CN104835916B - A kind of organic electroluminescence device of the luminescent layer that adulterated based on fluorescence - Google Patents
A kind of organic electroluminescence device of the luminescent layer that adulterated based on fluorescence Download PDFInfo
- Publication number
- CN104835916B CN104835916B CN201510190431.3A CN201510190431A CN104835916B CN 104835916 B CN104835916 B CN 104835916B CN 201510190431 A CN201510190431 A CN 201510190431A CN 104835916 B CN104835916 B CN 104835916B
- Authority
- CN
- China
- Prior art keywords
- layer
- fluorescence
- thickness
- luminescent layer
- organic electroluminescence
- 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.)
- Active
Links
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 68
- 230000005540 biological transmission Effects 0.000 claims abstract description 13
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims abstract description 6
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 15
- 239000002019 doping agent Substances 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 3
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 3
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 3
- QMXFUIUEGUOSEV-UHFFFAOYSA-N 3,4,5,6-tetra(carbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound N#Cc1c(C#N)c(c(c(c1-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12 QMXFUIUEGUOSEV-UHFFFAOYSA-N 0.000 claims description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 claims description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- 230000005525 hole transport Effects 0.000 claims description 2
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 1
- 230000005281 excited state Effects 0.000 abstract description 9
- -1 transparent anode Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000003111 delayed effect Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000007725 thermal activation Methods 0.000 description 5
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical group [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 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- QPZYNVHZZYFXRT-UHFFFAOYSA-N C1=CC=CC=C1.C1(=CC=CC=C1)C=1NC2=C(N1)C=CC=C2 Chemical compound C1=CC=CC=C1.C1(=CC=CC=C1)C=1NC2=C(N1)C=CC=C2 QPZYNVHZZYFXRT-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000003996 delayed luminescence Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
- H10K50/121—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants for assisting energy transfer, e.g. sensitization
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/20—Delayed fluorescence emission
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a kind of device architecture of Organic Light Emitting Diode (OLED), more particularly, to a kind of high-efficiency fluorescence doping organic electroluminescence device.The organic electroluminescence device of present invention preparation is made up of transparent substrates, transparent anode, hole transmission layer, the first exciton barrier-layer, luminescent layer, the second exciton barrier-layer, electron transfer layer, electron injecting layer and metallic cathode.Wherein luminescent layer is made up of host-guest system, and material of main part is a class singlet excited and the less organic molecule of triplet excited state energy level difference, and guest materials is the dye molecule of the high fluorescence efficiencies such as quinacridone derivative.Device external quantum efficiency of the present invention has exceeded the theoretical limit efficiency of conventional fluorescent device about 5%, can effectively improve the luminous efficiency of fluorescence OLED.The luminescent device of present invention preparation has the advantages that luminosity is high, cut-in voltage is low, efficiency high, efficiency roll-off are little.
Description
Technical field
The invention belongs to organic electroluminescence device technical field is and in particular to a kind of organic electroluminescence device
(OLED), such organic electroluminescence device is using having thermal activation delayed fluorescence (TADF, Thermally Activated
Delayed Fluorescence) characteristic organic material as material of main part and quinacridone fluorescent material doping prepare organic
The luminescent layer of electroluminescent device, device has very high efficiency.
Background technology
Organic electroluminescence device (OLEDs, Organic Light Emitting Diods) is using electronics and hole
Luminous in conjunction with the exciton producing.According to the supposition of electron spin statistical law, its singlet excitons producing and triplet
The ratio of exciton is 1:3, typically, using during small molecule fluorescent luminescent material, it is only capable of swashing using wherein 25% singlet state
Son, and remaining 75% triplet exciton loses because of radiationless transition.So the organic electroluminescence of general fluorescent material is sent out
Optical device internal quantum efficiency is less than 25%.And for phosphor material, it utilizes the spin coupling effect of heavy atom, substance
The energy of excited state can be transferred in triplet excited state by intersystem crossing (ISC), and then by the luminous i.e. phosphorescence of triplet excited state,
Therefore device internal quantum efficiency can reach 100% in theory.But, because high efficiency electromechanical phosphorescent material must contain iridium, platinum
Deng noble metal, there is expensive, natural resources shortage fatal shortcoming.In addition, current navy blue electromechanical phosphorescent material performance (colour purity
Degree, efficiency and stability) poor.So developing some aboundresources and relatively inexpensive stable high efficiency organic molecule is electroluminescent
Luminescent material seems particularly important.
