which incurs spin-orbital coupling and thus triplets and singlets are mixed. Thereby, inhibited transition is allowed and phosphorescent light emission at room temperature can effectively occur.
An iridium organic metallic complex has garnered interest due to excellent phosphorescent luminous efficiency, and phosphorescent light emitting materials including such a metallic complex have been reported [Sergey Lamansky et al. Inorg. Chem., 40, 1704-1711 , 2001 & J. Am. Chem. Soc, 123, 4304-4312, 2001].
Such an organic metallic complex for phosphorescent light emission is a
low molecular material that is applicable using a general dry process such as vacuum deposition. In the case of a polymer material, it can be applied to a device using a wet process such as spin coating, InkJet printing, or casting.
The wet process using a polymer allows ease of device manufacture compared with a dry process such as vacuum deposition, and has merits in terms of costs and scalability. However, polymer materials have problems of lower life-span, luminous efficiency, color purity, and so on compared with low molecular materials.
Therefore, in order to solve the problems, development of a low material that is applicable to a wet process due to high solubility has been required.
SUMMARY OF THE INVENTION
An exemplary embodiment of the present invention provides an organic metallic complex compound for an organic photoelectric device having improved luminous efficiency and solubility.
Another embodiment of the present invention provides the organic photoelectric device including the organic metallic complex compound for an organic photoelectric device.
The embodiments of the present invention are not limited to the above technical purposes, and a person of ordinary skill in the art can understand other technical purposes.
According to an embodiment of the present invention, an organic metallic complex compound for an organic photoelectric device represented by the following Chemical Formula 1 is provided.
[Chemical Formula 1]
In the above Chemical Formula 1 , n is an integer ranging from 1 to 3, a and b are independently integers of 0 or 1 , a cyclic compound group including Ci and Xi to X5, a cyclic compound group including C2, Y-i, and Xe to Xg, and a cyclic compound group including C3 and X10 to Xi4 are independently selected from the group consisting of an aliphatic cyclic compound, a hetero aliphatic cyclic compound, an aromatic cyclic compound, and a hetero aromatic cyclic compound,
M is a metal to form an octahedral complex,
L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms,
Ci to C3 are -C(Ri7)h-, where h is an integer of 0 or 1 ,
Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom,
Xi to Xi4 are independently C(Ri)j(R2)j, N(R3)k, Si(R4)0(R5)p, O, or S1 where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
Ri to R5 and R17 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, R16, OR16, N(R16J2, P(Rie)2, P(OR16)2) POR16, PO2R16, PO3R16, SR16, Si(R16)S, Si(CH3)2Ri6, Si(Ph)2R16, B(R16)2, B(OR16)2, C(O)R16, C(O)OR16, C(O)N(R16)2, CN, NO2, SOR16, SO2R16, and SO3R16,
R1 to R5 are present as independent substituents, or are fused together to form a cycle bound to the X1 to X14, at least one of Ri to R5 is selected from the group consisting of a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, and a substituted or unsubstituted biarylphenyl,
R16 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted
C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and
R1S is selected from the group consisting of a halogen, a nitro, a
substituted or unsubstituted C6 to C30 aryl, a substituted or unsubstituted C2 to C30 heteroaryl, a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C2 to C20 acyl, an amino, and a substituted or unsubstituted C1 to C20 alkoxy. According to a further embodiment of the present invention, an organic photoelectric device is provided that includes an organic thin layer disposed between a pair of electrodes. The organic thin layer includes the above organic metallic complex compound.
Hereinafter, further embodiments of the present invention will be described in detail.
The organic metallic complex compound for an organic photoelectric device suppresses molecular interaction and thus improves luminous efficiency and solubility.
The organic metallic complex compound can be applicable to a wet process such as spin coating, InkJet printing, casting, and so on due to excellent solubility during fabrication of an organic photoelectric device, resulting in a fabrication cost reduction of an organic photoelectric device.
BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is an exploded perspective view showing an organic photoelectric device according to one embodiment of the present invention.
<Description of Reference Numerals Indicating Primary Elements in the Drawings>
1 : organic photoelectric device 10: substrate
20: first electrode 30: second electrode 100: organic thin layer 110: first buffer layer 120: emission layer 130: second buffer layer
DETAILED DESCRIPTION OF THE INVENTION
Exemplary embodiments of the present invention will hereinafter be described in detail. However, these embodiments are only exemplary, and the present invention is not limited thereto but rather is defined by the scope of the appended claims. According to an embodiment of the present invention, an organic metallic complex compound for an organic photoelectric device represented by the following Chemical Formula 1 is provided.
