CN103420910A - Electron-transport blue luminescent material and use thereof - Google Patents
Electron-transport blue luminescent material and use thereof Download PDFInfo
- Publication number
- CN103420910A CN103420910A CN2012102614333A CN201210261433A CN103420910A CN 103420910 A CN103420910 A CN 103420910A CN 2012102614333 A CN2012102614333 A CN 2012102614333A CN 201210261433 A CN201210261433 A CN 201210261433A CN 103420910 A CN103420910 A CN 103420910A
- Authority
- CN
- China
- Prior art keywords
- electron
- compound
- luminescent material
- blue
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 45
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 8
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 4
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 abstract description 9
- 238000005401 electroluminescence Methods 0.000 abstract description 7
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 abstract description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 20
- 229940125904 compound 1 Drugs 0.000 description 16
- 239000011521 glass Substances 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000005525 hole transport Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IFIYWCPYVXIURY-UHFFFAOYSA-N acridin-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=NC2=C1 IFIYWCPYVXIURY-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical class C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001194 electroluminescence spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 1-phenyl-1H-benzimidazole-2-yl Chemical group 0.000 description 2
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 2
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 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 2
- LONBOJIXBFUBKQ-UHFFFAOYSA-N 2,7-dibromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC(Br)=CC=C3C2=C1 LONBOJIXBFUBKQ-UHFFFAOYSA-N 0.000 description 1
- AJYDOCCGNIBJBY-UHFFFAOYSA-N 2,7-dibromo-9,9-diphenylfluorene Chemical compound C12=CC(Br)=CC=C2C2=CC=C(Br)C=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 AJYDOCCGNIBJBY-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- SAYMLKNOCKBPMK-UHFFFAOYSA-N 3,6-dibromo-9-methylcarbazole Chemical compound BrC1=CC=C2N(C)C3=CC=C(Br)C=C3C2=C1 SAYMLKNOCKBPMK-UHFFFAOYSA-N 0.000 description 1
- JBWRZTKHMKVFMQ-UHFFFAOYSA-N 3,6-dibromo-9-phenylcarbazole Chemical compound C12=CC=C(Br)C=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 JBWRZTKHMKVFMQ-UHFFFAOYSA-N 0.000 description 1
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical group 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 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to the technical of organic electroluminescence and especially relates to an electron-transport blue luminescent material and its use in the field of organic electroluminescence. According to the electron-transport blue luminescent material, an aromatic compound or an aromatic heterocycle is connected to a 9th site of acridine, and because of high steric hindrance, the aromatic rings distortion-interact with each other so that the whole molecule has a non-planar structure and thus intermolecular aggregation and interaction are avoided and a wide band gap is formed; and the acridine group has a unique nitrogen-containing three-ring structure so that high fluorescence quantum efficiency and electron transmission performances are obtained. An experiment result shows that the electron-transport blue luminescent material has good heat stability and electroluminescent characteristics, can be used as a luminescent layer of a blue organic electroluminescent device and can efficiently emit blue light having high color purity.
Description
Technical Field
The present invention relates to the field of Organic electroluminescence, and in particular, to an electron-transporting blue Light Emitting material for an Organic Light-Emitting Diode (OLED), and an application of the material in the field of Organic electroluminescence.
Background
The phenomenon of organic electroluminescence has been found for over thirty years, and before 1987, the application of organic electroluminescent devices was limited due to their great defects (turn-on voltage > 200V). In recent decades, organic electroluminescence has reached or approached the practical stage due to the continuous breakthrough of material device technology.
Due to the years of investment and effort in various circles, the development of the OLED in basic science is greatly developed, but the organic electroluminescent device is a new technology developed in the last two decades, and a plurality of key problems are not really solved, mainly the important basic problems still exist in the aspects of optimization of luminescent materials, colorization technology, high-resolution display technology, active driving technology, packaging technology and the like, so that the organic electroluminescent device is short in service life and low in efficiency.