The fluorescence OLED enabling to break through 25% internal quantum efficiency restriction at present mainly employs delayed fluorescence machine
System, the triplet excited state energy in its energy effectively utilizes device.Its mechanism mainly has two classes, and a class is TTA (Triplet-
Triplet Annihilation, T-T annihilation) mechanism (see D.Kondakov, T.D.Pawlik,
T.K.Hatwar, and J.P.Spindler, J.Appl.Phys., 2009,106,124510).Another kind of is TADF
(Thermally Activated Delayed Fluorescence, thermal activation delayed fluorescence) mechanism (see H.Uoyama,
K.Goushi, K.Shizu, H.Nomura, C.Adachi, Nature., 2012,492,234).TTA mechanism is using two three
Weight state exciton merges generation singlet excitons, improves the mechanism that singlet excitons generate ratio, but its device imperial palace quantum effect
Rate only has 40%～62.5%.TADF mechanism is using having poor (the Δ E of less singlet state-triplet energy levelST) organic little point
Sub- material, its triplet exciton can be converted into singlet state by reverse intersystem crossing (RISC) this process under environment thermal energy and swash
The mechanism of son.Its device internal quantum efficiency can reach 100% in theory.But efficiency roll-off is larger under high illumination for its device, limit
Make its application in total colouring and white-light illuminating.
Conventional fluorescent dye molecule often has very high fluorescence quantum yield, but its doping OLED is due to being limited to
25% internal quantum efficiency, external quantum efficiency is generally less than 5%, and also there is a big difference with the efficiency of phosphorescent devices.As HONGGUANG dye
Material DCM is (see C.W.Tang, S.A.VanSlyke, and C.H.Chen, J.Appl.Phys., 1989,65,3610；
U.S.Pat.No.5,908,581), device efficiency<10cd/A；Green glow dyestuff quinacridone (see U.S.Pat.No.5,227,
252；5,593,788；CN1482127A；CN1219778；CN1660844), device efficiency<20cd/A etc..
TADF molecule is entrained in the material of main part of broad stopband mainly as guest materials and realizes efficient thermal activation at present
Delayed fluorescence (see Q.Zhang, J.Li, K.Shizu, S.Huang, S.Hirata, H.Miyazaki, C.Adachi,
J.Am.Chem.Soc.2012,134,14706；H.Uoyama,K.Goushi,K.Shizu,H.Nomura,C.Adachi,
Nature.,2012,492,234；T.Nishimoto,T.Yasuda,S.Y.Lee,R.Kondo,C.Adachi,
Mater.Horiz., document report 2014,1,264), is also had to have bipolarity as the material of main part use of phosphor material
Transport property, enable more balance carrier mobility (see D.D.Zhang, L.Duan, D.Q.Zhang, J.Qiao,
G.F.Dong, L.D.Wang, Y.Qiu, Organic Electronics., 2013,14,260), and as fluorescent material
Material of main part OLED more rare (see D.D.Zhang, L.Duan, C.Li, Y.L.Li, H.Y.Li, D.Q.Zhang,
Y.Qiu,Adv.Mater.2014,26,5050；Patent WO 2012133188 A1).
Content of the invention
Relatively low in order to solve the problems, such as conventional fluorescent dyestuff device efficiency, it is an object of the invention to using having substance
State-triplet energy level difference is less than the thermal activation delayed fluorescence material of 0.3eV as fluorescence OLED material of main part, by doping
The quinacridone guest materials with high efficiency photoluminescence quantum efficiency prepares luminescent layer.Material of main part in the case of electrical pumping
The electroexcitation state of middle generation realizes triplet excited state turning to singlet excited by the physical process of thermal activation delayed fluorescence
Become, then object is arrived by main bodyEnergy transfer makes doping fluorescent dye molecule be in singlet excited, finally, place
Fluorescence doping molecule in singlet excited returns to ground state in the way of radiation transistion, and high efficiency electroluminescent fluorescent is achieved, from
And improve the luminous efficiency of fluorescence OLED, the efficiency of electrochromic fluorescent devices can reach the level of electro phosphorescent device.
