WO2018120973A1 - 应用于有机发光二极管的主体材料 - Google Patents
应用于有机发光二极管的主体材料 Download PDFInfo
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- WO2018120973A1 WO2018120973A1 PCT/CN2017/105313 CN2017105313W WO2018120973A1 WO 2018120973 A1 WO2018120973 A1 WO 2018120973A1 CN 2017105313 W CN2017105313 W CN 2017105313W WO 2018120973 A1 WO2018120973 A1 WO 2018120973A1
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000011630 iodine Substances 0.000 claims abstract description 5
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims abstract description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 13
- 150000002431 hydrogen Chemical group 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
- 230000005669 field effect Effects 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 125000004093 cyano group Chemical group *C#N 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 33
- 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 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- XHQZXHMRBXBPEL-UHFFFAOYSA-N eaton reagent Chemical compound CS(O)(=O)=O.O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 XHQZXHMRBXBPEL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase 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
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004773 frontier orbital Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the invention relates to a novel organic light emitting diode main body material which is deposited into a thin film by vacuum deposition as a light emitting layer material for an organic light emitting diode device.
- OLEDs organic light-emitting diodes
- OLED devices have the characteristics of self-luminous, wide viewing angle, short reaction time and large area and flexible devices, and they have potential low cost advantages, making them a strong competitor for next-generation display and lighting technology. Based on these characteristics, OLED is also known as the 21st century star display product. Today, OLED display products have been commercialized. However, there are still problems such as low efficiency and short life, which are yet to be further studied.
- the organic light emitting diode is an electroluminescent device. Under voltage driving, electrons and holes respectively enter the light emitting layer through the electron transport layer and the hole transport layer to form an exciton; the exciton transmits energy to the organic molecule having the light emitting property, so that When it is excited, the excited state molecules return to the ground state and a radiation transition occurs to emit light. Since Forrest et al. reported on electroluminescent phosphorescent devices (PHOLEDs) in 1998, PHOLEDs have attracted much attention due to their ability to achieve 100% internal quantum efficiency using triplet and singlet exciton luminescence. PHOLED devices generally use a multi-layer structure, which has the advantage of facilitating the process of carrier injection, transport, and recombination.
- the guest material is typically doped in the host material to "dilute" the concentration of the guest material.
- the ideal host material should have a suitable frontier orbital energy level to achieve efficient energy transfer between the host and guest, good carrier transport properties to achieve electron and hole balance in the luminescent layer, and better thermal stability. Conducive to the formation of a stable amorphous film. Therefore, in order to obtain high-efficiency PHOLED devices, it is particularly important to develop new host materials.
- the widely used host material is a 4,4'-N,N'-dicarbazole biphenyl (CBP) having a symmetrical structure, which substantially conforms to the requirements of the OLED for the host material in terms of its photoelectric properties, but its glass
- the transition temperature is low, only 62 ° C, so CBP has the disadvantage of being easily crystallized.
- the difficulty of the transformation of the amorphous film into the crystalline film is mainly affected by the glass transition temperature (T g ) of the organic material, and the higher the glass transition temperature, the better the stability of the film. Therefore, it is necessary to develop a new high glass transition temperature host material.
- T g glass transition temperature
- the present invention provides a highly morphologically stable organic host material that can be applied to organic electroluminescent devices.
- the host material applied to the organic light emitting diode has the structure of the chemical formula (I):
- Ar is one of the following groups:
- R, R 2 are independently selected from hydrogen, C1-C4 alkyl substituted or unsubstituted C1-C4 alkyl, C1-C4 alkyl substituted or unsubstituted C2-C4 olefinic alkyl, C1-C4 alkyl substituted Or an unsubstituted C2-C4 alkynyl group, a C6-C10 group containing one or more substituents R 1 substituted or unsubstituted aryl, an aromatic hydrocarbon group, C5-C8 containing one or more substituents R 1 substituted or Unsubstituted heteroaryl containing one or more heteroatoms;
- R 1 is independently selected from the group consisting of fluorine F, chlorine chloride, bromine Br, iodine I, cyanoCN, and a C1-C4 alkyl group.
