CN102031104B - Bipolar phosphorescent main material containing anthracene derivatives of tetraphenyl silicane and carbazole and organic electroluminescent device - Google Patents
Bipolar phosphorescent main material containing anthracene derivatives of tetraphenyl silicane and carbazole and organic electroluminescent device Download PDFInfo
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Abstract
The invention discloses a bipolar phosphorescent main material containing anthracene derivatives of tetraphenyl silicane and carbazole and an organic electroluminescent device. The organic electroluminescent device has a layered doped structure, wherein a luminescent layer is made from bipolar phosphorescent main material doped series Ir (III) luminescent material which contains the anthracene derivatives of tetraphenyl silicane and carbazole. The series main material has relatively wide band gap, relatively high glass transition temperature (Tg) and excellent bipolarity of hole/electron transmission capability, is applied to the main material of green organic phosphorescent luminophor and also has the potential of red light and blue light application. The phosphorescent main material has the biggest characteristic of bipolar hole and electron transmission property and can be widely applied to the red, green and blue (RGB) base color doped phosphorescent main material. The manufacturing process is simple and the invention provides an excellent material for full-color display and illumination application.
Description
Technical field
The invention belongs to organic electroluminescent phosphorescent light body material and luminescent device field, be specifically related to the anthracene derivant phosphorescent light body material containing tetraphenyl-silicon and carbazole, and the organic electroluminescence device of this series material of main part.
Background technology
Phosphorescent organic electroluminescent diode (OLED) is because it can utilize triplet state and singlet state exciton, and internal quantum efficiency can reach 100% in theory, thereby causes insider's very big concern.In order to obtain higher electroluminescent phosphorescence efficiency, usually the heavy metal phosphor material is doped in material of main part and reduces concentration quenching and T-T annihilation.Thereby material of main part provides hole and electron recombination center to produce excited electronic state, then the excited energy of main body is passed to doping agent.Therefore, material of main part can either transmit hole also can transmit electronics, if hole and electronics can balance will improve the performance of device greatly in recombination region.In order to realize the carrier balance in luminous zone, material of main part formation double emitting layers or hybrid agent luminescent layer that use has hole and electron transport ability have obtained higher device performance, but such device architecture is more complicated, preparation technology is more loaded down with trivial details, therefore develop a kind of bipolar host material that simultaneously there is hole, electron transport ability for equilbrium carrier in luminous zone compound raising phosphorescence device performance, simplify preparation technology and there is very real meaning.Some research groups had developed a series of bipolar host material in recent years, obtained device performance preferably, such as people [Journal of Polymer Science:Part A:Polymer Chemistry such as KUN-MING YEH, Vo1.46,5180-5193 (2008)] by oxadiazole and carbazole derivative to being bonded into PCOn series bipolar host material, doping Ir (ppy)
3it is 19903cd/m that fabricate devices obtains high-high brightness
2, maximum current efficiency is 17.9cd/A.The people [J.Mater.Chem., 2009,19,6143-6148] such as Dehua Hu have reported two novel material of main part DMSiCBP and DPSiCBP, and the DPSiCBP of wherein take is main body doped F Iipic and obtains high-high brightness as 12130cd/m
2, maximum current efficiency is 6.5cd/A, higher than take device prepared as main body by CBP.The people [Organic Electronics, 11 (2010), 1624-1630] such as Hyoung-Yun Oh have reported to have ambipolar material of main part QuPB and NpyB, wherein NpyB doping Ir (phq)
2acac) prepare the ruddiness device and obtain maximum current efficiency 21cd/A, high-high brightness is 14440cd/m
2.The general character of these material of main parts is exactly all to have selected the electron type part to dock formation with carbazole group to have ambipolar material of main part, obtained device performance preferably, along with the increase efficiency decay of current density is very little, the visible this material of main part with bipolar structure has very large advantage.But above these material of main parts all also exist certain defect, improper such as HOMO/LUMO, the lower or triplet energies of second-order transition temperature (Tg) is low can't realize more high-performance blue-light device etc.This patent is intended to develop the phosphorescence bipolar host material that is applicable to three kinds of colors of red, green, blue.