The principle of the present invention is：
In the device of the present invention, adulterated with fluorescent material by the use of the organic molecule with TADF characteristic as material of main part
Prepare the luminescent layer of organic electroluminescence device, the doping content of fluorescent material is 0.5-1.0%, in the case of electrical pumping
The singlet excited generating in TADF material of main part and the ratio of triplet excited state are classified as 1:3, due to having less singlet state-triple
The TADF material of main part of state energy level difference its triplet excited state under environment thermal energy can be converted by inverse intersystem crossing (RISC) process
For singlet excited, when TADF material of main part has good energy match relation with doped luminescent material, host molecule is extremely
Between guest molecule, the leading mechanism of energy transfer is long-rangeType energy transfer, i.e. singlet state-singlet energy transfer side
Formula.Based on above-mentioned principle, guest molecule not only can obtain the energy of the main body singlet excited directly generating, and also can obtain warp
It is converted into the energy of the triplet exciton of singlet excitons by RISC process, its internal quantum efficiency also can reach 100% in theory,
Detailed process is as shown in Figure 1.Wherein solid line is advantageous process, and dotted line is unfavorable process, pitches as energy loss process.S0,H,
S0,GIt is respectively the ground state level of material of main part and guest materials, S1,H, S1,GIt is respectively material of main part and the substance of guest materials swashs
Send out state energy level, T1,H, T1,GThe triplet excited state energy level of material of main part and guest materials respectively, ISC is intersystem crossing process, RISC
It is inverse intersystem crossing process, PF is transient luminescence, and DF is delayed luminescence, and NR is nonradiative transition, and ET is energy transfer process.
The technical solution of the present invention is：
Organic electroluminescence device structure be on a transparent substrate be sequentially prepared nesa coating, hole transmission layer, first
Exciton barrier-layer, luminescent layer, the second exciton barrier-layer, electron transfer layer, electron injecting layer and negative electrode.Wherein luminescent layer is host and guest
The thin film of the material doped preparation of body, material of main part adopt TADF material 4CzIPN, 4CzPN or 2CzPN (see Nature, 2012,
492,235), it is characterized by singlet state-triplet energy level difference Δ EST<0.1eV, dopant material is using having high fluorescence quantum efficiency
Quinacridone derivative (QA) dye molecule DR1DR-QA or DR1DR2DR-QA, doping content be 0.3～1.5% (weight hundred
Divide content), the thickness range of luminescent layer is 15～40nm.
In above formula, R4It is the straight or branched alkyl containing 1～10 carbon；R5、R6It is the straight chain containing 1～6 carbon respectively
Or branched alkyl, F, Cl, carbazole, diphenylamines or triphenylamine.
Typical QA derivant is DFDB-QA, DCF3DB-QA, TFDB-QA or TCF3DB-QA etc..
First exciton barrier-layer is more than 3.0eV for band gap width and has electronic blocking and the material of hole transport performance,
As TCTA, TAPC or mCP etc., thickness is 3～20nm.
Second exciton barrier-layer is more than 3.0eV for band gap width and has the material of hole barrier and electronic transmission performance,
As TPBi, TmPyPB or BCP etc., thickness is 3～20nm.
Hole transmission layer is made up of NPB etc., and thickness is 20～50nm；Electron transfer layer is by BePP2Deng composition, thickness is 30
～60nm.
The material of electron injecting layer is LiF, and thickness is 0.5～1nm.
Cathode material can be the active metals such as aluminum, magnesium silver alloy, and its thickness is 200～2000nm.