The materials for the organic electroluminescent device mainly include electrode materials, carrier transport materials, and light emitting materials. Electrode materials are divided into cathode materials and anode materials, and carrier transport materials include electron transport materials and hole transport materials, among which light emitting materials are the most important materials in OLEDs. Red, green and blue light emission of high efficiency and high color purity is required for realizing color display. In red, green and blue luminescent display materials, the red and green luminescent materials have stable performance and long service life, and meet the practical requirements; however, many known blue materials can meet the requirements of full-color OLED display in terms of color purity, but the lifetime of the device still needs to be improved, and the practical conditions are not met.
In order to improve the performance of the organic electroluminescent device, research on luminescent materials is very important. The luminescent material must be chosen to meet several requirements: 1. fluorescent properties of high quantum efficiency; 2. good semiconductor characteristics; 3. good film forming property and thermal stability; 4. good light stability; 5. good carrier mobility. Generally, it is difficult to satisfy the requirements of high efficiency and high color purity of the blue light material at the same time because the blue light material has a wide band gap. How to balance the two aspects becomes the key for developing excellent blue light materials. The compound containing acridine group is a typical electron-deficient system, has good electron accepting capability and good electron transmission property. Therefore, the electron-deficient acridine group is introduced on the basis of the aromatic compound, and a high-efficiency blue light-emitting material is hopefully obtained.
Disclosure of Invention
The invention aims to solve the technical problem of providing an electron-transporting blue luminescent material which is used in an organic electroluminescent device, can meet the requirements of full-color OLED display, and has high color purity and high efficiency, and an application thereof.
The technical scheme for solving the technical problems is as follows: an electron-transporting blue light-emitting material has a structural formula shown in formula 1:
in the formula 1, the compound is shown in the specification,
wherein R is1～R8Selected from hydrogen radical or (C)1～C30) Any one of alkyl groups;
ar is one of the groups of the structure shown in formula 2:
in the formula (2), the first and second groups,
wherein R is selected from any one of the following groups:
hydrogen, alkyl of any length; or,
a group of aromatic compounds of benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyrene; or,
heterocyclic groups derived from aromatic groups.
Further, preferably, R represents hydrogen、C1～C30Any one of alkyl, benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, furan, thiophene, pyrrole, pyridine, pyran, quinoline, indole or carbazole groups.
The invention has the beneficial effects that:
1. the material is characterized in that an aromatic compound or an aromatic heterocycle is connected to the 9 th site of acridine, aromatic rings are mutually twisted and arranged due to higher steric hindrance, the whole molecule is in a non-planar structure, aggregation and interaction among molecules are avoided, and a wider band gap is provided. In addition, the acridine group has a unique nitrogen-containing tricyclic structure, so that the acridine group has high fluorescence quantum efficiency and electron transport performance.
2. The material has good thermal stability, and high glass transition temperature and decomposition temperature.
3. The material has good electroluminescent characteristic, and can be used as a luminescent layer of a blue organic electroluminescent device to obtain blue light emission with high color purity and efficiency.
5. The material can be used as a doping main body material of a blue luminescent material and has the potential of red and green application.
The preparation method of the electron-transporting blue luminescent material comprises the following steps:
the compound shown in the formula 1 is prepared by carrying out Suzuki reaction on 2, 7-dibromospirofluorene, substituted 3, 6-dibromocarbazole and substituted 2, 7-dibromofluorene and substituted 9-acridine boric acid.
Wherein in the step, the Suzuki reaction is carried out under the protection of nitrogen or other inert gases by using Pd (PPh)3)4Or palladium acetate is used as a catalyst, and the reflux reaction is carried out for 12 to 36 hours at the temperature of 80 to 100 ℃.
The invention preferably selects compounds 1-9 as representative materials, and the structural formulas of the compounds are shown as follows:
the invention synthesizes a series of new compounds based on acridine group, the acridine group has the performance of some fluorescent dyes due to the unique nitrogen-containing tricyclic structure, the molecular conjugation degree of the acridine group is enlarged by introducing spirofluorene, carbazole or fluorene group with larger conjugation structure, the vitrification temperature is improved, the molecular thermal stability is increased, in addition, the acridine group is a typical electron-deficient system and has good electron-accepting capability, so the electron-transporting blue luminescent material provided by the invention has good photoelectric property.