Summary of the invention
In order to obtain thering is ambipolar material of main part, the invention provides bipolarity phosphorescent light body material and the organic electroluminescence device of a series of anthracene derivants containing tetraphenyl-silicon and carbazole.
Technical scheme of the present invention is: a kind of bipolarity phosphorescent light body material of the anthracene derivant containing tetraphenyl-silicon and carbazole, and the structural formula of described material is suc as formula 1 expression:
Formula 1:
Wherein X is
one of.
X is anthryl.
X is 2-methyl anthryl.
X is 2-fluorine anthryl.
X is 2-trimethyl silane anthryl.
A kind of organic electroluminescence device, it is stratiform doping type structure, be followed successively by substrate (1), nesa coating (2), hole injection layer (3), hole transmission layer (4), luminescent layer (5), hole blocking layer (6), electron transfer layer (7), electron injecting layer (8), negative electrode (9) by substrate to negative electrode, it is characterized in that: luminescent layer (5) adopts the bipolarity phosphorescent light body material doping Ir (ppy) containing the anthracene derivant of tetraphenyl-silicon and carbazole
3.
Concrete protection example:
Compound 1 compound 2
Compound 3 compounds 4
The present invention series material of main part has wider band gap, higher Tg, more suitable LUMO, HOMO and have the bipolarity of good hole/electron transport ability.Be applicable to the material of main part of the organic phosphorescence twinkler of green glow, there are the potentiality of Red and blue light application simultaneously.Its maximum characteristics are that this phosphorescent light body material has ambipolar hole, electronic transmission performance, can be widely used in RGB three primary colours doping type phosphorescent light body material, with the carbazole derivative material of main part of reporting in the past, have very large difference.This manufacture craft is simple, for full-color display and lighting application provides good material.
The accompanying drawing explanation
Fig. 1 is organic electroluminescence device structural representation of the present invention.
Embodiment
Synthetic method below in conjunction with accompanying drawing and concrete embodiment to the bipolarity phosphorescent light body material of the anthracene derivant containing tetraphenyl-silicon and carbazole provided by the invention is elaborated, but the invention is not restricted to these embodiment.
Synthetic embodiment 1: compound 1 synthetic route example:
According to following reaction formula synthetic compound 1
Intermediate 1a is synthetic
19.0g (4-bromophenyl) tri-phenyl-silane is added in the 500mL there-necked flask to logical N
2protection, be cooled to-80 ℃, stirs lower n-Butyl Lithium (n-BuLi) 0.015mol that drips, and dropwises insulation reaction 30min, then drips tributyl borate 0.06mol, dropwises insulation reaction 1h, dropping dilute hydrochloric acid termination reaction.Reaction solution is poured in 200mL water, stirred 10min, standing 4h, filter the white solid of separating out, and sherwood oil boils to be washed, and 60 ℃ of oven dry obtain 12.0g intermediate 1a product.
Intermediate 1b is synthetic
The bromo-9-phenyl of 30.0g 3--9H-carbazole is added in the 500mL there-necked flask to logical N
2protection, be cooled to-80 ℃, stirs the lower n-BuLi of dropping 0.11mol, dropwises insulation reaction 30min, then drips tributyl borate 0.22mol, dropwises insulation reaction 1h, drips the dilute hydrochloric acid termination reaction.Detection reaction is separated out solid filtering in falling back fully, obtains crude product, and sherwood oil boils and wash, dry and obtain 20.2g white powder intermediate 1b.
Intermediate 1c is synthetic
By 3.4g 9-bromine anthracene, 7.2g 1a, 3.6g salt of wormwood, the 0.6g Tetrabutyl amonium bromide adds in the 250mL there-necked flask, logical N
2protection, then add 0.2g tetra-triphenylphosphine palladium (Pd (PPh
3)
4), solvent toluene, ethanol, each 60mL of water, be heated to 78 ℃ of back flow reaction 6h, the complete after washing of detection reaction, separatory, filter, and after concentrating, obtains 7.5g white powder solid intermediate 1c.
