CN103421487A - Novel electroluminescent material and application thereof - Google Patents
Novel electroluminescent material and application thereof Download PDFInfo
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- CN103421487A CN103421487A CN2013100133013A CN201310013301A CN103421487A CN 103421487 A CN103421487 A CN 103421487A CN 2013100133013 A CN2013100133013 A CN 2013100133013A CN 201310013301 A CN201310013301 A CN 201310013301A CN 103421487 A CN103421487 A CN 103421487A
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- GEQBRULPNIVQPP-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(-c2cc(-c3nc4ccccc4[n]3-c3ccccc3)cc(-c3nc(cccc4)c4[n]3-c3ccccc3)c2)nc2c1cccc2 Chemical compound c(cc1)ccc1-[n]1c(-c2cc(-c3nc4ccccc4[n]3-c3ccccc3)cc(-c3nc(cccc4)c4[n]3-c3ccccc3)c2)nc2c1cccc2 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a novel electroluminescent material and application thereof, particularly to the micromolecule luminescent material containing 2, 6-di-tert-butyl-anthracene and N-phenylcarbazole, and relates to the application of the material in the field of organic electroluminescence. The material uses 2, 6-di-tert-butyl-anthracene and N-phenylcarbazole as the center, and combines the advantages of the two, wherein the anthracene structure has relatively good color purity, can effectively avoids the aggregation between molecules by introducing two tert-butyl with large steric hindrance, and can increase the quality of the molecules, improve the glass transition temperature, and increase molecule thermal stability by introducing a carbazole group with relatively large conjugated structure. Additionally, with the certain hole transmission property and non-coplanarity, the carbazole unit can effectively reduce the production of exciplex; with suitable molecular energy level, the material can be used as the luminescent material in an OLED (Organic Light-Emitting Device).
Description
Technical field
The present invention relates to a kind of novel materials for electroluminescence and application thereof, be specifically related to a kind of small molecules luminescent material that contains 2,6-di-tert-butyl anthracene and N-phenyl carbazole, and relate to the application of this material in the organic electroluminescent field.
Background technology
In recent years, organic electroluminescence device (OLED), as a kind of technique of display that the huge applications prospect is arranged, is subject to people and more and more pays close attention to.Due to its intrinsic characteristic, as luminous, wide viewing angle, fast response time, can realize the plurality of advantages such as flexible demonstration, make it become the most favourable rival of technique of display of future generation.Due to all circles' lasting input and unremitting effort for many years, the organic electroluminescent technology has had greatly development, nowadays, has had a lot of commodity based on the OLED technique of display to realize industrialization.However, the problems such as it is short that organic electroluminescence device still exists the life-span, and efficiency is low, remain people to do further exploration.
Material for organic electroluminescence device mainly comprises electrode materials, carrier transmission material, luminescent material.Electrode materials is divided into cathode material and anode material, and carrier transmission material comprises electron transport material and hole mobile material, and wherein luminescent material occupies critical positions in OLED.
In order to realize full-color demonstration, need respectively the luminescent material of three kinds of colors of red, green, blue.At present, red light material and green light material can meet practical needs, and the blue emitting material of efficient stable is still less, and it is lower to exist luminous efficiency, the problems such as work-ing life is relatively short, this has affected the development of organic electroluminescence device to a great extent.
A good blue emitting material not only needs to have purity of color preferably, also will consider its thin film stability, efficiency, distillation performance etc. simultaneously.The anthracene class formation has purity of color preferably, but is easy to crystallization, by introducing the tertiary butyl of large steric hindrance, can effectively avoid molecular aggregates, and there is the N-phenyl carbazole unit of nonplanar structure by introducing, can increase molecular mass, improve second-order transition temperature, increase thin film stability.Therefore, by 2,6-di-tert-butyl anthracene and N-phenyl carbazole group are combined, will be hopeful to obtain well behaved blue emitting material.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of and is used in organic electroluminescence device, can obtain the novel materials for electroluminescence of efficient blue light.
The scheme that the present invention solves the problems of the technologies described above is as follows: a kind of novel materials for electroluminescence has structure as shown in Equation 1:
Wherein, described Ar
1And Ar
2Independent selection (formula 2) in following structure respectively can be the same or different:
That is, described Ar
1For any one in formula 2, described Ar
2For any one in formula 2.
The invention has the beneficial effects as follows:
Novel materials for electroluminescence of the present invention is applied in blue organic electroluminescent device, demonstrates higher efficiency, and its characteristics are:
1. with 2, centered by 6-di-tert-butyl anthracene and N-phenyl carbazole, take into account both advantages, the anthracene structure has purity of color preferably, by introducing the tertiary butyl of two large steric hindrances, can effectively avoid intermolecular gathering, and there is the carbazole group of larger conjugated structure by introducing, can increase molecular mass, improve second-order transition temperature, increase molecular heat stability.
2. there is electroluminescence characters preferably.Take the blue organic electroluminescent device that this compounds is luminescent material, the peak wavelength 440-452nm of device, the CIE coordinate (0.15,0.15-0.17), high-high brightness 3000-4500cd/m
2.