- R, R 2 are independently selected from hydrogen, C1-C4 alkyl, C6-C10 aryl or aromatic hydrocarbon group containing one or more substituents R 1 substituted or unsubstituted;
- R 1 is independently selected from the group consisting of fluorine F, chlorine chloride, bromine Br, iodine I, and a C1-C4 alkyl group.
- R is selected from the group consisting of hydrogen, methyl, tert-butyl, phenyl, tolyl, naphthyl;
- R 2 is independently selected from the group consisting of hydrogen H, C1-C4 alkyl, C6-C10 aryl or aromatic hydrocarbon group containing one or more substituents R 1 substituted or unsubstituted;
- R 1 is independently selected from the group consisting of fluorine F, chlorine chloride, bromine Br, and a C1-C4 alkyl group.
- R and R 2 are selected from the group consisting of hydrogen, tert-butyl, phenyl, and tolyl, and R 1 is selected from the group consisting of hydrogen and methyl.
- R, R 2 are selected from the group consisting of hydrogen, tert-butyl, phenyl, and R 1 is selected from hydrogen.
- An organic electroluminescent diode device comprising a cathode, an anode and an organic layer, the organic layer being one or more of a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer. It is important to note that these organic layers do not have to be present in every layer.
- the hole transport layer, the hole blocking layer, the light-emitting layer, and/or the electron transport layer contain the compound of the formula (I).
- the compound of the formula (I) is a host material applied to the light-emitting layer.
- the organic layer of the electronic device of the present invention has a total thickness of from 1 to 1000 nm, preferably from 1 to 500 nm, more preferably from 5 to 300 nm.
- the organic layer may be formed into a film by a vaporization or solution method.
- the compound represented by the formula (I) has the following structure
- the device experiments show that the organic host material of the invention has high glass transition temperature and high thermal stability, and the prepared organic electroluminescent device has good performance and stability, and has potential for application in the field of organic electroluminescent devices.
- Figure 1 is a DSC curve of Compound 1 of the present invention
- FIG. 2 is a structural view of an organic electroluminescent device of the present invention
- 10 represents a glass substrate
- 20 represents an anode
- 30 represents a hole injection layer
- 40 represents a hole transport layer
- 50 Representative of the luminescent layer
- 60 represents a hole blocking layer
- 70 represents an electron transport layer
- 80 represents an electron injecting layer
- 90 represents a cathode.
- the glass transition temperature of Compound 1 was measured by differential scanning calorimetry (DSC) at a heating and cooling rate of 20 ° C/min under nitrogen gas (Fig. 1).
- the glass transition temperature T g of Compound 1 was measured to be 159 °C.
- the glass transition temperature of CBP reported in the literature is only 62 °C.
- the compound of the present invention has a higher glass transition temperature than the commonly used commercially available material CBP.
- the present invention significantly improves the thermal stability of the electroluminescent device material, and more closely meets the requirements of the organic material for the electroluminescent device.
- the OLED is prepared by using the organic host material of the invention, as shown in FIG. 2
- the transparent conductive ITO glass substrate 10 (with the anode 20 on the surface) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
- the compound NPB was evaporated to form a hole transport layer 40 having a thickness of 40 nm.
- Ir(PPy) 3 (9%) and Compound 1 (91%) having a thickness of 30 nm were vapor-deposited on the hole transport layer as the light-emitting layer 50.
- a BCP having a thickness of 10 nm was vapor-deposited on the light-emitting layer as the hole blocking layer 60.
- Example 3 The method was the same as in Example 3 except that Ir(PPy) 3 (9%) and a commonly used commercially available compound CBP (91%) were used as the light-emitting layer to prepare a comparative organic light-emitting diode device.
