US20010037024A1 - Emitting materials used for organic EL based on tridentate ligands - Google Patents
Emitting materials used for organic EL based on tridentate ligands Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000003446 ligand Substances 0.000 title claims abstract description 26
- -1 cyano, amino Chemical group 0.000 claims abstract description 20
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims abstract description 15
- 229960003540 oxyquinoline Drugs 0.000 claims abstract description 15
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 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 claims abstract description 6
- 125000003368 amide group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000004404 heteroalkyl group Chemical group 0.000 claims abstract description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 125000004429 atom Chemical group 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract description 2
- 229910052738 indium Inorganic materials 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 47
- 238000005401 electroluminescence Methods 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 33
- 238000003786 synthesis reaction Methods 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 17
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 125000001624 naphthyl group Chemical group 0.000 description 15
- 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 12
- 238000007740 vapor deposition Methods 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 11
- 238000001819 mass spectrum Methods 0.000 description 11
- 239000010409 thin film Substances 0.000 description 11
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CHBGIQHEGBKNGA-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)iminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NC1=CC=CC=C1O CHBGIQHEGBKNGA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- CTQMJYWDVABFRZ-UHFFFAOYSA-N cloxiquine Chemical compound C1=CN=C2C(O)=CC=C(Cl)C2=C1 CTQMJYWDVABFRZ-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005092 sublimation method Methods 0.000 description 4
- JFEVWPNAOCPRHQ-UHFFFAOYSA-N chembl1316021 Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1O JFEVWPNAOCPRHQ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FHMMQQXRSYSWCM-UHFFFAOYSA-N 1-aminonaphthalen-2-ol Chemical compound C1=CC=C2C(N)=C(O)C=CC2=C1 FHMMQQXRSYSWCM-UHFFFAOYSA-N 0.000 description 2
- PEJOQASNBCUDMB-UHFFFAOYSA-N 2-aminonaphthalen-1-ol;hydrochloride Chemical compound [Cl-].C1=CC=CC2=C(O)C([NH3+])=CC=C21 PEJOQASNBCUDMB-UHFFFAOYSA-N 0.000 description 2
- ZHVPTERSBUMMHK-UHFFFAOYSA-N 3-aminonaphthalen-2-ol Chemical compound C1=CC=C2C=C(O)C(N)=CC2=C1 ZHVPTERSBUMMHK-UHFFFAOYSA-N 0.000 description 2
- FXKXCPJEZDDBHP-WWACPUNUSA-N C/C=N(/C)[Sn](OC)(OC)(OC)(OC)/N(C)=C\C.C/C=N(\C)C1(OC)(OC)N[IH]O1.C/N=N\C.COC1(C)(OC)N[IH]O1.II.II.II.II Chemical compound C/C=N(/C)[Sn](OC)(OC)(OC)(OC)/N(C)=C\C.C/C=N(\C)C1(OC)(OC)N[IH]O1.C/N=N\C.COC1(C)(OC)N[IH]O1.II.II.II.II FXKXCPJEZDDBHP-WWACPUNUSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RIUHJJQCONMSCU-VDAUHYBOSA-N C/C=N(/C)[Sn](OC)(OC)(OC)(OC)/N(C)=C\C.II.II Chemical compound C/C=N(/C)[Sn](OC)(OC)(OC)(OC)/N(C)=C\C.II.II RIUHJJQCONMSCU-VDAUHYBOSA-N 0.000 description 1
- TVRSDQGWEJXGSP-SZKNIZGXSA-N C/C=N(\C)C1(OC)(OC)N[IH]O1.II Chemical compound C/C=N(\C)C1(OC)(OC)N[IH]O1.II TVRSDQGWEJXGSP-SZKNIZGXSA-N 0.000 description 1
- BQHDYSNXOOJECG-LWFKIUJUSA-N C/N=N\C.COC1(C)(OC)N[IH]O1.II Chemical compound C/N=N\C.COC1(C)(OC)N[IH]O1.II BQHDYSNXOOJECG-LWFKIUJUSA-N 0.000 description 1
- XFVWYBDWVVCUIP-UHFFFAOYSA-N C1=CC2=C(C=C1)C1=C(C=C2)OC23(OC4=CC=CC5=C4/N2=C\C=C/5)OC2=C(C=CC=C2)/N3=C/1.C1=CC2=C(C=C1)OC13(OC4=CC=CC5=C4/N1=C\C=C/5)OC1=C(C=CC=C1)/N3=C/2.C1=CC=C2C(=C1)OC1C3=C(C=CC=C3)OC34(OC5=C(C=CC=C5)/C=N\3C3=C(C=CC=C3)O4)[N@@]21.ClC1=CC=C2OC34(OC5=C(C=CC=C5)/C=N\3C3=C(C=CC=C3)O4)/N3=C/C=C\C1=C23 Chemical compound C1=CC2=C(C=C1)C1=C(C=C2)OC23(OC4=CC=CC5=C4/N2=C\C=C/5)OC2=C(C=CC=C2)/N3=C/1.C1=CC2=C(C=C1)OC13(OC4=CC=CC5=C4/N1=C\C=C/5)OC1=C(C=CC=C1)/N3=C/2.C1=CC=C2C(=C1)OC1C3=C(C=CC=C3)OC34(OC5=C(C=CC=C5)/C=N\3C3=C(C=CC=C3)O4)[N@@]21.ClC1=CC=C2OC34(OC5=C(C=CC=C5)/C=N\3C3=C(C=CC=C3)O4)/N3=C/C=C\C1=C23 XFVWYBDWVVCUIP-UHFFFAOYSA-N 0.000 description 1