The structural formula of layers of material is as follows：
The preparation method of organic electroluminescence device of the present invention is as follows：
Using the vacuum-deposited method of hot evaporation, prepare nesa coating on a transparent substrate, and control thickness to sink successively
Long-pending hole transmission layer, the first exciton barrier-layer, luminescent layer, the second exciton barrier-layer, electron transfer layer, electron injecting layer and the moon
Pole.Organic electroluminescence device of the present invention can be used for preparing flat faced display, lighting source, signal lighties or direction board
Deng.
Brief description
Fig. 1：Electroluminescent device operation principle schematic diagram involved in the present invention；
Fig. 2：The overall structure diagram of OLED of the present invention；
Fig. 3：(luminescent layer is 4CzIPN to OLED of the present invention:0.5%DFDB-QA) luminescent spectrum schematic diagram；
Fig. 4：(luminescent layer is 4CzIPN to OLED of the present invention:0.5%TCF3DB-QA) luminescent spectrum schematic diagram；
Fig. 5：(luminescent layer is 4CzIPN to OLED of the present invention:0.5%DFDB-QA) current efficiency-brightness-power
Efficiency schematic diagram；
Fig. 6：OLED luminescent layer of the present invention is 4CzIPN:0.5%TCF3DB-QA) current efficiency-brightness-work(
Rate efficiency schematic diagram.
The structure of the electroluminescent device of present invention preparation is as shown in figure 1, each component names are：Clear glass or other saturating
Bright substrate 1, attachment ITO (indium tin oxide) anode 2 on a transparent substrate, NPB (N, N'- bis- (1- naphthyl)-N, N'- hexichol
Base -1,1'- biphenyl -4,4'- diamidogen) hole transmission layer 3, TCTA (4,4', 4 "-three (9- carbazyl) triphenylamine), the first exciton
Barrier layer 4, the luminescent layer 5 of material of the present invention, the second exciton barrier-layer 6, three (phenylbenzimidazol) benzene (TPBI) electricity
Sub- transport layer 7, LiF electron injecting layer 8, metal Al are as negative electrode 9.
Material of main part used by comparative device luminescent layer is Alq3.
Electroluminescent device is using the material of main part 4CzIPN and fluorescent material DFDB- with TADF characteristic in the present invention
Maximum power efficiency 53.4lm/W of the electroluminescent device of QA doping preparation, and using not having the material of main part of TADF characteristic
As Alq3With maximum power efficiency 11.6lm/W of the electroluminescent device of DFDB-QA doping preparation, the former efficiency is the latter
4.6 times (see embodiments 1).Above-mentioned enforcement explanation, using the material of main part with TADF characteristic and fluorescent material Proper Match
The efficiency of electroluminescent device can very significantly be improved with doping.
Specific embodiment
The following examples be in order to enumerate typical example to illustrate using have the material of main part of TADF characteristic with glimmering
Photodoping material construction luminescent layer simultaneously prepares high efficiency electroluminescent device, rather than limit the present invention using embodiment.
Embodiment 1：Device [ITO/NPB/mCP/4CzIPN:0.5%DFDB-QA/BCP/BePP2/LiF/Al]
The thick ITO conducting glass substrate of 15mm × 15mm × 1mm is cleaned by ultrasonic 5 minutes with ITO cleanout fluid, deionized water
It is cleaned by ultrasonic 5 minutes, acetone is cleaned by ultrasonic 20 minutes, isopropanol is cleaned by ultrasonic 20 minutes.After drying, plasma (plasma)
Process 5 minutes.In fine vacuum 5 × 10-5It is sequentially depositing hole transmission layer NPB, thickness is 35nm under Pa；First exciton barrier-layer
MCP, thickness is 5nm；The method depositing light emitting layer that double source steams altogether, wherein material of main part are 4CzIPN, and object dopant material is
DFDB-QA, doping content is 0.5% (weight percentage), and thickness is 30nm；Second exciton barrier-layer BCP, thickness is 5nm；
Electron transfer layer BePP2, thickness is 40nm.Redeposited electron injecting layer LiF, thickness is 1nm；Metallic cathode Al, thickness
100nm.This device cut-in voltage is 2.7V, high-high brightness 113100cd/m2, maximum power efficiency 53.4lm/W.