[Chemical Formula 1]
In the above Chemical Formula 1 ,
n is an integer ranging from 1 to 3, a and b are independently integers of 0 or 1 , a cyclic compound group including Ci and Xi to X5, a cyclic compound group including C2, Y-i, and X6 to X9, and a cyclic compound group including C3 and X10 to Xi4 are independently selected from the group consisting of an aliphatic cyclic compound, an hetero aliphatic cyclic compound, an aromatic cyclic compound, and a hetero aromatic cyclic compound,
M is a metal to form an octahedral complex,
L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms,
Ci to C3 are -C(Ri7)h-, where h is an integer of 0 or 1 ,
Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom,
Xi to Xi4 are independently C(Ri)i(R2)j, N(R3)k, Si(R4)0(R5)p, O, or S, where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
Ri to R5, and Ri7 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, R16, OR16, N(R16)2, P(R16)2, P(OR16)2, POR16, PO2R16, PO3R16, SR16, Si(R16)3, Si(CHs)2R16, Si(Ph)2R16, B(R16)2, B(OR16)2, C(O)R16, C(O)OR16, C(O)N(R16)2, CN, NO2, SOR16, SO2R16, and SO3R16,
Ri to R5 are present as independent substituents, or are fused together to form a cycle bound to the Xi to Xu, at least one of Ri to R5 is selected from the group consisting of a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, and a substituted or unsubstituted biarylphenyl,
R16 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and
Ri5 is selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene. As used herein, the term "heteroatom" refers to an atom selected from the group consisting of nitrogen (N), oxygen (O), sulfur (S), and phosphorus (P).
The terms "hetero aliphatic cyclic compound", "hetero aromatic cyclic compound", "heteroalkyl", and "heteroaryl" respectively refer to an aliphatic cyclic compound, an aromatic cyclic compound, an alkyl, and an aryl including 1 to 3 heteroatoms selected from the group consisting of nitrogen (N), oxygen (O), sulfur (S), and phosphorus (P), and the remainder being carbon.
In the present specification, when specific definition is not provided, the term "substituted" refers to one substituted with at least a substituent selected from the group consisting of a halogen, a cyano, a hydroxy, an amino, a
substituted or unsubstituted C6 to C30 aryl, and a substituted or unsubstituted C2 to C30 heteroaryl instead of hydrogen.
When the cyclic compound group including Ci and Xi to X5, the cyclic compound group including C2, Yi, and X6 to Xg, and the cyclic compound group including C3 and X10 to Xu independently form an aliphatic cyclic compound, or a hetero aliphatic cyclic compound, Xi to XH are independently C(Ri)(R2), N(R3),
Si(R5)(Re), O, or S, and Ci to C3 are C(Ri7). In the case, h, i, j, k, o, and p are 1.
When the cyclic compound group including Ci and Xi to X5, the cyclic compound group including C2, Yi, and X6 to Xg, and the cyclic compound group including C3 and X10 to Xi4 independently form an aromatic cyclic compound or a hetero aromatic cyclic compound, Xi to Xu are independently C(Ri), N(R3),
Si(R5)(R6), O, or S, and Ci to C3 are C. In the case, h, j, k, 0, and p are O, and I is 1.
When X1 to X14 are independently C(ROi(R2)J, N(R3)k, Si(R4)0(R5)p, O, or S, i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2.
C1 and Xi to X4 form a pentacyclic compound if a is 0 in the above Chemical Formula 1 , and Ci and X-i to X4 are a hexacyclic compound if a is 1 in the above Chemical Formula 1. C2, Y1, and X7 to Xg form a pentacyclic compound if b is 0, and C2, Y1, and X7 to Xg form a hexacyclic compound if b is 1.
It is preferable that the cyclic compound group including Ci and Xi to X5, the cyclic compound group including C2, Yi, and X6 to Xg, and the cyclic compound group including C3 and Xi0 to Xu are independently selected from the
group consisting of an aromatic cyclic compound and a hetero aromatic cyclic compound.