- LWXZQTKOJYVEMM-JYBDOIPRSA-A C1=CC=C2C(=C1)C=CC1=C2/C=N2C3=C/C=C/C=C3\O[Sn]/234(OC2=CC=CC=C2N3=CC2=C(C=CC3=C2C=CC=C3)O4)O1.C1=CC=C2C(=C1)O[Sn]134(OC5=C(C=C6C=CC=CC6=C5)C=N21)OC1=C(C=C2C=CC=CC2=C1)/C=N3/C1=C/C=C\C=C\1O4.C1=CC=C2C(=C1)O[Sn]134(OC5=C(C=CC6=C5C=CC=C6)C=N21)OC1=C(C=CC2=C1C=CC=C2)/C=N3/C1=C/C=C\C=C\1O4.C1=CC=C2C(=C1)O[Sn]134(OC5=C(C=CC=C5)C=N21)OC1=C(C=CC=C1)/C=N3/C1=C/C=C\C=C\1O4 Chemical compound C1=CC=C2C(=C1)C=CC1=C2/C=N2C3=C/C=C/C=C3\O[Sn]/234(OC2=CC=CC=C2N3=CC2=C(C=CC3=C2C=CC=C3)O4)O1.C1=CC=C2C(=C1)O[Sn]134(OC5=C(C=C6C=CC=CC6=C5)C=N21)OC1=C(C=C2C=CC=CC2=C1)/C=N3/C1=C/C=C\C=C\1O4.C1=CC=C2C(=C1)O[Sn]134(OC5=C(C=CC6=C5C=CC=C6)C=N21)OC1=C(C=CC2=C1C=CC=C2)/C=N3/C1=C/C=C\C=C\1O4.C1=CC=C2C(=C1)O[Sn]134(OC5=C(C=CC=C5)C=N21)OC1=C(C=CC=C1)/C=N3/C1=C/C=C\C=C\1O4 LWXZQTKOJYVEMM-JYBDOIPRSA-A 0.000 description 1
- FWSCPHZAWLIIBK-SMOKJAFBSA-N CC12(OC3=C(C=CC=C3)/N=N/C3=C(C=CC=C3)O1)OC1=C(C=CC=C1)C1=N2C2=CC=CC=C2O1.CC12(OC3=CC=C(Cl)C4=C3/N1=C\C=C/4)OC1=C(C=CC=C1)/N=N/C1=C(C=CC=C1)O2.CC12(OC3=CC=CC4=C3/N1=C\C=C/4)OC1=C(C=CC=C1)/N=N/C1=C(C=CC3=C1C=CC=C3)O2.CC12(OC3=CC=CC4=C3/N1=C\C=C/4)OC1=C(C=CC=C1)/N=N/C1=C(C=CC=C1)O2 Chemical compound CC12(OC3=C(C=CC=C3)/N=N/C3=C(C=CC=C3)O1)OC1=C(C=CC=C1)C1=N2C2=CC=CC=C2O1.CC12(OC3=CC=C(Cl)C4=C3/N1=C\C=C/4)OC1=C(C=CC=C1)/N=N/C1=C(C=CC=C1)O2.CC12(OC3=CC=CC4=C3/N1=C\C=C/4)OC1=C(C=CC=C1)/N=N/C1=C(C=CC3=C1C=CC=C3)O2.CC12(OC3=CC=CC4=C3/N1=C\C=C/4)OC1=C(C=CC=C1)/N=N/C1=C(C=CC=C1)O2 FWSCPHZAWLIIBK-SMOKJAFBSA-N 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Definitions
- This invention relates to novel emitting materials for organic electroluminescence (EL) devices.
- organic EL organic electroluminescence
- the early efficient devices have been reported in C. W. Tang, S. A. Van Slyke, Appl. Phys. Lett. 1987, 51-913 ⁇ 915 and U.S. Pat. No. 4,720,432 issued Jan. 19, 1988.
- Great improvements have been made since 1987 and many new materials have been synthesized and used in organic EL devices.
- the primary object of this invention is provide to a series of stable complexes based on many kinds of tridentate ligands. These materials exhibited strong fluorescence and excellent amorphous properties in solid state. Both of these characters are conducive to forming high quality amorphous films.
- Another object of the invention is provide to the use of such novel complexes as thermal stable emitting materials for organic light-emitting diodes (OLEDs).
- OLEDs organic light-emitting diodes
- This invention disclosed here a series of stable complexes which have a tridentate ligand. Almost all of these complexes have the high Tg more than 200° C.
- the advantage of these materials lies in their excellent thermal stability and good performance to form amorphous films.
- the materials in this invention have made some progress in improving the compatibility with other layers materials. These materials have some unique characteristics that will be conducive to forming high quality amorphous films.
- Such novel complexes can be used as a thermal stable emitting material for OLEDs.
- a series of emitting colors have been obtained from these materials including green, yellow, and red, some of which are remain rare now. And the color position in the color coordinates system shows strong potential as a red light-emitting material for organic electroluminescence.
- These materials can be used as emitting materials or electronic transport materials in organic EL devices.
- FIG. 1 is the NMR-H′ spectrum of Complex 1.
- FIG. 2 is the mass spectrum of Complex 1.
- FIG. 3 is the high-resolution mass spectrum of Complex 1.
- FIG. 4 is the computer search result of the high-resolution mass spectrum of Complex 1.
- FIG. 5 is the high-resolution mass spectrum of Complex 12.
- FIG. 6 is the computer search result of the high-resolution mass spectrum of Complex 12.
- FIG. 7 is the color position in the color coordinates system (CIE 1931) for the device 3 comprising Complex 12, with the following layer structure: ITO/TPD/Complex 12 (100:1 ⁇ 15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1).
- FIG. 8 is the EL spectra for the device 1 comprising Complex 23, with the following layer structure: ITO/TPD (60 nm)/Complex 23/MgAg (10:1)
- a series of emitting materials used for organic EL based oil tridentate ligands are characterized as Formula 1, Formula 2 and Formula 3.
- I is a bidentate ligand such as 8-hydroxyquinoline and 2-(o-hydroxyphenyl)-benzoxazole
- II, III are unsubstituted or substituted aryl groups.
- the substituted groups can have 1-8 carbon atoms, halogen, cyano, amino, amido, sulfonyl, carbonyl, aryl, or heteroalkyl groups.
- the ligand including II and III is a tridentate ligand with three chelate atoms: two oxygen atoms and one nitrogen atom.
- the central metal atoms can be trivalent or tetravalent atoms such as Al, In, Ga, Tl, and Sn.
- These emitting materials should possess good thermal stability and high purity.
- the glass transition temperature (Tg) is a key parameter to determine the stability of the amorphous materials.