The invention takes the compounds 1 and 9 as examples, and also provides an application example of the electron-transporting blue luminescent material in the field of organic electroluminescence. The prepared blue organic electroluminescent device generally comprises an ITO conductive glass substrate (anode), a hole transport layer [ N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB) ], a luminescent layer [ used alone or doped with 9,9' - (1, 3-phenyl) di-9H-carbazole (MCP) ], an electron transport layer [1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) ], an electron injection Layer (LiF) and a cathode layer (Al) which are sequentially stacked. All functional layers can adopt vacuum evaporation or solution film forming process. The molecular structural formulae of some of the organic compounds used in the device are shown below:
of course, the functional layer of the device of the present invention is not limited to the use of the above materials, and these materials may be replaced with other materials, for example, the hole transport layer may be replaced with N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), etc., and the electron transport layer may be replaced with 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), tris (8-hydroxyquinoline) aluminum (Alq3),4, 7-diphenyl-1, 10-phenanthroline (BPhen), etc. The molecular structural formula of the above material is as follows:
drawings
FIG. 1 is a voltage-current density-luminance curve of a blue organic electroluminescent device using compound 1 as the light emitting layer;
FIG. 2 is a current density-power efficiency-lumen efficiency curve of a blue organic electroluminescent device using compound 1 as the light-emitting layer;
FIG. 3 shows that compound 1 is used as the light-emitting layer of blue organic electroluminescent device, which reaches 100cd/m2Electroluminescence spectrum of time;
FIG. 4 is a voltage-current density-luminance curve of a blue organic electroluminescent device using compound 9 as the light emitting layer;
FIG. 5 is a graph of current density-power efficiency-lumen efficiency for a blue organic electroluminescent device using Compound 9 as the emissive layer;
FIG. 6 shows that compound 9 is used as the light-emitting layer of blue organic electroluminescent device, which reaches 100cd/m2Electroluminescence spectrum of time;
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Examples of compound sample preparation:
example 12, 7-diaziridine (Compound 1)
Into a three-necked flask were charged 1.19g of 2, 7-dibromospirofluorene (2.5 mmol) and 1.77g of 9-acridineboronic acid (7.5 mmol), which were dissolved in a mixed solventHydrolysis (70 mL toluene, 35mL ethanol) followed by 50mL Na2CO3The aqueous solution (2M) was stirred with nitrogen for 1 hour to remove oxygen from the reaction flask. Then Pd (PPh) is added3)40.183g (0.16 mmol) are refluxed with vigorous stirring, and the course of the reaction is controlled by thin-layer chromatography. After 24 hours of reaction, 50mL of deionized water was added to the reaction mixture, insoluble matter was removed by filtration, the aqueous phase and the organic phase were separated, the aqueous phase was extracted with dichloromethane (20 mL × 3), the organic phase was mixed and then concentrated to about 5mL by distillation under reduced pressure, separation was performed by column chromatography, and the eluent was dichloromethane: n-hexane =1:5 (volume ratio), whereby 1.45g of a yellow solid (the objective product) was obtained. The crude product was purified by sublimation to give 0.96g of pure product (57% yield).
MS (m/z): 670.3. Elemental analysis (C)51H30N2): theoretical values of C91.32, H4.51, N4.18, found values of C91.55, H4.30, N4.05.
Example 22, 7-bis (1, 2,3,4,5,6,7, 8-octamethylazedinyl) spirofluorene (Compound 2)
Prepared by the synthetic method of compound 1 in example 1 starting with 2, 7-dibromospirofluorene and 1,2,3,4,5,6,7, 8-octamethyl-9-acridinium boronic acid.
MS (m/z) 894.6. Elemental analysis (C)67H62N2): 89.89 theoretical values of C, 6.98 theoretical values of H, 3.13 theoretical values of N, 89.65 practical values of H, 3.21 theoretical values of N, and 3.08 theoretical values of N.
Example 33, 6-Diazepinylcarbazole (Compound 3)
The compound 1 of example 1 was synthesized using 3, 6-dibromocarbazole and 9-acridineboronic acid as starting materials.
MS (m/z): 521.8. Elemental analysis (C)38H23N3): theoretical values of C87.50, H4.44, N8.06, found values of C87.56, H4.31, N8.12.