Comparative device structure [ITO/NPB/mCP/Alq3:0.5%DFDB-QA/BCP/BePP2/ LiF/Al] device open
Voltage is 3.0V, high-high brightness 46140cd/m2, maximum power efficiency 11.6lm/W.
Embodiment 2：Device [ITO/NPB/mCP/4CzIPN:0.5%TCF3DB-QA/BCP/BePP2/LiF/Al]
The thick ITO conducting glass substrate of 15mm × 15mm × 1mm is cleaned by ultrasonic 5 minutes with ITO cleanout fluid, deionized water
It is cleaned by ultrasonic 5 minutes, acetone is cleaned by ultrasonic 20 minutes, isopropanol is cleaned by ultrasonic 20 minutes.After drying, plasma is processed 5 minutes.
In fine vacuum 5 × 10-5It is sequentially depositing hole transmission layer NPB, thickness is 35nm under Pa；First exciton barrier-layer mCP, thickness is
5nm；The method depositing light emitting layer that double source steams altogether, wherein material of main part are 4CzIPN, and object dopant material is TCF3DB-QA, mixes
Miscellaneous concentration is 0.5% (weight percentage), and thickness is 30nm；Second exciton barrier-layer BCP, thickness is 5nm；Electron transfer layer
BePP2, thickness is 40nm.Redeposited electron injecting layer LiF, thickness is 1nm and metallic cathode Al, thickness 100nm.This device is opened
Opening voltage is 2.8V, high-high brightness 106200cd/m2, maximum power efficiency 46.1lm/W.
Comparative device structure [ITO/NPB/mCP/Alq3:0.5%TCF3DB-QA/BCP/BePP2/ LiF/Al] device open
Opening voltage is 3.0V, high-high brightness 50240cd/m2, maximum power efficiency 12.5lm/W.
Embodiment 3：Device [ITO/NPB/mCP/4CzIPN:0.5%DCF3DB-QA/BCP/BePP2/LiF/Al]
The thick ITO conducting glass substrate of 15mm × 15mm × 1mm is cleaned by ultrasonic 5 minutes with ITO cleanout fluid, deionized water
It is cleaned by ultrasonic 5 minutes, acetone is cleaned by ultrasonic 20 minutes, isopropanol is cleaned by ultrasonic 20 minutes.After drying, plasma is processed 5 minutes.
In fine vacuum 5 × 10-5It is sequentially depositing hole transmission layer NPB, thickness is 35nm under Pa；First exciton barrier-layer mCP, thickness is
5nm；The method depositing light emitting layer that double source steams altogether, wherein material of main part are 4CzIPN, and object dopant material is DCF3DB-QA, mixes
Miscellaneous concentration is 0.5% (weight percentage), and thickness is 30nm；Second exciton barrier-layer BCP, thickness is 5nm；Electron transfer layer
BePP2, thickness is 40nm.Redeposited electron injecting layer LiF, thickness is 1nm and metallic cathode Al, thickness 100nm.This device is opened
Opening voltage is 3.0V, high-high brightness 96500cd/m2, maximum power efficiency 45.3lm/W.
Comparative device structure [ITO/NPB/mCP/Alq3:0.5%DCF3DB-QA/BCP/BePP2/ LiF/Al] device open
Opening voltage is 3.2V, high-high brightness 49170cd/m2, maximum power efficiency 11.6lm/W.
Embodiment 4：Device [ITO/NPB/mCP/4CzIPN:0.5%TFDB-QA/BCP/BePP2/LiF/Al]
The thick ITO conducting glass substrate of 15mm × 15mm × 1mm is cleaned by ultrasonic 5 minutes with ITO cleanout fluid, deionized water
It is cleaned by ultrasonic 5 minutes, acetone is cleaned by ultrasonic 20 minutes, isopropanol is cleaned by ultrasonic 20 minutes.After drying, plasma processes minute.