- the high Tg could minimize the probability of the crystallization in amorphous thin films, especially under the condition of a high temperature.
- the Tg of tris(8-hydroxyquinoline) aluminum (Alq3) is about 175° C., far below its decomposing temperature. Almost all of these complexes according to the invention have the high Tg more than 200° C. Meanwhile, these materials can be used as emitting materials or electronic transport materials in organic EL devices.
- the first step is the synthesis of the tridentate ligands.
- the ligands described in Formula 1 and Formula 3 are shiff bases, which can be synthesized by conventional shiff base synthesis methods comprising the steps: heating the mixture of o-hydroxy-aryl aldehyde and o-hydroxy-aryl alcohol and recrystallization in an organic solvent.
- the ligands described in Formula 2 can be synthesized by the method of Willstatter (Anal. Chem., 35,1144).
- the second step includes a chemical reaction in an organic solvent controlled by organic bases.
- Inorganic aluminum salts or organic aluminum compounds in solvent are added with the solution of ligands.
- the product was collected by filtration and washed with solvents.
- the compounds were further purified by the train sublimation method.
- the EL devices are fabricated by conventional vacuum vapor deposition method under a vacuum condition or spin coating method at room temperature.
- said complexes can be used in OLEDs serving as emitting materials or electron transport materials.
- OLEDs serving as emitting materials or electron transport materials.
- they are heated by conventional vacuum vapor deposition method; when used as dyes of these layers in the EL devices, they also can be treated with spin coating method.
- the OLEDs are fabricated on the ITO coated glasses after carefully cleaning.
- the material is vaporized to form a thin layer after a thin layer of hole transport material was prepared on a glass plate.
- the electron transport layer is optional for OLEDs.
- a thin film of metal that is used as cathode is formed by conventional vacuum vapor deposition method.
- the advantage of these materials lies in their excellent thermal stability and good performance to form amorphous films.
- Some incompatibilities with the hole transport materials also exist in many emitting complexes that would lead to phase separation.
- the materials in this invention have made some progress in improving the compatibilities with other layers materials. These materials have some unique characteristics that will be conducive to forming high quality amorphous films.
- Such novel complexes can be used as a thermal stable emitting material for OLEDs.
- a series of emitting colors have been obtained from these materials including green, yellow, and red, some of which are remain rare now.
- the color position in the color coordinates system shows strong potential as a red light-emitting material for organic electroluminescence.
- the introductions of tridentate ligands in the complex structure open a new route for exploring new materials for organic EL.
- example 1 ⁇ example 11 are directed to the preparation and use of Complex 1 ⁇ Complex 11.
- (device 1) The EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10 ⁇ 3 Pa vacuum at room temperature.
- the methods can be found in the following references: C. W. Tang and S. A. Vanslyke: Appl. Phys. Lett. 51 (1987) 913; Zilan Shen, Paul E. Burrows, Vladimir Bulovic, Stephen R. Forrest and Mark E. Thompson: Science 276(1997) 2009; Philip S. Bryan, Frank V. Lovecchio, Steven A. Vanslyke, Rochester: U.S. Pat. No. 5,141,671 (1992).
- N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine was used as the hole transport layer material.
- the following layer structures of were prepared: indium-tin-oxide (ITO)/TPD (60 nm)/Complex 1 (40 nm)/MgAg(10:1).
- ITO indium-tin-oxide
- TPD TPD
- Complex 1 40 nm
- MgAg(10:1 MgAg(10:1
- the maximum brightness of the device was up to 2000 cd/m 2 .
- the EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.5 lm/W, which was shown in table 5.
- the EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material.
- TPD N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine
- the following layer structure of devices was prepared: ITO/TPD (60 nm)/Complex 1 (40 nm)/Alq3 (20 nm)/MgAg (10:1).
- the maximum brightness of the device was up to 3000 cd/m 2 .
- the EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.7 lm/W, which was shown in table 5.
- the EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material.
- TPD N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine
- the following layer structures of was prepared: ITO/TPD; Complex 1 (100:1 ⁇ 15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1).
- the maximum brightness of the device was up to 2500 cd/m 2 .
- the EL emission was at 535 ⁇ 577 nm (depending on the concentration of Complex 1 in the thin film) and the maximum luminous efficiencies up to 1.8 lm/W, which was shown in table 5.
- Example 12 are directed to the preparation and use of Complex 12 ⁇ Complex 22, in which L1 ⁇ L7 represent the tridentate ligands listed in table 2.
- the product was collected by filtration and washed with ethanol rapidly, then dried under an infrared lamp. The obtained product power showed strong red fluorescence under an ultraviolet lamp.
- the materials were further purified by an improved train sublimation method.
- the L1 ligand was obtained by the typical synthesis method of azobenzene.
- the molecular structure of Complex 12 was supported by high-resolution mass spectrum (MS) shown in FIG. 5 and element analysis. High-resolution MS found: 383.0845240. Calc. for C21H14O3N3Al: 383.0845062 (shown in FIG. 6); Element analysis found: C, 65.9; H, 3.89; N, 10.68. Calc. For Complex 12: C, 65.80; H, 3.66; N, 10.97.
- (device 1) The EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD (60 nm)/Complex 12(40 nm)/MgAg(10:1). The maximum brightness of the device was up to 120 cd/m 2 and the EL emission was at around 640 nm, which was shown in table 8.
- TPD N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine
- the EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material.
- TPD N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine
- the following layer structures of was prepared: ITO/TPD (60 nm)/Complex 12(40 nm)/Alq3 (20 nm)/MgAg(10:1).
- the maximum brightness of the device was up to 150 cd/m 2 and the EL emission was at around 635 nm, which was shown in table 8.
- the EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material.
- TPD N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine
- the following layer structures of was prepared: ITO/TPD; Complex 12 (100:1 ⁇ 15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1).
- the maximum brightness of the device was up to 150 cd/m 2 and the EL emission was at 625 ⁇ 645 nm (depending on the concentration of Complex 1 in the thin film), which was shown in table 8.
- Example 23 ⁇ example 29 are directed to Complex 23 ⁇ Complex 29. All the tridentate ligands are the same as the tridentate ligands used in the first group complexes. So the synthesis of these ligands are referred to the example 1 ⁇ example 11.