Ri to R5 are preferably selected from the group consisting of substituents represented by the following Chemical Formulae 2 to 6.
[Chemical Formula 2]
[Chemical Formula 3]
[Chemical Formula 4]
[Chemical Formula 6]
In the above Chemical Formulae 2 to 6,
X21 to X28, X31 to X38, and X51 to X66 are independently selected from the group consisting of CRi8 and N,
Ris and R" are independently selected from the group consisting of hydrogen, a halogen, R16, ORi6, N(Ri6)2, P(Rie)2l P(ORi6)2, PORi6, PO2R16, PO3R16, SRi6, Si(Rie)3, Si(CH3)2Ri6, Si(Ph)2Ri6, B(Ri6)2, B(ORi6)2, C(O)Ri6, C(O)OR16, C(O)N(R16)2, CN, NO2, SOR16, SO2R16, and SO3R16,
Ri6 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted
C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl,
R1 is selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene, and
An to Ar4 are selected from the group consisting of a substituted or unsubstituted C6 to C30 aryl and a substituted or unsubstituted C2 to C30 heteroaryl.
The organic metallic complex compound represented by the above Chemical Formula 1 is preferably selected from the group consisting of the following Chemical Formulae 7 to 9.
[Chemical Formula 7]
[Chemical Formula 9]
In the above Chemical Formulae 7 to 9, ni is an integer ranging from 1 to 3, n2 and n3 are independently integers ranging from 1 to 5, a and b are independently integers of 0 or 1 , the cyclic compound group including Ci and Xi to Xs, the cyclic compound group including C2, Yi, and X6 to X9, and the cyclic compound group including C3 and Xi0 to Xu are independently selected from the group consisting of an aliphatic cyclic compound, a hetero aliphatic cyclic compound, an aromatic
cyclic compound, and a hetero aromatic cyclic compound,
M is a metal to form an octahedral complex,
L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms,
Ci to C3 are -C(Ri7)h-, where h is an integer of 0 or 1 ,
Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom, X1 to X14 are independently C(ROi(R2)J, N(R3)k, Si(R4)0(R5)p, O, or S, where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
X-I5 to X30 are independently selected from the group consisting of CRi8 and N, Ri to R5, Ri7, R181 R". and R"" are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, Ri6, ORi6, N Ri62, P Ri62, P ORi62, PORi6, PO2Ri6, PO3Ri6, SRi6, Si R1β3l Si CH32Ri6, Si (Ph)2Ri6, B Ri62, B ORi62, C (O)R16, C(O)ORi61 C(O)N Ri62, CN, NO2, SO2, SORi6, SO2Ri6, and SO3Ri6,
Ri to R5 are present as independent substituents, or are fused together to form a cycle bound to the Xi to Xi4,
Ri6 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl,
a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and
R15, R1, and R'" are independently selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene.
The L is preferably selected from the group consisting of ligands represented by the following Chemical Formulae 10 to 16.
[Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12]
[Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15]
In the above Chemical Formulae 10 to 16,
Ri to R3 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, R16, ORi6, N(R16)2, P(Riβ)2, P(ORi6)2, PORi6, PO2Ri6, PO3Ri6, SR16, Si(Rie)3l Si(CH3)2Ri6, Si(Ph)2Ri6, B(Ri6)2l B(ORi6)2, C(O)R16, C(O)ORi6, C(O)N(R-Ie)2, CN, NO2, SOR16, SO2R16, and SO3R16, R16 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, ni is an integer ranging from 1 to 3, n2, n4, and ns are integers ranging from 1 to 4, and n3 is an integer of 1 or 2.
M is preferably selected from the group consisting of a Group 8 element and a Group 10 element of the periodic table that is capable of forming an octahedral complex. An element selected from the group consisting of Ir, Pt,
Rh, and Pd is more preferable, and Ir is still more preferable.
According to a further embodiment of the present invention, an organic photoelectric device that includes an organic thin layer disposed between a pair of electrodes is provided. The organic thin layer includes the above polymer. In one embodiment, the organic photoelectric device may be an organic light emitting diode.
The organic photoelectric device includes a first electrode disposed on a substrate, an organic thin layer including the organic metallic complex compound disposed on the first electrode, and a second electrode disposed on the organic thin layer.
The first electrode may include transparent and highly conductive indium tin oxide (ITO), indium-zinc-oxide (IZO), or so on.