In fine vacuum 5 × 10-5It is sequentially depositing hole transmission layer NPB, thickness is 35nm under Pa；First exciton barrier-layer mCP, thickness is
5nm；The method depositing light emitting layer that double source steams altogether, wherein material of main part are 4CzIPN, and object dopant material is TFDB-QA, doping
Concentration is 0.5% (weight percentage), and thickness is 30nm；Second exciton barrier-layer BCP, thickness is 5nm；Electron transfer layer
BePP2, thickness is 40nm.Redeposited electron injecting layer LiF, thickness is 1nm and metallic cathode Al, thickness 100nm.This device is opened
Opening voltage is 2.8V, high-high brightness 95300cd/m2, maximum power efficiency 47.1lm/W.
Comparative device structure [ITO/NPB/mCP/Alq3:0.5%TFDB-QA/BCP/BePP2/ LiF/Al] device open
Voltage is 3.1V, high-high brightness 50320cd/m2, maximum power efficiency 12.3lm/W.
Claims (6)
1. a kind of based on fluorescence adulterate luminescent layer organic electroluminescence device it is characterised in that：Successively by transparent substrates, transparent
Conducting film, hole transmission layer, the first exciton barrier-layer, luminescent layer, the second exciton barrier-layer, electron transfer layer, electron injecting layer
With negative electrode composition；The thin film of guest materials doping preparation based on luminescent layer, material of main part is structural formula TADF material as follows
Material 4CzIPN, 4CzPN or 2CzPN, dopant material be structural formula quinacridone derivative DR1DR-QA as follows or
DR1DR2DR-QA, doping percetage by weight is 0.3～1.5%；
Wherein, R4It is the straight or branched alkyl containing 1～10 carbon；R5、R6It is the straight or branched containing 1～6 carbon respectively
Alkyl, F, Cl, carbazole, diphenylamines or triphenylamine.
2. as claimed in claim 1 a kind of based on fluorescence adulterate luminescent layer organic electroluminescence device it is characterised in that：Mix
Miscellaneous material is DFDB-QA, DMeDB-QA, TCF3DB-QA or TMeDB-QA, its structural formula is as follows,
3. a kind of organic electroluminescence device of the luminescent layer that adulterated based on fluorescence as claimed in claim 1 or 2, its feature exists
In：First exciton barrier-layer is more than 3.0eV for band gap width and has electronic blocking and the material of hole transport performance；Second swashs
Sub- barrier layer is more than 3.0eV for band gap width and has the material of hole barrier and electronic transmission performance.
4. as claimed in claim 3 a kind of based on fluorescence adulterate luminescent layer organic electroluminescence device it is characterised in that：The
One exciton barrier-layer is TCTA, TAPC or mCP, and thickness is 3～20nm；Second exciton barrier-layer is TPBi, TmPyPB or BCP,
Thickness is 3～20nm；Hole transmission layer is NPB, and thickness is 20～50nm；Electron transfer layer is BePP2, thickness be 30～
60nm；Electron injecting layer is LiF, and thickness is 0.5～3nm；Negative electrode is aluminum or magnesium silver alloy, and thickness is 50～200nm；Luminescent layer
Thickness be 15～40nm.
5. the organic electroluminescence device of a kind of luminescent layer that adulterated based on fluorescence as described in claim 1,2 or 4, its feature exists
In：For preparing flat faced display, lighting source, signal lighties or direction board.