- the EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(n-methylphenyl)benzidine (TPD) was used as the hole transport layer material.
- TPD N,N′-diphenyl-N,N′-di(n-methylphenyl)benzidine
- the following layer structures of was prepared: ITO/TPD (60 nm)/Complex 23(40 nm)/MgAg(10:1).
- the maximum brightness of the device was up to 2000 cd/m 2 .
- the EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.5 lm/W, which was shown in FIG. 8 and in table 10.
- the EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material.
- TPD N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine
- the following layer structures of was prepared: ITO/TPD (60 nm)/Complex 23 (40 nm)/Alq3 (20 nm)/MgAg (10:1).
- the maximum brightness of the device was up to 3000 cd/m2.
- the EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.7 lm/W, which was shown in table 10.
- the EL device was fabricated by conventional vacuum vapor deposition method under a 2 ⁇ 10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material.
- TPD N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine
- the following layer structures of was prepared: ITO/TPD: Complex 23 (100:1 ⁇ 15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1).
- the maximum brightness of the device was up to 2500 cd/m 2 .
- the EL emission was at 535 ⁇ 577 nm (depending on the concentration of Complex 1 in the thin film) and the maximum luminous efficiencies up to 1.8 lm/W, which was shown in table 10.
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Abstract
A series of emitting materials used for organic EL based on tridentate ligands are characterized as Formula 1, Formula 2 and Formula 3. where: I is a bidentate ligand such as 8-hydroxyquinoline and 2-(o-hydroxyphenyl)-benzoxazole, II, III are unsubstituted or substituted aryl groups. The substituted groups can have 1-8 carbon atoms, halogen, cyano, amino, amido, sulfonyl, carbonyl, aryl, or heteroalkyl groups. The ligand including II and III is a tridentate ligand with three chelate atoms: two oxygen atoms and one nitrogen atom. The central metal atoms can be trivalent or tetravalent atoms such as Al, In, Ga, Tl, and Sn. These materials can be used as emitting materials or electronic transport materials in organic EL devices.
Description
- This invention relates to novel emitting materials for organic electroluminescence (EL) devices. As a promising technology for flat panel display, organic EL has attracted more and more attentions. The early efficient devices have been reported in C. W. Tang, S. A. Van Slyke, Appl. Phys. Lett. 1987, 51-913˜915 and U.S. Pat. No. 4,720,432 issued Jan. 19, 1988. Great improvements have been made since 1987 and many new materials have been synthesized and used in organic EL devices. There are diverse emitting materials used in fabrication of organic EL devices with blue, green, yellow, and red emission.
- The primary object of this invention is provide to a series of stable complexes based on many kinds of tridentate ligands. These materials exhibited strong fluorescence and excellent amorphous properties in solid state. Both of these characters are conducive to forming high quality amorphous films.
- Another object of the invention is provide to the use of such novel complexes as thermal stable emitting materials for organic light-emitting diodes (OLEDs).
- This invention disclosed here a series of stable complexes which have a tridentate ligand. Almost all of these complexes have the high Tg more than 200° C. The advantage of these materials lies in their excellent thermal stability and good performance to form amorphous films. The materials in this invention have made some progress in improving the compatibility with other layers materials. These materials have some unique characteristics that will be conducive to forming high quality amorphous films. Such novel complexes can be used as a thermal stable emitting material for OLEDs. In addition, a series of emitting colors have been obtained from these materials including green, yellow, and red, some of which are remain rare now. And the color position in the color coordinates system shows strong potential as a red light-emitting material for organic electroluminescence. These materials can be used as emitting materials or electronic transport materials in organic EL devices.
- FIG. 1 is the NMR-H′ spectrum of
Complex 1. - FIG. 2 is the mass spectrum of
Complex 1. - FIG. 3 is the high-resolution mass spectrum of
Complex 1. - FIG. 4 is the computer search result of the high-resolution mass spectrum of
Complex 1. - FIG. 5 is the high-resolution mass spectrum of
Complex 12. - FIG. 6 is the computer search result of the high-resolution mass spectrum of
Complex 12. - FIG. 7 is the color position in the color coordinates system (CIE 1931) for the
device 3 comprisingComplex 12, with the following layer structure: ITO/TPD/Complex 12 (100:1˜15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1). - FIG. 8 is the EL spectra for the
device 1 comprisingComplex 23, with the following layer structure: ITO/TPD (60 nm)/Complex 23/MgAg (10:1) - In accordance with the present invention, a series of emitting materials used for organic EL based oil tridentate ligands are characterized as Formula 1, Formula 2 and Formula 3. where: I is a bidentate ligand such as 8-hydroxyquinoline and 2-(o-hydroxyphenyl)-benzoxazole, II, III are unsubstituted or substituted aryl groups. The substituted groups can have 1-8 carbon atoms, halogen, cyano, amino, amido, sulfonyl, carbonyl, aryl, or heteroalkyl groups. The ligand including II and III is a tridentate ligand with three chelate atoms: two oxygen atoms and one nitrogen atom. The central metal atoms can be trivalent or tetravalent atoms such as Al, In, Ga, Tl, and Sn.
- These emitting materials should possess good thermal stability and high purity. The glass transition temperature (Tg) is a key parameter to determine the stability of the amorphous materials. The high Tg could minimize the probability of the crystallization in amorphous thin films, especially under the condition of a high temperature. The Tg of tris(8-hydroxyquinoline) aluminum (Alq3) is about 175° C., far below its decomposing temperature. Almost all of these complexes according to the invention have the high Tg more than 200° C. Meanwhile, these materials can be used as emitting materials or electronic transport materials in organic EL devices.