Intermediate 1d is synthetic
7.5g intermediate 1c is dissolved with the 50mL methylene dichloride, add N-bromo-succinimide (NBS:2.4g, 0.15mol) in batches, under room temperature, react 2h, the complete after washing of detection reaction, the concentrated 7.4g white powder solid intermediate 1d that obtains.
Compound 1 is synthetic
By 7.0g intermediate 1d, 3.44g intermediate 1b, 3.8g salt of wormwood, the 0.6g Tetrabutyl amonium bromide adds in the 250mL there-necked flask, logical N
2protection, then add 0.2g Pd (PPh
3)
4, toluene, ethanol, each 70mL of water, 75 ℃ of back flow reaction 8h, the complete after washing of detection reaction, separatory, filter, and after concentrating, obtains the faint yellow compound 1 of 7.2g, purity 99.2%.
Compound 1:NMR (400M, CDCl3) δ (ppm): 8.58 (s, 1H), 8.00-7.80 (d, 8H), 7.79-7.76 (m, 2H), 7.70-7.60 (m, 1H) 7.58-7.45 (d, 15H) 7.40-7.20 (d, 12H).
Synthetic compound 2 adopts the method for synthetic embodiment 1 synthetic, during difference is to synthesize, with 2-methyl-9-bromine anthracene, replaces 9-bromine anthracene.
Compound 2:NMR (400M, CDCl
3) δ (ppm): 8.60 (d, 1H), 8.00-7.80 (s, 7H), 7.79-7.76 (d, 2H), 7.70-7.60 (m, 1H) 7.58-7.45 (d, 15H) 7.40-7.20 (d, 10H), 2.40 (m, 3H).
Synthetic compound 3 adopts the method for synthetic embodiment 1 synthetic, during difference is to synthesize, with the fluoro-9-bromine of 2-anthracene, replaces 9-bromine anthracene.
Compound 3:NMR (400M, CDCl
3) δ (ppm): 8.58 (s, 1H), 8.00-7.80 (d, 7H), 7.79-7.74 (m, 1H), 7.70-7.60 (d, 2H), 7.58-7.45 (s, 16H) 7.40-7.20 (s, 11H).
Synthetic compound 4 adopts the method for synthetic embodiment 1 synthetic, during difference is to synthesize, with 2-TMS-9-bromine anthracene, replaces 9-bromine anthracene.
Compound 4:NMR (400M, CDCl
3) δ (ppm): 8.90 (s, 1H), 8.20-7.80 (d, 7H), 7.79-7.74 (m, 1H), 7.70-7.60 (m, 2H), 7.58-7.45 (d, 17H) 7.40-7.20 (d, 10H), 0.28 (d, 9H).
Embodiment 1
The present invention selects compound 1 (or compound 2, compound 3, compound 4) to do luminescent layer matrix, closes iridium with three (2-phenylpyridines) and [is called for short Ir (ppy)
3] make the phosphorescence dopant material, adopt heating coevaporation technique high-performance electric phosphorescent device.Substrate 1 is selected glass or transparent plastics, nesa coating 2 be 20 Ω/sqITO (tin indium oxide) film as anode, by after substrate cleaning at high-purity O
2plasma under atmosphere (plasma bombardment) processes 10 minutes, then in high vacuum (3～2 * 10
-4pa), under, the hole injection layer 3 that deposit thickness is 45nm on nesa coating 2, select TCTA (4,4 ', 4 ' '-tri-carbazyl triphenylamine; Then deposition hole transmission layer 4 on hole injection layer 3, select NPB[N, N '-bis-(1-naphthyl)-N, N '-biphenyl diamine], thickness is 25nm; Then depositing light emitting layer 5 on hole transmission layer, luminescent layer 5 adopts co-deposition methods to evaporate compound 1 (or compound 2, compound 3, compound 4) simultaneously and three (2-phenylpyridines) close iridium [abbreviation Ir (ppy)
3], its mass ratio is 100: X (X=6,8,10), and the light emitting layer thickness with different levels of doping is 25nm; Deposition hole blocking layer 6 above luminescent layer, the material of hole blocking layer 6 is TPBi (1,3,5-tri-(N-phenyl 2-benzimidazolyl-) benzene), thickness is 10nm; Deposit afterwards electron transfer layer 7 on hole blocking layer, electron transfer layer 7 selects three (oxine) aluminium [to be called for short Alq
3], thickness is 25nm; On electron transfer layer 7, deposition LiF is as electron injecting layer 8 afterwards, and its thickness is 1nm; Finally deposition cathode 9 on electron injecting layer 8, select metal A l, and its thickness is 200nm.