The substrate may be a glass substrate or a flexible substrate.
The organic thin layer includes at least one of a first buffer layer for hole injection or transport, disposed on the first electrode, an emission layer disposed on the first buffer layer, and a second buffer layer for electron injection or transport, disposed on the emission layer. At least one layer of the organic thin layer includes the organic metallic complex compound according to one embodiment of the present invention. The first buffer layer may include at least one selected from the group consisting of a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer, and combinations thereof. The second buffer layer may include at least one selected from the group consisting of an electron injection layer
(EIL), an electron transport layer (ETL), an electron blocking layer, and
combinations thereof.
The organic metallic complex compound can be applicable to a wet process such as spin coating, InkJet printing, casting, and the like during fabrication of an organic thin layer due to excellent solubility. FIG. 1 is an exploded perspective view of an organic photoelectric device according to one embodiment of the present invention.
Referring to FIG. 1 , the organic photoelectric device 1 includes a first electrode (anode, 20) including a transparent conductive metal oxide, an organic thin layer 100 including a light emitting region, and a second electrode (cathode, 30) that are sequentially disposed on a substrate 10.
The substrate 10 may be a glass substrate or a flexible substrate.
The first electrode 20 is disposed on the substrate 10. The first electrode 20 is made of a transparent conductive metal oxide such as ITO or IZO. The organic thin layer 100 is disposed on the first electrode 20. The organic thin layer 100 includes an emission layer 120, a first buffer layer 110, and a second buffer layer 130. At least one layer of the organic thin layer 100 includes the organic metallic complex compound according to one embodiment of the present invention. The first and second buffer layers 110 and 130 may include at least one selected from the group consisting of a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), and an electron injection layer (EIL), and may respectively further include an electron blocking layer or a hole blocking layer to improve light emitting characteristics of the emission layer 120.
The second electrode 30 is disposed on the second buffer layer 130. The second electrode 30 may be formed using lithium (Li)1 magnesium (Mg), calcium (Ca), aluminum (Al)1 AI:Li, Ba:Li, or Ca:Li having a small work function.
When the organic photoelectric device 1 is applied with an electric field, the holes and electrons are injected from the first electrode 20 and the second electrode 30, respectively. The injected holes and electrons are recombined on the emission layer of the organic thin layer 100 to provide light emitting excitons.
The provided light emitting excitons emit light by transiting to the ground state.
The following examples illustrate the present invention in more detail. However, it is understood that the present invention is not limited by these examples.
(Preparation of Organic Metallic Complex Compound)
(Example 1)
An organic metallic complex compound represented by the following Chemical Formula 14 was prepared based on the following Reaction Scheme 1.
[Reaction Scheme 1]
Chemical Formula 14
1g (0.9 mmol) of [lr(ppy)2CI]2, 1.64g (2.33 mmol) of a ligand a, and 1.3g of potassium carbonate were dissolved in anhydrous glycerol, and reacted while being heated and agitated in a nitrogen atmosphere at 2000C for 24 hours.
After the reaction, the reactant was poured into distilled water and solids were filtered off. Then, the organic metallic complex compound represented by Chemical Formula 14 was obtained by dissolving the filtered solids in chloroform and performing silica gel column chromatography. (Example 2)
An organic metallic complex compound represented by the following Chemical Formula 15 was prepared based on the following Reaction Scheme 2.
[Reaction Scheme 2]
The organic metallic complex compound represented by Chemical Formula 15 was prepared according to the same method as Example 1 , except that a ligand b was used.
(Example 3)
An organic metallic complex compound represented by the following Chemical Formula 16 was prepared based on the following Reaction Scheme 3.
[Reaction Scheme 3]
{litppy)jC%
The organic metallic complex compound represented by Chemical Formula 16 was prepared according to the same method as Example 1 , except that a ligand c was used.
(Preparation of Organic Photoelectric Device) A first electrode was formed of ITO in a size of 20mm x 20mm x 0.7mm on a glass substrate of 15Ω/cm2 and 1200A, which was produced by the Corning Company. The substrate with the first electrode formed therein went through
ultrasonic rinsing in isopropyl alcohol and deionized water for 5 minutes, respectively, and then went through UV ozone cleaning for 30 minutes.
The upper part of the first electrode was spin-coated with poly(ethylenedioxy)thiophene (PEDOT). An emission layer was formed on top of the PEDOT.