- Typical complexes of the
Formula 1 were shown in below table 1.TABLE 1 I 8-hydroxy- 5-Cl-8-hydroxy- 2-(o-hydroxyphenyl)- II, III quinoline quinoline benzoxazole II = phenyl Complex 1 Complex 2Complex 3III = phenyl II = 1,2 Complex 4Complex 5substituted naphthyl III = phenyl II = 2,3 Complex 6substituted naphthyl III = phenyl II = 3,4 Complex 7 substituted naphthyl III = phenyl II = phenyl Complex 8 Complex 9 III = 1,2 substituted naphthyl II = phenyl Complex 10 III = 2,3 substituted naphthyl II = phenyl Complex 11 III = 3,4 substituted naphthyl -
- Typical complexes of the
Formula 2 were shown in below table 2.TABLE 2 I 2-(o-hydroxy- 8-hydroxy- 5-Cl-8-hydroxy- phenyl)- II, III quinoline quinoline benzoxazole L1 II = phenyl Complex 12 Complex 13 Complex 14III = phenyl L2 II = 1,2 Complex 15Complex 16substituted naphthyl III = phenyl L3 II = 2,3 Complex 17substituted naphthyl III = phenyl L4 II = 3,4 Complex 18substituted naphthyl III = phenyl L5 II = phenyl Complex 19 Complex 20III = 1,2 substituted naphthyl L6 II = phenyl Complex 21 III = 2,3 substituted naphthyl L7 II = phenyl Complex 22 III = 3,4 substituted naphthyl -
- Typical complexes of the Formula 3 were shown in below table 3.
TABLE 3 II 1,2 2,3 3,4 substituted substituted substituted III phenyl naphthyl naphthyl naphthyl phenyl Complex 23 Complex 27Complex 28 Complex 29 1,2 substituted Complex 24naphthyl 2,3 substituted Complex 25naphthyl 3,4 substituted Complex 26 naphthyl -
- All the above these compounds can be prepared by the following two steps: the first step is the synthesis of the tridentate ligands, the second step is the synthesis of the objective complexes.
- The first step is the synthesis of the tridentate ligands. The ligands described in Formula 1 and
Formula 3 are shiff bases, which can be synthesized by conventional shiff base synthesis methods comprising the steps: heating the mixture of o-hydroxy-aryl aldehyde and o-hydroxy-aryl alcohol and recrystallization in an organic solvent. The ligands described in Formula 2 can be synthesized by the method of Willstatter (Anal. Chem., 35,1144). - The second step includes a chemical reaction in an organic solvent controlled by organic bases. Inorganic aluminum salts or organic aluminum compounds in solvent are added with the solution of ligands. The product was collected by filtration and washed with solvents. The compounds were further purified by the train sublimation method.
- The EL devices are fabricated by conventional vacuum vapor deposition method under a vacuum condition or spin coating method at room temperature. As described above, said complexes can be used in OLEDs serving as emitting materials or electron transport materials. When used as electron transport and emitting layers in the EL devices, they are heated by conventional vacuum vapor deposition method; when used as dyes of these layers in the EL devices, they also can be treated with spin coating method.
- The OLEDs are fabricated on the ITO coated glasses after carefully cleaning. The material is vaporized to form a thin layer after a thin layer of hole transport material was prepared on a glass plate. The electron transport layer is optional for OLEDs. As the last step, a thin film of metal that is used as cathode is formed by conventional vacuum vapor deposition method.
- The advantage of these materials lies in their excellent thermal stability and good performance to form amorphous films. Some incompatibilities with the hole transport materials also exist in many emitting complexes that would lead to phase separation. The materials in this invention have made some progress in improving the compatibilities with other layers materials. These materials have some unique characteristics that will be conducive to forming high quality amorphous films. Such novel complexes can be used as a thermal stable emitting material for OLEDs. In addition, a series of emitting colors have been obtained from these materials including green, yellow, and red, some of which are remain rare now. And the color position in the color coordinates system shows strong potential as a red light-emitting material for organic electroluminescence. The introductions of tridentate ligands in the complex structure open a new route for exploring new materials for organic EL.
- The following non-limiting example further serves to illustrate the invention.
- As described below, the example 1˜example 11 are directed to the preparation and use of
Complex 1˜Complex 11. - Synthesis of the Complex 1:
-
Complex 1 was synthesized through a reaction in the ethanol solution of 8-hydroxyquinoline, salicylidene-o-aminophenol and AlCl3 as follows. First, a solution of 8-hydroxyquinioline (0.05M) and piperidine (0.05M) in 100 ml ethanol was added to a solution of AlCl3.6H2O (0.5M) in 10 ml ethanol very slowly with an intensive stirring. Then, a solution of salicylidene-o-aminophenol (0.01M) and piperidine (0.02M) in 500 ml ethanol was introduced slowly. The mixture was stirred for about 1 hour and cooled to room temperature and kept in dark for about 10 hours. A yellow precipitate was formed when equivalent amount water was poured into the solution. The product was collected by filtration and washed with ethanol rapidly, then dried under an infrared lamp. The obtained product power showed strong yellow fluorescence under an ultraviolet lamp. The materials were further purified by an improved train sublimation method. The salicylidene-o-aminophenol ligand was obtained by heating the mixture of 2-aminophenol and 2-hydroxy-salicylic aldehyde in ethanol solution and the following recrystallization. The molecular structure ofComplex 1 was supported by high-resolution mass spectrum (MS) shown in FIG. 3, nuclear magnetic resonance (NMR) shown in FIG. 1 and element analysis. High-resolution MS found: 382.08793. Calc. for C22H15O3N2Al: 382.08981 (shown in FIG. 4); Element analysis found: C, 68.85; H, 3.83; N, 7.17. Calc. For Complex 1: C, 69.11; H, 3.93; N, 7.33. - Fabrication of four EL devices with complex 1:
- 1. (device 1) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10−3 Pa vacuum at room temperature. For example, the methods can be found in the following references: C. W. Tang and S. A. Vanslyke: Appl. Phys. Lett. 51 (1987) 913; Zilan Shen, Paul E. Burrows, Vladimir Bulovic, Stephen R. Forrest and Mark E. Thompson: Science 276(1997) 2009; Philip S. Bryan, Frank V. Lovecchio, Steven A. Vanslyke, Rochester: U.S. Pat. No. 5,141,671 (1992). N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of were prepared: indium-tin-oxide (ITO)/TPD (60 nm)/Complex 1 (40 nm)/MgAg(10:1). The maximum brightness of the device was up to 2000 cd/m2. The EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.5 lm/W, which was shown in table 5.