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明涉及应用于有机发光二极管的主体材料，具有式(I)所述的结构，其中，其中，R、R2独立选自氢，C1-C4烷基取代或未取代的C1-C4烷基，C1-C4烷基取代或者未取代的C2-C4烯烷基，C1-C4烷基取代或者未取代的C2-C4炔烷基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳基、芳烃基，C5-C8的含有一个或者多个取代基R1取代或未取代的含有一个或者多个杂原子的杂芳基，R1独立选自氟F，氯Cl，溴Br，碘I，氰基CN，C1-C4的烷基；Ar为N-芳基咔唑。实验结果表明，本发明的有机主体材料具有高玻璃化转变温度，热稳定性高，所制备的有机发光器件性能良好且稳定。
Description
本发明涉及新型有机发光二极管主体材料，通过真空沉积成薄膜，作为发光层材料用于有机发光二极管器件。
近年来，有机发光二极管(OLED)作为一种有巨大应用前景的照明、显示技术，受到了学术界与产业界的广泛关注。OLED器件具有自发光、广视角、反应时间短及可制备大面积和柔性器件等特性，而且其还具有潜在的低成本优势，使其成为下一代显示、照明技术的有力竞争者。基于这些特性，OLED也被誉为21世纪明星显示产品。如今，OLED显示产品已经实现了商业化。但仍然存在效率低、寿命短等问题，有待人们进一步研究。
有机发光二极管为电致发光器件，在电压驱动下，电子和空穴分别经电子传输层和空穴传输层进入发光层复合形成激子；激子将能量传递给有发光特性的有机分子，使其受激发，激发态分子回到基态时发生辐射跃迁而发光。自1998年Forrest等人报道了电致磷光发光器件(PHOLED)以来，PHOLED因其可以利用三线态和单线态激子发光而实现100％内量子效率而备受关注。PHOLED器件通常采用多层结构，其优点在于可以方便地调节载流子注入、传输及复合等过程。在发光层中，当客体掺杂浓度较高时，会出现浓度淬灭和T1-T1湮灭，导致发光效率降低。为了解决这些问题，通常将客体材料掺杂在主体材料中，从而“稀释”客体材料的浓度。理想的主体材料应具有合适的前线轨道能级以实现主客体间有效地能量转移，良好的载流子传输性能以便在发光层中实现电子和空穴的平衡，和较好的热稳定性以利于形成稳定的非晶态薄膜。因此，为了获得高效PHOLED器件，开发新型主体材料尤为重要。
目前，广泛使用的主体材料为具有对称结构的4,4'-N,N'-二咔唑联苯(CBP)，就其光电性能而言基本上符合OLED对主体材料的要求，但其玻璃化转变温度较低，仅为62℃，因此CBP具有容易结晶的缺点。有机层材料一旦结晶，会使得分子间的电荷跃迁机制与正常非晶态薄膜机制不相同，能量转移方式也会发生变化。最终导致主客体间不能有效地进行能量转移，降低器件的使用寿命。非晶薄膜向晶态薄膜的转变难易程度主要受有机材料的玻璃化转变温度(Tg)影响，玻璃化转变温度越高，则薄膜的稳定性越好。因此，开发新型高玻璃化转变温度主体材料十分必要。
发明内容
针对上述材料的缺陷，本发明提供一种可应用在有机电致发光器件上的高形态稳定性的有机主体材料。
应用于有机发光二极管的主体材料，具有化学式(I)的结构：
Ar为下列基团中的一个：
其中，R、R2独立选自氢，C1-C4烷基取代或未取代的C1-C4烷基，C1-C4烷基取代或者未取代的C2-C4烯烷基，C1-C4烷基取代或者未取代的C2-C4炔烷基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳基、芳烃基，C5-C8的含有一个或者多个取代基R1取代或未取代的含有一个或者多个杂原子的杂芳基；
R1独立选自氟F，氯Cl，溴Br，碘I，氰基CN，C1-C4的烷基。
优选地，R、R2独立选自氢，C1-C4烷基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳基、芳烃基；
R1独立选自氟F，氯Cl，溴Br，碘I，C1-C4的烷基。
更优选地，R选自氢，甲基，叔丁基，苯基，甲苯基，萘基；
R2独立选自氢H，C1-C4烷基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳基、芳烃基；
R1独立选自氟F，氯Cl，溴Br，C1-C4的烷基。
进一步优选：R、R2选自氢，叔丁基，苯基，甲苯基，R1选自氢、甲基。
特别优选：R、R2选自氢，叔丁基，苯基，R1选自氢。