6. as claimed in claim 3 a kind of based on fluorescence adulterate luminescent layer organic electroluminescence device it is characterised in that：With
In preparing flat faced display, lighting source, signal lighties or direction board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510190431.3A CN104835916B (en) | 2015-04-11 | 2015-04-11 | A kind of organic electroluminescence device of the luminescent layer that adulterated based on fluorescence |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510190431.3A CN104835916B (en) | 2015-04-11 | 2015-04-11 | A kind of organic electroluminescence device of the luminescent layer that adulterated based on fluorescence |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104835916A CN104835916A (en) | 2015-08-12 |
| CN104835916B true CN104835916B (en) | 2017-03-08 |
Family
ID=53813656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510190431.3A Active CN104835916B (en) | 2015-04-11 | 2015-04-11 | A kind of organic electroluminescence device of the luminescent layer that adulterated based on fluorescence |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104835916B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887444B (en) * | 2015-12-15 | 2020-01-10 | 昆山工研院新型平板显示技术中心有限公司 | Organic light emitting display device and display apparatus |
| CN105418533B (en) * | 2015-12-18 | 2019-02-19 | 昆山国显光电有限公司 | A kind of feux rouges thermal activation delayed fluorescence material and organic electroluminescence device |
| CN106920884B (en) * | 2015-12-25 | 2019-08-16 | 昆山工研院新型平板显示技术中心有限公司 | A kind of organic electroluminescence device |
| CN106920883B (en) | 2015-12-25 | 2019-01-08 | 昆山工研院新型平板显示技术中心有限公司 | A kind of organic electroluminescence device |
| CN106997926B (en) * | 2016-01-26 | 2019-07-05 | 昆山工研院新型平板显示技术中心有限公司 | A kind of white light quantum point electroluminescent device |
| CN106997927B (en) * | 2016-01-26 | 2019-06-07 | 昆山工研院新型平板显示技术中心有限公司 | A kind of quanta point electroluminescent device |
| CN106997890B (en) * | 2016-01-26 | 2020-05-15 | 昆山工研院新型平板显示技术中心有限公司 | Color display device based on quantum dot electroluminescent device |
| CN106997889B (en) * | 2016-01-26 | 2019-10-15 | 昆山工研院新型平板显示技术中心有限公司 | A kind of RGB color display device based on quanta point electroluminescent device |
| US10217953B2 (en) | 2016-02-18 | 2019-02-26 | Boe Technology Group Co., Ltd. | Quantum dot light-emitting device, fabricating method thereof, and display substrate |
| CN107068881B (en) * | 2016-04-25 | 2019-12-03 | 中节能万润股份有限公司 | A kind of organic electroluminescence device containing acridones compound and its application |
| CN108011040B (en) * | 2016-10-31 | 2020-07-17 | 昆山工研院新型平板显示技术中心有限公司 | Green light organic electroluminescent device |
| CN107253950B (en) | 2017-05-17 | 2019-12-10 | 上海天马有机发光显示技术有限公司 | Compound, preparation method and organic light-emitting display device |
| CN108346751B (en) * | 2017-08-21 | 2019-06-11 | 广东聚华印刷显示技术有限公司 | Electroluminescent device and its luminescent layer and application |
| CN108484596B (en) * | 2018-03-09 | 2020-05-19 | 安徽科技学院 | Preparation method of organic luminescent material based on quinacridone and luminescent device thereof |
| CN109088008B (en) * | 2018-08-23 | 2021-01-26 | 京东方科技集团股份有限公司 | Organic light-emitting device and display panel |
| CN109256474B (en) * | 2018-09-03 | 2021-11-16 | 云谷（固安）科技有限公司 | Organic electroluminescent device and display device |
| CN110903236B (en) * | 2019-12-17 | 2022-11-29 | 武汉大学 | Dark blue electroluminescent material and preparation method and application thereof |
| CN112117388B (en) * | 2020-09-23 | 2023-10-24 | 京东方科技集团股份有限公司 | Organic electroluminescent device, display panel and display device |
| CN115768226B (en) * | 2023-01-05 | 2023-08-11 | 季华恒烨(佛山)电子材料有限公司 | Organic electroluminescent device and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9783734B2 (en) * | 2011-02-28 | 2017-10-10 | Kyulux, Inc. | Delayed fluorescence material and organic electroluminescence device |
| US20150249218A1 (en) * | 2012-09-03 | 2015-09-03 | Hodogaya Chemical Co., Ltd. | Compound having indenoacridan ring structure, and organic electroluminescent device |
| CN103985822B (en) * | 2014-05-30 | 2017-05-10 | 广州华睿光电材料有限公司 | Organic mixture, composite containing organic mixture, organic electronic device and application |
-
2015
- 2015-04-11 CN CN201510190431.3A patent/CN104835916B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104835916A (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104835916B (en) | A kind of organic electroluminescence device of the luminescent layer that adulterated based on fluorescence | |