- 2. (device 2) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structure of devices was prepared: ITO/TPD (60 nm)/Complex 1 (40 nm)/Alq3 (20 nm)/MgAg (10:1). The maximum brightness of the device was up to 3000 cd/m2. The EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.7 lm/W, which was shown in table 5.
- 3. (device 3) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD; Complex 1 (100:1˜15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1). The maximum brightness of the device was up to 2500 cd/m2. The EL emission was at 535˜577 nm (depending on the concentration of
Complex 1 in the thin film) and the maximum luminous efficiencies up to 1.8 lm/W, which was shown in table 5. - 4. (device 4) Both
Complex 1 and some polymer (such as poly(N-vinylcarbazole) (PVK)) were dissolved in some organic solvent (such as C2H4Cl2). The thin film of mixture ofComplex 1 and polymer was prepared by spin coating method. The following layer structures of was prepared: ITO/PVK: Complex 1 (100:1˜15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1). The maximum brightness of the device was up to 1800 cd/m2. The EL emission was at 505˜573 nm (depending on the concentration ofComplex 1 in the thin film) and the maximum luminous efficiencies up to 1.8 lm/W, which was shown in table 5. - According to the synthesis procedures of
Complex 1,Complex 2 was prepared by replacing 8-hydroxyquinoline with 5-Cl-8-hydroxyquinoline. The data for identifying this complex was shown in the following table 4. - The four kinds of devices were prepared similar to the processes of
Complex 1. The performances of these devices were shown in the following table 5. - According to the synthesis procedures of
Complex 1,Complex 3 was prepared by replacing 8-hydroxyquinoline with 2-(o-hydroxyphenyl)-benzoxazole. The data for identifying this complex was shown in the following table 4. - The four kinds of devices were prepared similar to the processes of
Complex 1. The performances of these devices were shown in the following table 5. - According to the synthesis procedures of
Complex 1,Complex 4 was prepared by replacing 2-hydroxy-salicylic aldehyde with 2-hydroxy-naphthyl aldehyde. The data for identifying this complex was shown in the following table 4. - According to the synthesis procedures of
Complex 4,Complex 5 was prepared by replacing 8-hydroxyquinoline with 5-Cl-8-hydroxyquinoline. The data for identifying this complex was shown in the following table 4. - According to tie synthesis procedures of
Complex 4,Complex 6 was prepared by replacing 2-hydroxy-naphthyl aldehyde with 3-hydroxy-2-naphthyl aldehyde. The data for identifying this complex was shown in the following table 4. - According to the synthesis procedures of
Complex 4, Complex 7 was prepared by replacing 2-hydroxy-naphthyl aldehyde with 1-hydroxy-2-naphthyl aldehyde. The data for identifying this complex was shown in the following table 4. - According to the synthesis procedures of
Complex 4,Complex 8 was prepared by replacing 2-aminophenol with 2-hydroxy-1-naphthyl amine. The data for identifying this complex was shown in the following table 4. - According to the synthesis procedures of
Complex 8, Complex 9 was prepared by replacing 8-hydroxyquinoline with 5-Cl-8-hydroxyquinoline. The data for identifying this complex was shown in the following table 4. - According to the synthesis procedures of
Complex 4,Complex 10 was prepared by replacing 2-aminophenol with 3-hydroxy-2-naphthyl amine. The data for identifying this complex was shown in the following table 4. - According to the synthesis procedures of
Complex 4, Complex 11 was prepared by replacing 2-aminophenol with 1-hydroxy-2-naphthyl amine. The data for identifying this complex was shown in the following table 4.TABLE 4 Production Cal. for Complex yield Structural Formula Element analysis No. % C % H % N % C % H % N % 1 75 69.11 3.93 7.33 68.8 3.8 7.17 2 68 63.39 3.36 6.72 62.9 3.27 6.82 3 70 69.64 3.80 6.25 70.2 3.79 6.20 4 74 72.22 3.94 6.48 73.1 3.82 6.56 5 64 66.88 3.43 6.00 67.7 3.29 6.18 6 72 72.22 3.94 6.48 72.7 3.84 6.53 7 63 72.22 3.94 6.48 73.1 3.86 6.51 8 74 72.22 3.94 6.48 73.4 3.83 6.54 9 69 66.88 3.43 6.00 67.1 3.40 6.11 10 66 72.22 3.94 6.48 72.9 3.89 6.53 11 61 72.22 3.94 6.48 73.2 3.88 6.50 -
TABLE 5 Device No. Complex 1Complex 2Complex 31 Brightness/cd/m2 2000 800 600 (12V) The maximum 573 568 563 wavelength/ nm 2 Brightness/cd/m2 3000 1000 900 (12V) The maximum 573 567 562 wavelength/ nm 3 Brightness/cd/m2 2500 >1500 >1100 (12V) The maximum 535˜577 537˜569 538˜566 wavelength/ nm 4 Brightness/cd/ m 21800 >1200 >860 (12V) The maximum 505˜573 531˜569 537˜564 wavelength/nm - The following example 12˜example 22 are directed to the preparation and use of
Complex 12˜Complex 22, in which L1˜L7 represent the tridentate ligands listed in table 2. - Synthesis of the Complex 12:
-
Complex 12 was synthesized through a reaction in the ethanol solution of 8-hydroxyquinoline, o,o′-dihydroxyazobenzene (L1) and AlCl3. First, a solution of 8-hydroxyquinoline (0.05M) and piperidine (0.05M) in 100 ml ethanol was added to a solution of AlCl3.6H2O (0.5M) in 10 ml ethanol very slowly with an intensive stirring. Then, a solution of L1 (0.01M) and piperidine (0.02M) in 500 ml ethanol was introduced slowly. The mixture was stirred for about 1 hour and cooled to room temperature and kept in dark for about 10 hours. A scarlet precipitate was formed when equivalent amount water was poured into the solution. The product was collected by filtration and washed with ethanol rapidly, then dried under an infrared lamp. The obtained product power showed strong red fluorescence under an ultraviolet lamp. The materials were further purified by an improved train sublimation method. The L1 ligand was obtained by the typical synthesis method of azobenzene. The molecular structure ofComplex 12 was supported by high-resolution mass spectrum (MS) shown in FIG. 5 and element analysis. High-resolution MS found: 383.0845240. Calc. for C21H14O3N3Al: 383.0845062 (shown in FIG. 6); Element analysis found: C, 65.9; H, 3.89; N, 10.68. Calc. For Complex 12: C, 65.80; H, 3.66; N, 10.97. - Fabrication of four EL devices with complex 12:
- 1. (device 1) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD (60 nm)/Complex 12(40 nm)/MgAg(10:1). The maximum brightness of the device was up to 120 cd/m2 and the EL emission was at around 640 nm, which was shown in table 8.