In the present invention, the preparation method of novel materials for electroluminescence is as follows:
By 2,6-di-t-butyl-9, the 10-dibromoanthracene carries out the Suzuki linked reaction from boric acid or the boric acid ester of the N-phenyl carbazole of different the position of substitution respectively, obtains target compound.
In above-mentioned steps, the Suzuki linked reaction is carried out under nitrogen protection, and catalyzer is Pd (PPh
3)
4Or palladium, 60～100 ℃ of temperature of reaction, 12～36 hours reaction times.
By aforesaid method, prepare luminescent material BECz(formula a) and BEP(formula b) reaction process as follows:
Reaction process
Novel materials for electroluminescence provided by the invention is with 2, centered by 6-di-tert-butyl anthracene and N-phenyl carbazole, take into account both advantages, the anthracene structure has purity of color preferably, by introducing the tertiary butyl of two large steric hindrances, can effectively avoid intermolecular gathering, and there is the carbazole group of larger conjugated structure by introducing, can increase molecular mass, improve second-order transition temperature, increase molecular heat stability.In addition, carbazole unit has certain hole transport character and non-coplanarity, can effectively reduce the generation of exciplex, and this material has applicable molecular entergy level, can be used as the blue emitting material in organic electroluminescence device.
The present invention also provides the application example of above-mentioned luminescent material for the organic electroluminescence device luminescent layer.Prepared blue organic electroluminescent device generally comprises ITO Conducting Glass (anode), the hole transmission layer (NPB) of stack successively, luminescent layer (BECz), electron transfer layer (TPBI), electron injecting layer (LiF) and cathode layer (Al).The all functions layer all adopts vacuum evaporation process to make.In this device, the molecular structural formula of organic compound more used is as follows:
The functional layer of device of the present invention is not limited to use above-mentioned materials, and these materials can replace with other materials, to device performance to be further improved, can be with replacements such as TPD as hole transmission layer, and electron transfer layer can be used Alq
3Deng replacement.The molecular structural formula of these materials is as follows:
Certainly, the OLED device that the material provided by the present invention of usining makes as luminescent layer, device performance has the space of further lifting, as mode is mixed in use, luminescent material is disperseed etc., and this also should be understood to, belongs to protection category of the present invention.
The accompanying drawing explanation
Fig. 1 is uv-visible absorption spectra and the fluorescence emission spectrum of BECz in chloroformic solution according to embodiment 1 preparation;
Fig. 2 is usingd BECz as the luminescent layer of blue organic electroluminescent device, the voltage-to-current densimetric curve of device in embodiment 2;
Fig. 3 is usingd BECz as the luminescent layer of blue organic electroluminescent device, the voltage-brightness curve of device in embodiment 2;
Fig. 4 is usingd BECz as the luminescent layer of blue organic electroluminescent device, the current density of device-current efficiency curve in embodiment 2;
Fig. 5 is usingd BECz as the luminescent layer of blue organic electroluminescent device, the current density of device-effect rate curve in embodiment 2;
Fig. 6 is usingd BECz as the luminescent layer of blue organic electroluminescent device in embodiment 2, device is 4200cd/m in brightness
2The time electroluminescent spectrum figure;
Fig. 7 is uv-visible absorption spectra and the fluorescence emission spectrum of BEP in chloroformic solution according to embodiment 3 preparations;
Embodiment
Below in conjunction with accompanying drawing, principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Preparation and the character of embodiment 1 luminescent material BECz:
1 luminescent material BECz's is synthetic
In the 250mL there-necked flask, add 1.3g2,6-di-t-butyl-9,10-dibromoanthracene (2.9mmol) and 2.5gN-phenyl-3-carbazole boric acid ester (6.8mmol), add mixed solvent (70mL toluene, 35mL ethanol), then adds 20mL K
2CO
3The aqueous solution (2M), logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask, add Pd (PPh
3)
40.183g(0.158mmol), under strong stirring, reflux, successive reaction 24h.Add the 50mL deionized water in reaction solution, 150mL ethyl acetate, separatory, collect organic phase, concentrating under reduced pressure, thick product carries out purifying through column chromatography, eluent is ethyl acetate: normal hexane (1:10), obtain the 1.8g yellow solid, use tetrahydrofuran (THF): dehydrated alcohol (1:2) recrystallization obtains the 1.5g faint yellow solid, use the chemical gas-phase deposition system purification that further distils, 370 ℃ of sublimation temperatures, obtain the faint yellow target compound of 1.05g, productive rate 47%.
1H NMR (CDCl3, TMS, δ): 8.28-8.29 (d, 2H), (8.11-8.16 dd, 2H), 7.72-7.78 (m, 8H), (7.62-7.71 m, 6H), 7.50-7.57 (m, 6H), (7.44-7.49 m, 2H), 7.38-7.42 (m, 2H), 7.28-7.34 (m, 2H), (1.23 S, 18H). high resolution mass spectrum, molecular formula C
58H
48N
2, theoretical value 772.3817,, test value 772.3794.