| TWI673894B (en) | Organic electroluminescent device | |
| CN109192874B (en) | A kind of organic electroluminescence device and display device | |
| TWI640532B (en) | Phosphorescent organic electroluminescent device | |
| CN106068267B (en) | Electronic buffer material and organic electroluminescent device comprising the same | |
| CN109817818B (en) | Organic electroluminescent device and display device | |
| CN108011047B (en) | Red light organic electroluminescent device | |
| CN104393181B (en) | Red organic electroluminescent device and preparation method thereof | |
| CN108832008B (en) | Application of exciplex in organic light-emitting diode | |
| CN111416049B (en) | Application of double-exciplex host material in preparation of phosphorescent OLED device | |
| CN108011040A (en) | A kind of green organic electrofluorescence device | |
| CN102136550A (en) | White light organic electroluminescent device and preparation method thereof | |
| CN109638170B (en) | Organic electro-optic element | |
| CN102683608B (en) | Organic electroluminescent device and preparation method of organic electroluminescent device | |
| CN105884786A (en) | Benzofuran [2,3-b ] pyrazine derivative and application thereof in organic electroluminescent device | |
| CN108963099B (en) | Composition for organic electroluminescent element and organic electroluminescent element | |
| CN111740020B (en) | High-efficiency long-service-life blue light device | |
| CN108807710A (en) | Undoped organic electroluminescence device and the preparation method of connecting with the complementary white light of doping | |
| CN113066935A (en) | White organic electroluminescent device with double-excited-base compound as main body | |
| CN105261706A (en) | Planar heterojunction sensitized organic fluorescence light-emitting diode and preparation method therefor | |
| CN107026242B (en) | A kind of organic iridium of dark blue light (III) complex OLED device | |
| CN106008574A (en) | Multi-functional triarylborane derivative for body materials of organic electrophosphorescence devices and thermotropic delayed fluorescence material | |
| CN104218156A (en) | Organic light emission diode device and preparation method thereof | |
| CN109994632B (en) | Organic electroluminescent device | |
| CN112382729A (en) | Blue light fluorescence organic light emitting diode with TTA process-containing hybrid local charge transfer material as main body and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170818 Address after: Room 5, building A, zone, No. 2499, Wei Shan Road, high tech Zone, Changchun, Jilin, China Patentee after: Jilin University Science Park Development Center Address before: 130012 Changchun Qianjin Street, Jilin, No. 2699 Patentee before: Jilin University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20171009 Address after: 130012 Jilin province Changchun high tech District No. 3333 North Street North Grand Changchun science and technology park a first floor of building C2-1 Patentee after: Jilin Jida Incubator Co. Ltd. Address before: Room 5, building A, zone, No. 2499, Wei Shan Road, high tech Zone, Changchun, Jilin, China Patentee before: Jilin University Science Park Development Center |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171127 Address after: 130000 Jilin province Changchun Beihu Sheng Technology Development Zone No. 3333 North Street North Lake Science and technology park a B1-1 8 storey building 801 room 002 block Patentee after: Jilin meta synthetic electronic material Limited by Share Ltd Address before: 130012 Jilin province Changchun high tech District No. 3333 North Street North Grand Changchun science and technology park a first floor of building C2-1 Patentee before: Jilin Jida Incubator Co. Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 130000 Jilin province Changchun Beihu Sheng Technology Development Zone No. 3333 North Street North Lake Science and technology park a B1-1 8 storey building 801 room 002 block Patentee after: Jilin Yuanhe Electronic Material Co.,Ltd. Address before: 130000 Jilin province Changchun Beihu Sheng Technology Development Zone No. 3333 North Street North Lake Science and technology park a B1-1 8 storey building 801 room 002 block Patentee before: Jilin meta synthetic electronic material Limited by Share Ltd. |
|
| CP01 | Change in the name or title of a patent holder |