- 2. (device 2) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD (60 nm)/Complex 12(40 nm)/Alq3 (20 nm)/MgAg(10:1). The maximum brightness of the device was up to 150 cd/m2 and the EL emission was at around 635 nm, which was shown in table 8.
- 3. (device 3) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD; Complex 12 (100:1˜15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1). The maximum brightness of the device was up to 150 cd/m2 and the EL emission was at 625˜645 nm (depending on the concentration of
Complex 1 in the thin film), which was shown in table 8. - 4. (device 4) Both
Complex 1 and some polymer (such as PVK) were dissolved in some organic solvent (such as C2H4Cl2). The thin film of mixture ofComplex 1 and polymer was prepared by spin coating method. The following layer structures of was prepared: ITO/PVK: Complex 12 (100:1˜15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1). The maximum brightness of the device was up to 130 cd/m2 and the EL emission was at 605˜645 nm (depending on the concentration ofComplex 1 in the thin film), which was shown in table 8. - According to the synthesis procedures of
Complex 12, Complex 13 was prepared by replacing 8-hydroxyquinoline with 5-Cl-8-hydroxyquinoline. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 12,Complex 14 was prepared by replacing 8-hydroxyquinoline with 2-(o-hydroxyphenyl)-benzoxazole. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 12,Complex 15 was prepared by replacing L1 with L2. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 15,Complex 16 was prepared by replacing 8-hydroxyquinoline with 5-Cl-8-hydroxyquinoline. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 15,Complex 17 was prepared by replacing L1 with L3. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 15,Complex 18 was prepared by replacing L1 with L4. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 15,Complex 19 was prepared by replacing L1 with L5. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 19,Complex 20 was prepared by replacing 8-hydroxyquinoline with 5-Cl-8-hydroxyquinioline. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 15,Complex 21 was prepared by replacing L1 with L6. The data for identifying this complex was shown in the following table 7. - According to the synthesis procedures of
Complex 15,Complex 22 was prepared by replacing L1 with L7. The data for identifying this complex was shown in the following table 7.TABLE 7 Production Cal. for Complex yield Structural Formula Element analysis No. % C % H % N % C % H % N % 12 78 65.80 3.66 10.97 65.9 3.89 10.68 13 66 60.36 3.11 10.06 60.4 3.32 10.22 14 65 66.82 9.35 6.25 66.6 3.80 9.31 15 69 69.28 3.70 9.70 68.9 3.88 9.86 16 67 64.17 3.21 8.98 64.0 3.33 8.91 17 75 69.28 3.70 9.70 68.9 3.87 9.82 18 70 69.28 3.70 9.70 69.3 3.79 9.65 19 77 69.28 3.70 9.70 69.1 3.84 9.68 20 74 64.17 3.21 8.98 64.2 3.36 8.89 21 73 69.28 3.70 9.70 68.9 3.79 9.62 22 75 69.28 3.70 9.70 68.8 3.80 9.67 -
TABLE 8 Device No. Complex 121 Brightness/cd/m2 (25V) 120 The maximum wavelength/nm 640 2 Brightness/cd/m2 (25V) 150 The maximum wavelength/nm 635 3 Brightness/cd/m2 (25V) 150 The maximum wavelength/nm 625˜645 4 Brightness/cd/m2 (25V) 130 The maximum wavelength/nm 605˜645 - The following example 23˜example 29 are directed to
Complex 23˜Complex 29. All the tridentate ligands are the same as the tridentate ligands used in the first group complexes. So the synthesis of these ligands are referred to the example 1˜example 11. - Synthesis of the Complex 23:
-
Complex 23 was synthesized through a reaction in the ethanol solution of salicylidene-o-aminophenol and SnCl4. The salicylidene-o-aminophenol ligand was obtained by heating the mixture of 2-aminophenol and 2-hydroxy-salicylic aldehyde in ethanol solution and the following recrystallization. A solution of salicylidene-o-aminophenol (0.01M) and piperidine (0.02M) in 500 ml ethanol was added to a solution of SnCl4 (0.25M) in 10 ml ethanol very slowly with an intensive stirring. A light yellow precipitate was formed. The mixture was stirred for about 1 hour and cooled to room temperature and kept in dark for about 10 hours. The product was collected by filtration and washed with ethanol rapidly, then dried under an infrared lamp. The obtained product power showed strong yellow fluorescence under an ultraviolet lamp. The materials were further purified by an improved train sublimation method. The molecular structure ofComplex 23 was supported by element analysis. Element analysis found: C, 57.68; H, 3.34; N, 5.18. Calc. For Complex 23: C, 57.703; H, 3.329; N, 5.178. - Fabrication of the devices with complex 23:
- 1. (device 1) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(n-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD (60 nm)/Complex 23(40 nm)/MgAg(10:1). The maximum brightness of the device was up to 2000 cd/m2. The EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.5 lm/W, which was shown in FIG. 8 and in table 10.
- 2. (device 2) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD (60 nm)/Complex 23 (40 nm)/Alq3 (20 nm)/MgAg (10:1). The maximum brightness of the device was up to 3000 cd/m2. The EL emission was at around 573 nm and the maximum luminous efficiencies up to 1.7 lm/W, which was shown in table 10.