As for a host material for the emission layer, a 1 :1 mixture of polyvinylcarbazole (PVK) and 4,4'-N,N'-dicarbazolebiphenyl (CBP) was used.
The organic metallic complex compounds prepared according to Examples 1 to
3 were used in a content of 7% as dopants. The emission layer was spin-coated to a thickness of 500A.
A hole blocking layer was formed to a thickness of 50A on the emission layer through vacuum-deposition of bis(2-methyl-8-quinolinolate)-4-(phenylphenolate)aluminum (BAIq).
Subsequently, an electron transport layer (ETL) was formed at a thickness of 200.A on the hole blocking film through vacuum-deposition of tris(8-hydroxy-quinolate)aluminum (AIq3).
An organic photoelectric device was fabricated by sequentially vacuum-depositing LiF on an electron transport layer (ETL) to a thickness of 10A to form an electron injection layer (EIL), and vacuum-depositing Al as a second electrode.
(Measurement of Organic Photoelectric Device Performance)
To determine the characteristics of the organic photoelectric device fabricated above, initial driving voltage (which is also referred to as "turn-on voltage"), maximum luminance (cd/m2), driving voltage (V) at a luminance of
1000cd/m2, current efficiency (cd/A), and electric power efficiency (Im/W) were measured. The results are shown in the following Table 1.
Also, photoluminescence (PL) intensities of the organic metallic complex compounds prepared according to Examples 1 to 3 were measured, and the measurement results are shown in the following Table 1.
[Table 1]
Referring to Table 1 , although the organic photoelectric device was fabricated not through vacuum deposition but through spin-coating, which is a wet process, the organic metallic complex compound used in the organic thin layer showed high efficiency of about 26cd/A in case of Example 1 , and all had maximum luminance of over 10,000cd/m2.
Also, the driving voltage ranged from 4.2 V to 4.6 V, and the driving voltage at 1000cd/m2 ranged from 8.4 V to 10.2 V. The organic metallic complex compound according to an embodiment of
the present invention shows an excellent solubility characteristic in an organic solvent, such as toluene, chloroform, or chlorobenzene, due to decreased Van der Waals force among molecules, which is different from lr(ppy)3 or lr(mppy)3 that are known to be effective among green phosphorescent light emitting organic metallic complex compounds. This proves that the use of the organic metallic complex compound makes it possible to easily fabricate an organic photoelectric device even through a wet process.
When a bulky substituent is introduced into the organic metallic complex compound of the present invention, the organic metallic complex compound can improve solubility since molecules therein become apart from one another, and crystallinity decreases. The organic metallic complex compound suppresses intermolecular interaction and thus improves luminous efficiency and electrical characteristics.
Therefore the organic metallic complex compound according to one embodiment of the present invention may be usefully applied to a phosphorescent light emitting material of an organic photoelectric device.
While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims
1. An organic metallic complex compound for an organic photoelectric device represented by the following Chemical Formula 1 : [Chemical Formula 1]
wherein, in the above Chemical Formula 1 , n is an integer ranging from 1 to 3, a and b are independently integers of 0 or 1 , the cyclic compound group including Ci and Xi to X5, the cyclic compound group including C2, Yi, and X6 to X9, and the cyclic compound group including C3 and X10 to Xi4 are independently selected from the group consisting of an aliphatic cyclic compound, a hetero aliphatic cyclic compound, an aromatic cyclic compound, and a hetero aromatic cyclic compound,
M is a metal to form an octahedral complex, L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms, Ci to C3 are -C(Ri7)h-, where h is an integer of 0 or 1 ,
Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom,
Xi to Xi4 are independently C(ROi(R2)J, N(R3)k, Si(R4)0(R5)p, O, or S, where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
Ri to R5 and R17 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, Ri6, ORi6, N(Ri6)2, P(Rie)2, P(ORi6)2) POR16, PO2Ri6, PO3Ri6, SRi6, Si(Ri6)S, Si(CH3)2Ri6, Si(Ph)2Ri6, B(R16)2, B(ORi6)2, C(O)Ri6, C(O)ORi6, C(O)N(Ri6)2, CN, NO2, SORi6, SO2Ri6, and SO3R16,
Ri to R5 are present as independent substituents, or are fused together to form a cycle bound to the Xi to Xu, at least one of Ri to R5 is selected from the group consisting of a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, and a substituted or unsubstituted biarylphenyl,
Ri6 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and
Ri5 is selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene, wherein the term "substituted" refers to one substituted with at least a substituent selected from the group consisting of a halogen, a cyano, a hydroxy, an amino, a substituted or unsubstituted C6 to C30 aryl, and a substituted or unsubstituted C2 to C30 heteroaryl instead of hydrogen.