Example 4N-methyl-3, 6-diaziridylcarbazole (Compound 4)
Prepared by the synthesis method of the compound 1 in the example 1 by using N-methyl-3, 6-dibromocarbazole and 9-acridine boric acid as starting materials.
MS (m/z) 535.7. Elemental analysis (C)39H25N3): theoretical values of C87.45, H4.70, N7.84, found values of C87.66, H4.84, N7.72.
Example 5N-phenyl-3, 6-diaziridylcarbazole (Compound 5)
Prepared by the synthesis method of the compound 1 in the example 1 by using N-phenyl-3, 6-dibromocarbazole and 9-acridineboronic acid as starting materials.
MS (m/z): 597.3. Elemental analysis (C)44H27N3): theoretical values C88.42, H4.55, N7.03, found C88.38, H4.47, N7.12.
Example 72, 7-diaziridine (Compound 7)
Prepared by the synthetic method of compound 1 in example 1 using 2, 7-dibromofluorene and 9-acridineboronic acid as starting materials.
MS (m/z) 520.6. Elemental analysis (C)39H24N2): 89.97 theoretical values of C, 4.65 theoretical values of H, 5.38 theoretical values of N, 89.78 practical values of H, 4.67 theoretical values of N, 5.43 theoretical values of N.
Example 82, 7-diaziridyl-9, 9-dimethylfluorene (Compound 8)
Prepared by the synthetic method of compound 1 in example 1 using 2, 7-dibromo-9, 9-dimethylfluorene and 9-acridineboronic acid as starting materials.
MS (m/z): 548.9. Elemental analysis (C)41H28N2): 89.75 for theoretical value C, 5.14 for H, 5.11 for N, 89.80 for observed value C, 5.05 for H, 5.07 for N.
Example 92, 7-diaziridyl-9, 9-diphenylfluorene (Compound 9)
The compound 1 of example 1 was synthesized using 2, 7-dibromo-9, 9-diphenylfluorene and 9-acridineboronic acid as starting materials.
MS (m/z): 672.8. Elemental analysis (C)51H32N2): theoretical values of C91.04, H4.79, N4.16, found values of C91.00, H4.84, N4.08.
Organic electroluminescent device example:
device example 1 use of Compound 1 as a light-emitting layer in an organic electroluminescent device
This example prepares an electron-transporting blue organic electroluminescent device as follows:
a) cleaning of ITO (indium tin oxide) glass: respectively ultrasonically cleaning ITO glass by deionized water, acetone and ethanol for 15 minutes, and then treating the ITO glass in a plasma cleaner for 2 minutes;
b) vacuum evaporation or solution film formation is carried out on the anode ITO glass to form a hole transport layer NPB with the thickness of 50 nm;
c) vacuum evaporating a luminescent layer compound 1 on the hole transport layer NPB, wherein the thickness of the luminescent layer compound 1 is 30 nm;
d) vacuum evaporating an electron transport layer TPBI with the thickness of 30nm on the light-emitting layer;
e) vacuum evaporating an electron injection layer LiF on the electron transport layer TPBI, wherein the thickness of the electron injection layer LiF is 1 nm;
f) and vacuum evaporating cathode Al on the electron injection layer LiF, wherein the thickness of the cathode Al is 100 nm.
The structure of the device is ITO/NPB (50 nm)/compound 1(30nm)/TPBI (30nm)/LiF (1nm)/Al (100 nm). The voltage-current density-luminance curve of the device using the compound 1 prepared in example 1 as the light emitting layer of the device is shown in fig. 1, and the current density-power efficiency-lumen efficiency curve is shown in fig. 2. The starting voltage of the device is 5.5V, and the maximum brightness reaches 3136cd/m2The maximum current efficiency reached 0.44 cd/A. FIG. 3 shows the device at 100cd/m2The CIE coordinate of the electroluminescence spectrum of (0.1)8,0.14)。
Device example 2 use of Compound 9 as a light-emitting layer in an organic electroluminescent device
This example prepares an electron-transporting blue organic electroluminescent device as follows:
a) cleaning of ITO (indium tin oxide) glass: respectively ultrasonically cleaning ITO glass by deionized water, acetone and ethanol for 15 minutes, and then treating the ITO glass in a plasma cleaner for 2 minutes;
b) vacuum evaporation or solution film formation is carried out on the anode ITO glass to form a hole transport layer NPB with the thickness of 50 nm;
c) vacuum evaporating a luminescent layer compound 9 on the hole transport layer NPB, wherein the thickness of the luminescent layer compound is 30 nm;
d) vacuum evaporating an electron transport layer TPBI with the thickness of 30nm on the light-emitting layer;
e) vacuum evaporating an electron injection layer LiF on the electron transport layer TPBI, wherein the thickness of the electron injection layer LiF is 1 nm;
f) and vacuum evaporating cathode Al on the electron injection layer LiF, wherein the thickness of the cathode Al is 100 nm.