有机电致发光二极管器件，包括阴极、阳极和有机层，所述有机层为空穴传输层、发光层、空穴阻挡层、电子传输层中的一层或多层。需要特别指出，这些有机层不必每层都存在。
所述空穴传输层、空穴阻挡层、发光层和/或电子传输层中含有式(I)所述的化合物。
所述式(I)所述的化合物为应用于发光层中的主体材料。
本发明的电子器件有机层的总厚度为1-1000nm，优选1-500nm，更优选5-300nm。
所述有机层可以通过蒸渡或溶液法形成薄膜。
如上面提到的，本发明的式(I)所述的化合物如下，但不限于所列举的结构：
再优选：式(I)所表示化合物为以下结构
器件实验表明，本发明的有机主体材料具有高玻璃化转变温度，热稳定性高，所制备的有机电致发光器件性能良好且稳定，有潜力应用于有机电致发光器件领域。
图1为本发明化合物1的DSC曲线，
图2为本发明的有机电致发光器件结构图，
其中10代表为玻璃基板，20代表为阳极，30代表为空穴注入层，40代表为空穴传输层，50
代表发光层，60代表空穴阻挡层，70代表电子传输层，80代表电子注入层，90代表为阴极。
为了更详细叙述本发明，特举以下例子，但是不限于此。
实施例1
化合物1的合成路线
化合物b的合成
氮气保护下，将五氧化二磷(0.8g,5.6mmol)加入甲烷磺酸(9.2g,95.6mmol)中，室温搅拌2h，使其充分溶解，呈粘稠状油状物(伊顿试剂)。随后，将伊顿试剂(1mL)逐滴加入化合物a(3.2g,10.0mmol)(参考文献J.Mater.Chem.C.,2(12),2160-2168合成)和三苯甲醇(2.86g，11.0mmol)的二氯甲烷(100mL)中。滴加完毕后，室温下搅拌2h。反应液水洗三次，无水硫酸钠干燥。减压除去溶剂后，粗产物经重结晶得白色固体(4.2g,产率74.4％)。1H NMR(400 MHz，CDCl3,δ):8.01(s,1H),7.94(d,J＝7.6Hz,1H),7.69(d,J＝8.8Hz,2H),7.44(d,J＝8.8,2H),7.36(d,J＝3.6Hz,2H),7.32–7.18(m,18H).
化合物1的合成
将化合物b(2.0g,3.5mmol)、化合物c(1.44g,3.9mmol)(参考文献J.Mater.Chem.C.,1(24),3871-3878合成)、Pd(PPh3)4(208mg,0.2mmol)、四氢呋喃(30mL)和碳酸钾水溶液(2M,5mL)依次加入Schlenk管中。抽真空，通入氮气，反复进行三次。氮气保护下，回流过夜。冷至室温后，将上述反应液加入水中，经二氯甲烷萃取三次，合并有机相。有机相经无水硫酸钠干燥后，减压蒸除溶剂，剩余物经柱层析分离得白色固体(2.1g,产率81.6％),升华后纯度为99.8％。1H NMR(400 MHz,CDCl3,δ):8.17(d,J＝8.0Hz,2H),8.05(s,1H),7.98(d,J＝7.6Hz,1H),7.90-7.87(m,4H),7.72-7.69(m,4H),7.52(s,1H),7.50(s,2H),7.46-7.38(m,4H),7.34-7.19(m,19H)。玻璃化转变温度为159℃。
实施例2
玻璃化转变温度测试：
在氮气保护下，以20℃/min的加热和冷却速率用示差扫描量热法(DSC)测试化合物1的玻璃化转变温度(图1)。测得化合物1的玻璃化转变温度Tg为159℃。而文献所报道的CBP的玻璃化转变温度仅为62℃。
可见，本发明中的化合物比常用市售材料CBP具有更高的玻璃化转变温度，本发明显著提高了电致发光器件材料的热稳定性，更符合电致发光器件对有机材料的要求。
实施例3
有机电致发光器件1的制备
使用本发明的有机主体材料制备OLED，见图2
首先，将透明导电ITO玻璃基板10(上面带有阳极20)依次经：洗涤剂溶液和去离子水，乙醇，丙酮，去离子水洗净，再用氧等离子处理30秒。
然后，在ITO上蒸渡10nm厚的MoO3作为空穴注入层30。
然后，蒸渡化合物NPB,形成40nm厚的空穴传输层40。
然后，在空穴传输层上蒸渡30nm厚的Ir(PPy)3(9％)与化合物1(91％)作为发光层50。
然后，在发光层上蒸渡10nm厚的BCP作为空穴阻挡层60。
然后，在空穴阻挡层上蒸渡30nm厚的30nm厚的AlQ3作为电子传输层70。
最后，蒸渡1nm LiF为电子注入层80和100nm Al作为器件阴极90。
器件中所述结构式
所制备的器件在20mA/cm2的工作电流密度下，亮度4362cd/m2,电流效率为21.8cd/A发射绿光CIEx为0.318,CIEy为0.618。
比较例
有机电致发光器件2的制备
方法同实施例3，但使用Ir(PPy)3(9％)和常用市售化合物CBP(91％)作为发光层，制作对比用有机发光二极管器件。