2. The organic metallic complex compound of claim 1 , wherein the Ri to R5 are independently selected from the group consisting of substituents represented by the following Chemical Formulae 2 to 6: [Chemical Formula 2]
[Chemical Formula 4]
R1
Ar-f ^Ar2
[Chemical Formula 5]
wherein, in the above Chemical Formulae 2 to 6,
X21 to X28, X31 to X38, and X51 to X66 are independently selected from the group consisting of CR18 and N,
R18 and R" are independently selected from the group consisting of hydrogen, a halogen, R161 OR16, N(R16)2, P(Riβ)2, P(ORi6)2, PORi6, PO2Ri6, PO3Ri6, SRi6, Si(Ri6)3, Si(CH3)2Rie, Si(Ph)2Ri6, B(R16)2, B(OR16)2, C(O)R16, C(O)ORi6, C(0)N(Riβ)2, CN, NO2, SOR16, SO2Ri6, and SO3Ri6, Ri6 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, R1 is selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene, and
Ar-i to Ar4 are selected from the group consisting of a substituted or unsubstituted C6 to C30 aryl and a substituted or unsubstituted C2 to C30 heteroaryl, wherein the term "substituted" refers to one substituted with at least a substituent selected from the group consisting of a halogen, a cyano, a hydroxy, an amino, a substituted or unsubstituted C6 to C30 aryl, and a substituted or unsubstituted C2 to C30 heteroaryl instead of hydrogen.
3. The organic metallic complex compound of claim 1 , wherein the organic metallic complex compound represented by the above Chemical Formula 1 is selected from the group consisting of the following Chemical Formulae 7 to 9:
[Chemical Formula 7]
[Chemical Formula 9]
M is a metal to form an octahedral complex,
L is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom, or a monovalent anionic didentate ligand of a monovalent anion bound to M through a coordinate covalent bond with two heteroatoms,
Ci to C3 are -C(Ri7)h-, where h is an integer of 0 or 1 ,
Yi is a monovalent anionic didentate ligand bound to M through a coordinate covalent bond with an sp2 carbon and a heteroatom,
Xi to X14 are independently C(Ri)i(R2)j, N(R3)k, Si(R4)o(R5)Pl O, or S, where i, j, k, o, and p are independently integers of 0 or 1 , and i+j and o+p are independently integers of 1 or 2,
Xi5 to X30 are independently selected from the group consisting of CRi8 and N,
Ri to R5, Ri7, Ri8, R", and R"" are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, Ri6, OR16, N R162, P R162, P OR162, POR16, PO2Ri6, PO3Ri6, SRi6, Si R163, Si CH32Ri6, Si (Ph)2Ri6, B Ri62, B ORi62, C (O)Ri6, C(O)OR16, C(O)N R162, CN, NO2, SO2, SOR16, SO2R16, and SO3R16,
R1 to R5 are present as independent substituents, or are fused together to form a cycle bound to the X1 to X14,
Ri6 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and R15, R1, and R1" are independently selected from the group consisting of a single bond, a substituted or unsubstituted C6 to C30 arylene, a substituted or unsubstituted C2 to C30 heteroarylene, and a substituted or unsubstituted C1 to C20 alkylene, wherein the term "substituted" refers to one substituted with at least a substituent selected from the group consisting of a halogen, a cyano, a hydroxy, an amino, a substituted or unsubstituted C6 to C30 aryl, and a substituted or unsubstituted C2 to C30 heteroaryl instead of hydrogen.
4. The organic metallic complex compound of claim 1 , wherein the cyclic compound group including Ci and Xi to X5, the cyclic compound group including C2, Yi, and X6 to Xg, and the cyclic compound group including C3 and
X-io to Xi4 are independently selected from the group consisting of an aromatic cyclic compound and a hetero aromatic cyclic compound.