- 3. (device 3) The EL device was fabricated by conventional vacuum vapor deposition method under a 2×10-3 Pa vacuum at room temperature. N,N′-diphenyl-N,N′-di(m-methylphenyl)benzidine (TPD) was used as the hole transport layer material. The following layer structures of was prepared: ITO/TPD: Complex 23 (100:1˜15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1). The maximum brightness of the device was up to 2500 cd/m2. The EL emission was at 535˜577 nm (depending on the concentration of
Complex 1 in the thin film) and the maximum luminous efficiencies up to 1.8 lm/W, which was shown in table 10. - 4. (device 4) Both
Complex 23 and some polymer (such as PVK) were dissolved in some organic solvent (such as C2H4Cl2). The thin film of mixture ofComplex 1 and polymer was prepared by spin coating method. The following layer structures of was prepared: ITO/PVK: Complex 1 (100:1˜15:1 by weight) (60 nm)/Alq3 (40 nm)/MgAg (10:1). The maximum brightness of the device was up to 1800 cd/m2. The EL emission was at 505˜573 nm (depending on the concentration ofComplex 1 in the thin film) and the maximum luminous efficiencies up to 1.8 lm/W, which was shown in table 10. - According to the synthesis procedures of
Complex 23,Complex 24 was prepared by replacing 2-hydroxy-salicylic aldehyde with 2-hydroxy-naphthyl aldehyde. The data for identifying this complex was shown in the following table 9. - According to the synthesis procedures of
Complex 23,Complex 25 was prepared by replacing 2-hydroxy-naphthyl aldehyde with 3-hydroxy-2-naphthyl aldehyde. The data for identifying this complex was shown in the following table 9. - According to the synthesis procedures of
Complex 23, Complex 26 was prepared by replacing 2-hydroxy-naphthyl aldehyde with 1-hydroxy-2-naphthyl aldehyde. The data for identifying this complex was shown in the following table 9. - According to the synthesis procedures of
Complex 23,Complex 27 was prepared by replacing 2-aminophenol with 2-hydroxy-1-naphthyl amine. The data for identifying this complex was shown the following table 9. - According to the synthesis procedures of
Complex 23, Complex 28 was prepared by replacing 2-aminophenol with 3-hydroxy-2-naphthyl amine. The data for identifying this complex was shown the following table 9. - According to the synthesis procedures of
Complex 23, Complex 29 was prepared by replacing 2-aminophenol with 1-hydroxy-2-naphthyl amine. The data for identifying this complex was shown in the following table 9.TABLE 9 Production Cal. for Complex yield/ Structural Formula Element analysis No. % C % H % N % C % H % N % 23 89 57.70 3.33 5.18 57.68 3.34 5.18 24 82 60.94 3.386 4.740 60.76 3.42 4.80 25 79 60.94 3.186 4.740 60.81 3.43 4.79 26 80 60.34 3.386 4.740 60.77 3.46 4.81 27 63 60.94 3.386 4.740 60.72 3.38 4.78 28 71 60.94 3.386 4.740 60.69 3.49 4.88 29 61 60.94 3.386 4.740 60.73 3.50 4.82 -
TABLE 10 Device No. Complex 231 Brightness/cd/m2 (15V) 85 The maximum wavelength/nm 606 2 Brightness/cd/m2 (15V) 160 The maximum wavelength/nm 605 3 Brightness/cd/m2 (15V) 210 The maximum wavelength/nm 575˜615 4 Brightness/cd/m2 (15V) 160 The maximum wavelength/nm 565˜615
Claims (9)
4. The compound of wherein the subsituents of the aryl groups I, II or III are independently selected from the group consisting of 1-8 carbon atoms, halogen, cyano, amino, amido, sulfonyl, carbonyl, aryl, or heteroalkyl groups.
claim 1
5. The compound of wherein the subsituents of the aryl groups I, II or III are independently selected from the group consisting of 1-8 carbon atoms, halogen, cyano, amino, amido, sulfonyl, carbonyl, aryl, or heteroalkyl groups.
claim 2
6. The compound of wherein the subsituents of the aryl groups II or III are independently selected from the group consisting of 1-8 carbon atoms, halogen, cyano, amino, amido, sulfonyl, carbonyl, aryl, or heteroalkyl groups.
claim 3
7. A yellow fluorescent material comprising a compound according to .
claim 1
8. A red fluorescent material comprising a compound according to .
claim 2
9. A yellow fluorescent material comprising a compound according to .
claim 3
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CN00100040A | 2000-01-07 |
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Cited By (2)
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WO2002050547A3 (en) * | 2000-12-19 | 2003-09-12 | Amersham Biosciences Uk Ltd | Fluorescent dye complexes |
JP2004162002A (en) * | 2002-06-13 | 2004-06-10 | Qinghua Univ | Organic el material and its application |
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WO2010078413A1 (en) | 2008-12-31 | 2010-07-08 | Apinee, Inc. | Preservation of wood, compositions and methods thereof |
US9878464B1 (en) | 2011-06-30 | 2018-01-30 | Apinee, Inc. | Preservation of cellulosic materials, compositions and methods thereof |
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US4178382A (en) * | 1978-06-19 | 1979-12-11 | Uniroyal, Inc. | N-substituted triorganostannylhydro-carbylcarboxylic acid hydrazides |
EP0162811B1 (en) * | 1984-05-22 | 1989-10-11 | Ciba-Geigy Ag | Process for the photochemical stabilisation of materials containing polyamide fibres |
US4720432A (en) | 1987-02-11 | 1988-01-19 | Eastman Kodak Company | Electroluminescent device with organic luminescent medium |
US5141671A (en) | 1991-08-01 | 1992-08-25 | Eastman Kodak Company | Mixed ligand 8-quinolinolato aluminum chelate luminophors |
CA2211022A1 (en) * | 1995-12-21 | 1997-07-03 | Idemitsu Petrochemical Co., Ltd. | Organic aluminoxy compound and catalyst for producing polymer |
JPH09286925A (en) * | 1996-02-23 | 1997-11-04 | Fuji Photo Film Co Ltd | Schiff's base quinone complex and optically recording material containing the same |
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WO2002050547A3 (en) * | 2000-12-19 | 2003-09-12 | Amersham Biosciences Uk Ltd | Fluorescent dye complexes |
JP2004162002A (en) * | 2002-06-13 | 2004-06-10 | Qinghua Univ | Organic el material and its application |
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US6410766B2 (en) | 2002-06-25 |
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