The uv-visible absorption spectra of 2 BECz and fluorescence spectrum
As shown in Figure 1, the solvent of use is chloroform for the uv-visible absorption spectra of BECz sterling under solution state and fluorescence spectrum.The fluorescence spectrum main peak 447nm of BECz, for sky blue luminous.
The present embodiment prepares blue organic electroluminescent device by the following method:
A) clean the ITO(tin indium oxide) glass: use respectively deionized water, acetone, ethanol ultrasonic cleaning ito glass respectively 30 minutes, then process 5 minutes in the plasma clean device;
B) vacuum evaporation hole transmission layer NPB on the anode ito glass, thickness is 50nm;
C) on hole transmission layer NPB, vacuum evaporation luminescent layer BECz, thickness is 30nm;
D) on luminescent layer BECz, vacuum evaporation electron transfer layer TPBI, thickness is 30nm;
E) on electron transfer layer TPBI, vacuum evaporation electron injecting layer LiF, thickness is 1nm;
F) on electron injecting layer LiF, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/NPB (50nm)/BECz (30nm)/TPBI (30nm)/LiF (1nm)/Al (100nm).BECz prepared by the embodiment 1 of usining is as the luminescent layer of this device, and as shown in Figure 2, as shown in Figure 3, as shown in Figure 4, current density-the effect rate curve as shown in Figure 5 for current density-current efficiency curve for voltage-brightness curve for the voltage-to-current densimetric curve of this device.The bright voltage that opens of device is 5.0V, and high-high brightness reaches 4200cd/m
2, maximum current efficiency 2.27cd/A, effect rate 0.65lm/W.Fig. 6 is 4200cd/m for this device in brightness
2The time electroluminescent spectrum figure, the CIE coordinate is positioned at (0.15,0.17).
Preparation and the character of embodiment 3 luminescent material BEP:
1 luminescent material BEP's is synthetic
In the 500mL there-necked flask, add 1.2g2,6-di-t-butyl-9,10-dibromoanthracene (2.67mmol) and 2.84g4-carbazole phenylo boric acid (6.4mmol), add mixed solvent (75mL toluene, 38mL ethanol), then adds 25mL K
2CO
3The aqueous solution (2M), logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask, add Pd (PPh
3)
40.21g, under strong stirring, reflux, successive reaction 36h.Add the 70mL deionized water in reaction solution, 150mL ethyl acetate, separatory, collect organic phase, concentrating under reduced pressure, thick product carries out purifying through column chromatography, eluent is trichloromethane: normal hexane (1:3), obtain the thick product of 1.6g, use trichloromethane: ethyl acetate (1:10) recrystallization obtains the 1.2g white solid, use the chemical gas-phase deposition system purification that further distils, 330 ℃ of sublimation temperatures, obtain 1.02g white object thing, productive rate 49.4%.
1H NMR (CDCl3, TMS, δ): 8.22-8.23 (d, 4H), (7.82-7.88 m, 6H), 7.74-7.79 (m, 6H), 7.62-7.66 (d, 4H), (7.57-7.60 m, 2H), 7.50-7.55 (m, 4H), 7.35-7.40 (m, 4H), (1.36 S, 18H). high resolution mass spectrum, molecular formula C
58H
48N
2, theoretical value 772.3817, test value 772.3802.
The uv-visible absorption spectra of 2 BEP and fluorescence spectrum
As shown in Figure 7, the solvent of use is chloroform for the uv-visible absorption spectra of BEP sterling under solution state and fluorescence spectrum.The fluorescence spectrum main peak 435nm of BEP is blue-light-emitting.
The foregoing is only embodiments of the invention, is not limitation of the present invention.The present invention aims to provide a kind of efficient blue light material; using the OLED device of material provided by the present invention as luminescent layer; device performance has the space of further lifting; as mode is mixed in use; luminescent material is disperseed; or use other material to replace TPBI as electron transfer layer etc., similar improvement all should be understood to, belongs to protection category of the present invention.
Claims (2)
1. a novel materials for electroluminescence, is characterized in that, the structural formula of described electroluminescent material is as follows:
In formula, described Ar
1For any one in following structural formula:
Described Ar
2For any one in following structural formula:
2. novel materials for electroluminescence as claimed in claim 1 is as the application of blue emitting material in organic electroluminescence device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586353A (en) * | 2018-06-15 | 2018-09-28 | 华南理工大学 | A kind of luminous organic material and its preparation method and application based on anthracene and its derivative |
| CN112239414A (en) * | 2020-09-29 | 2021-01-19 | 华南理工大学 | Blue organic semiconductor material based on 2, 6-di-tert-butyl anthracene and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586353A (en) * | 2018-06-15 | 2018-09-28 | 华南理工大学 | A kind of luminous organic material and its preparation method and application based on anthracene and its derivative |
| CN112239414A (en) * | 2020-09-29 | 2021-01-19 | 华南理工大学 | Blue organic semiconductor material based on 2, 6-di-tert-butyl anthracene and preparation method and application thereof |
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