5. The organic metallic complex compound of claim 1 , wherein the L is selected from the group consisting of ligands represented by the following Chemical Formulae 10 to 16: [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12]
[Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15]
[Chemical Formula 16]
Ri to R3 are independently selected from the group consisting of hydrogen, a halogen, a substituted or unsubstituted fluorene, a substituted or unsubstituted carbazole, a substituted or unsubstituted arylamine, a substituted or unsubstituted biarylphenyl, Ri6, ORi6, N(R16^, P(Rie)2, P(ORi6)2, PORi6,
PO2Ri6, PO3Ri6, SRi6, Si(Ri6)3, Si(CH3)2Ri6, Si(Ph)2Ri6, B(R16)2, B(ORi6)2, C(O)Ri6, C(O)OR16, C(O)N(Riβ)2, CN1 NO2, SOR16, SO2R16, and SO3R16,
R16 is selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl, a substituted or unsubstituted C2 to C30 alkenyl, a substituted or unsubstituted C2 to C30 alkynyl, a substituted or unsubstituted C1 to C30 heteroalkyl, a substituted or unsubstituted C3 to C40 aryl, and a substituted or unsubstituted C3 to C40 heteroaryl, and n-i is an integer ranging from 1 to 3, n2, fy, and n5 are integers ranging from 1 to 4, and n3 is an integer of 1 or 2, wherein the term "substituted" refers to one substituted with at least a substituent selected from the group consisting of a halogen, a cyano, a hydroxy, an amino, a substituted or unsubstituted C6 to C30 aryl, and a substituted or unsubstituted C2 to C30 heteroaryl instead of hydrogen.
6. The organic metallic complex compound of claim 1 , wherein M is selected from the group consisting of a Group 8 element and a Group 10 element of the periodic table.
7. The organic metallic complex compound of claim 1 , wherein M is selected from the group consisting of Ir, Pt, Rh, and Pd.
8. The organic metallic complex compound of claim 1 , wherein M is Ir.
9. An organic photoelectric device comprising an organic layer between a pair of electrodes, wherein the organic layer includes the organic metallic complex compound according to one of claims 1 to 8.
10. The organic photoelectric device of claim 9, wherein the organic thin layer is an emission layer.
11. The organic photoelectric device of claim 9, wherein the organic thin layer further comprises a layer selected from the group consisting of a hole injection layer (HIL), a hole transport layer (HTL), a hole blocking layer, and a combination thereof.
12. The organic photoelectric device of claim 9, wherein the organic thin layer further comprises a layer selected from the group consisting of an electron injection layer (EIL), an electron transport layer (ETL), an electron blocking layer, and a combination thereof.
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| US13/117,506 US20110291083A1 (en) | 2008-11-27 | 2011-05-27 | Organometallic complex compounds for photoelectric device and organic photoelectric device including the same |
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| JP2012222268A (en) * | 2011-04-13 | 2012-11-12 | Konica Minolta Holdings Inc | Organic electroluminescent element material, organic electroluminescent element, display device, and lighting device |
| WO2013045402A1 (en) * | 2011-09-28 | 2013-04-04 | Solvay Sa | Light emitting material |
| DE102013202923B4 (en) | 2012-02-24 | 2021-09-16 | Semiconductor Energy Laboratory Co., Ltd. | Phosphorescent organometallic iridium complex, light-emitting element, light-emitting device, electronic device and lighting device |
| WO2014011483A1 (en) * | 2012-07-09 | 2014-01-16 | Georgia Tech Research Corporation | Oxadiazole and triazole meta-linked n-phenyl carbazole ambipolar host materials |
| JP2020138934A (en) * | 2019-02-28 | 2020-09-03 | 住友化学株式会社 | Metal complex and composition containing the metal complex |
| CN113490673A (en) * | 2019-02-28 | 2021-10-08 | 住友化学株式会社 | Metal complex and composition comprising the same |
| JP7298187B2 (en) | 2019-02-28 | 2023-06-27 | 住友化学株式会社 | Metal complex and composition containing said metal complex |
| EP3971196A4 (en) * | 2019-05-15 | 2022-06-29 | Mitsubishi Chemical Corporation | Iridium complex compound, composition containing said compound and solvent, organic electroluminescent element containing said compound, display device and lighting device |
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| Publication number | Publication date |
|---|---|
| US20110291083A1 (en) | 2011-12-01 |
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