器件中所述结构式
所制备的器件在20mA/cm2的工作电流密度下，亮度为3021cd/m2,电流效率达到15.1cd/A，发射绿光CIEx为0.321,CIEy为0.613。
对比实施例3和比较例的实验结果可见，相比于广泛使用的主体材料CBP，使用本发明的有机材料制备的器件具有更好的电致发光性能，更符合高性能有机半导体器件对主体材料的要求。
Claims (8)
- 一种应用于有机发光二极管的主体材料，具有化学式(I)的结构：
其中，Ar为下列N-芳基咔唑基团中的一个：
R、R2独立选自氢，C1-C4烷基取代或未取代的C1-C4烷基，C1-C4烷基取代或者未取代的C2-C4烯烷基，C1-C4烷基取代或者未取代的C2-C4炔烷基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳烃基，C5-C8的含有一个或者多个取代基R1取代或未取代的含有一个或者多个杂原子的杂芳基；R1独立选自氟F，氯Cl，溴Br，碘I，氰基CN，C1-C4的烷基。 - 根据权利要求1所述的主体材料，R、R2独立选自氢，C1-C4烷基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳基、芳烃基；R1独立选自氟F，氯Cl，溴Br，碘I，C1-C4的烷基。
- 根据权利要求2所述的主体材料，R独立选自氢，甲基，叔丁基，苯基，甲苯基，萘基；R2独立选自氢H，C1-C4烷基，C6-C10的含有一个或者多个取代基R1取代或未取代的芳基、芳烃基；R1独立选自氟F，氯Cl，溴Br，C1-C4的烷基。
- 根据权利要求3所述的主体材料，其中R、R2独立选自氢，叔丁基，苯基，甲苯基，R1选自氢、甲基。
- 根据权利要求4所述的主体材料，其中R、R2独立选自氢，叔丁基，苯基，R1为 氢。
- 根据权利要求5所述的主体材料，为下列化合物中的一个：
- 根据权利要求6所述的主体材料，为下述化合物：
- 权利要求1-7任一主体材料在有机电致发光器件，有机场效应晶体管，有机太阳能电池和有机光电传感器上的应用。
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| CN104144909A (zh) * | 2011-12-28 | 2014-11-12 | 索尔维公司 | 可交联芳基胺化合物 |
| US20160071625A1 (en) * | 2013-05-22 | 2016-03-10 | Konica Minolta, Inc. | Charge-transporting thin film |
| US20160079548A1 (en) * | 2013-05-22 | 2016-03-17 | Konica Minolta, Inc. | Electronic device, organic electroluminescent element, organic thin-film solar cell, and dye-sensitized solar cell |
| CN105566199A (zh) * | 2014-10-14 | 2016-05-11 | 北京化工大学 | 一类共轭芳炔基咔唑化合物 |
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| CN104144909A (zh) * | 2011-12-28 | 2014-11-12 | 索尔维公司 | 可交联芳基胺化合物 |
| US20160071625A1 (en) * | 2013-05-22 | 2016-03-10 | Konica Minolta, Inc. | Charge-transporting thin film |
| US20160079548A1 (en) * | 2013-05-22 | 2016-03-17 | Konica Minolta, Inc. | Electronic device, organic electroluminescent element, organic thin-film solar cell, and dye-sensitized solar cell |
| CN105566199A (zh) * | 2014-10-14 | 2016-05-11 | 北京化工大学 | 一类共轭芳炔基咔唑化合物 |
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