The structure of the device is ITO/NPB (50 nm)/compound 9(30nm)/TPBI (30nm)/LiF (1nm)/Al (100 nm). The voltage-current density-luminance curve of the device with the compound 9 as the light emitting layer is shown in fig. 4, and the current density-power efficiency-lumen efficiency curve is shown in fig. 5. The starting voltage of the device is 4.5V, and the maximum brightness reaches 6860cd/m2The maximum current efficiency is improved to 0.951 cd/A. FIG. 6 shows the device at 100cd/m2The CIE coordinates of the electroluminescence spectrum of (0.15, 0.12).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. An electron-transporting blue light-emitting material characterized by the following structural formula:
wherein R is1～R8Are respectively selected from hydrogen or (C)1～C30) Any one of alkyl groups;
ar is one of the groups of the following structure:
wherein R is selected from any one of the following groups:
hydrogen, alkyl of any length; or,
a group of aromatic compounds of benzene, biphenyl, naphthalene, anthracene, phenanthrene, or pyrene; or,
heterocyclic groups derived from aromatic groups.
2. The electron-transporting blue light-emitting material according to claim 1, wherein R is preferably selected from hydrogen and C1～C30Any one of alkyl, benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, furan, thiophene, pyrrole, pyridine, pyran, quinoline, indole or carbazole groups.
3. Use of the electron-transporting blue light-emitting material according to any one of claims 1 to 2 as an organic electroluminescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102614333A CN103420910A (en) | 2012-07-26 | 2012-07-26 | Electron-transport blue luminescent material and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102614333A CN103420910A (en) | 2012-07-26 | 2012-07-26 | Electron-transport blue luminescent material and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103420910A true CN103420910A (en) | 2013-12-04 |
Family
ID=49646341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102614333A Pending CN103420910A (en) | 2012-07-26 | 2012-07-26 | Electron-transport blue luminescent material and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103420910A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109532A (en) * | 2014-04-03 | 2014-10-22 | 烟台万润精细化工股份有限公司 | Electron transfer material and its application |
| CN107482132A (en) * | 2017-08-22 | 2017-12-15 | 长春海谱润斯科技有限公司 | A kind of organic luminescent device |
| CN109912433A (en) * | 2019-03-07 | 2019-06-21 | 北京诚志永华显示科技有限公司 | New compound, electroluminescent organic material, organic electroluminescence device, electronic device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11111458A (en) * | 1997-09-29 | 1999-04-23 | Toyo Ink Mfg Co Ltd | Organic electroluminescent device material and organic electroluminescent device using the same |
| CN1571763A (en) * | 2002-08-27 | 2005-01-26 | 佳能株式会社 | Fluorene compound and organic lumnescent device using the same |
| JP2005112784A (en) * | 2003-10-08 | 2005-04-28 | Canon Inc | Metacyclophane compound and organic electroluminescent device using the same |
| WO2011154131A1 (en) * | 2010-06-10 | 2011-12-15 | Novaled Ag | Electronic device comprising an organic semiconducting material |
-
2012
- 2012-07-26 CN CN2012102614333A patent/CN103420910A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11111458A (en) * | 1997-09-29 | 1999-04-23 | Toyo Ink Mfg Co Ltd | Organic electroluminescent device material and organic electroluminescent device using the same |
| CN1571763A (en) * | 2002-08-27 | 2005-01-26 | 佳能株式会社 | Fluorene compound and organic lumnescent device using the same |
| JP2005112784A (en) * | 2003-10-08 | 2005-04-28 | Canon Inc | Metacyclophane compound and organic electroluminescent device using the same |
| WO2011154131A1 (en) * | 2010-06-10 | 2011-12-15 | Novaled Ag | Electronic device comprising an organic semiconducting material |
Non-Patent Citations (2)
| Title |
|---|
| PENG ZHAOKUAI等: ""New Fluorene Derivatives for Blue Electroluminescent Devices: Influence of Substituents on Thermal Properties, Photoluminescence, and Electroluminescence"", 《J. PHYS. CHEM.》 * |
| SE HUN KIM等: ""Highly efficient deep-blue emitting organic light emitting diode based on the multifunctional fluorescent molecule comprising covalently bonded carbazole and anthracene moieties"", 《J. MATER. CHEM.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109532A (en) * | 2014-04-03 | 2014-10-22 | 烟台万润精细化工股份有限公司 | Electron transfer material and its application |
| CN104109532B (en) * | 2014-04-03 | 2016-01-06 | 中节能万润股份有限公司 | A kind of electron transport material and application thereof |
| CN107482132A (en) * | 2017-08-22 | 2017-12-15 | 长春海谱润斯科技有限公司 | A kind of organic luminescent device |
| CN109912433A (en) * | 2019-03-07 | 2019-06-21 | 北京诚志永华显示科技有限公司 | New compound, electroluminescent organic material, organic electroluminescence device, electronic device |
| CN109912433B (en) * | 2019-03-07 | 2022-04-08 | 石家庄诚志永华显示材料有限公司 | Compound, organic electroluminescent material, organic electroluminescent device, and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113443998B (en) | Triarylamine organic compound and organic light-emitting device thereof | |
| KR101565200B1 (en) | New compound and organic light emitting device using the same | |
| JP2014131983A (en) | Amine derivative, organic luminescent material, and organic electroluminescent element using the same | |
| CN102775398A (en) | Novel bipolar material and application thereof | |
| CN112679534A (en) | Heterocyclic organic electroluminescent material, preparation method, application and device thereof | |
| CN111808127B (en) | Compound, display panel and display device | |
| KR102225901B1 (en) | Multicyclic compound and organic light emitting device comprising the same | |
| CN115043785B (en) | Organic compound, organic electroluminescent device and electronic apparatus | |
| CN116783207A (en) | Organometallic complex and organic electroluminescent device including the same | |
| CN115304567A (en) | Organic compound, preparation method thereof and organic electroluminescent device | |
| CN111499618A (en) | Compound and organic photoelectric device comprising same | |
| CN106187963A (en) | One is containing anthracene compounds and preparation method thereof and a kind of organic luminescent device | |
| CN102795983A (en) | Anthraquinone derivative material and preparation method and application thereof | |
| CN112778139A (en) | Compound and application thereof | |
| KR101896009B1 (en) | Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof | |
| CN109400487A (en) | A kind of fluorene kind derivative and its organic electroluminescence device | |
| KR101324150B1 (en) | Organic compounds for organic electro luminescente device and organic electro luminescent device using same | |
| CN111004207A (en) | Organic compound, electronic device, and electronic apparatus | |
| CN103420910A (en) | Electron-transport blue luminescent material and use thereof | |
| CN116478198B (en) | Organic compound, preparation method thereof and organic electroluminescent device | |
| Liu et al. | Efficient Non‐doped Blue Fluorescent Organic Light‐Emitting Diodes Based on Anthracene–Triphenylethylene Derivatives | |
| CN115490601B (en) | Organic compound, electronic component, and electronic device | |
| CN114605389B (en) | Thermal activation delay fluorescent material and device thereof | |
| TWI428312B (en) | 9,10-bisphenylphenanthrene derivative and organic light emitting diode using the same | |
| CN111423436B (en) | Organic compound and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 264006 Shandong city of Yantai Province Economic and Technological Development Zone Wuzhi Mountain Road No. 11 Applicant after: In energy-conservation ten thousand profit limited-liability company Address before: 264006 Shandong city of Yantai Province Economic and Technological Development Zone Wuzhi Mountain Road No. 11 Applicant before: :YANTAI VALIANT FINE CHEMICALS Co., LTD. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: TO: CHINA ENERGY CONSERVATION VALIANT CO., LTD. |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20131204 |