All organic films adopt the thermal evaporation process deposits to complete.The thickness of film adopts the film thickness monitoring instrument to monitor, measure luminosity with luminance meter, except doping agent, the vaporator rate of all organic materialss is
the vaporator rate of LiF is
the vaporator rate of metal A l is
When using device architecture: ITO/2-TNATA (45nm)/NPB (25nm)/compound 1: Ir (ppy)
3[100: 6-10 (25nm)]/TPBi (10nm)/Alq
3(25nm)/LiF (1nm)/Al (200nm) is tested, as compound 1: Ir (ppy)
3device performance the best of=100: 8: high-high brightness 50000cd/m
2, high-high brightness efficiency 28cd/A, peak value spectrum 532nm, chromaticity coordinates (0.28,0.63).
2-TNATA compound structure in device architecture is: 4,4 ', 4 " (N, N ', N " (β-Nai Ji) aniline) triphenylamine.
Claims (6)
1. the bipolarity phosphorescent light body material containing the anthracene derivant of tetraphenyl-silicon and carbazole, the structural formula of described material is suc as formula 1 expression:
Formula 1:
Wherein X representative
one of.
2. the bipolarity phosphorescent light body material of the anthracene derivant containing tetraphenyl-silicon and carbazole according to claim 1, is characterized in that X is
.
3. the bipolarity phosphorescent light body material of the anthracene derivant containing tetraphenyl-silicon and carbazole according to claim 1, is characterized in that X is
.
4. the bipolarity phosphorescent light body material of the anthracene derivant containing tetraphenyl-silicon and carbazole according to claim 1, is characterized in that X is
.
5. the bipolarity phosphorescent light body material of the anthracene derivant containing tetraphenyl-silicon and carbazole according to claim 1, is characterized in that X is
.
6. an organic electroluminescence device, it is stratiform doping type structure, be followed successively by substrate (1), nesa coating (2), hole injection layer (3), hole transmission layer (4), luminescent layer (5), hole blocking layer (6), electron transfer layer (7), electron injecting layer (8), negative electrode (9) by substrate to negative electrode, it is characterized in that: luminescent layer (5) adopts bipolarity phosphorescent light body material doping Ir (ppy)
3, the bipolarity phosphorescent light body material that described phosphorescent light body material is the anthracene derivant containing tetraphenyl-silicon and carbazole claimed in claim 1.
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| CN102898350B (en) * | 2011-07-25 | 2014-12-10 | 海洋王照明科技股份有限公司 | Anthracene derivative organic semiconductor material, preparation method and applications thereof |
| JP5825043B2 (en) * | 2011-10-26 | 2015-12-02 | コニカミノルタ株式会社 | ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, METHOD FOR PRODUCING ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE |
| CN103172652A (en) * | 2011-12-22 | 2013-06-26 | 海洋王照明科技股份有限公司 | Tetraphenyl silicon containing organic semiconductor material and preparation method thereof and organic electroluminescent device |
| CN103304540B (en) * | 2012-03-09 | 2016-08-03 | 海洋王照明科技股份有限公司 | Phosphorescent light body material, its preparation method and electroluminescent device |
| CN103305211B (en) * | 2012-03-09 | 2016-01-13 | 海洋王照明科技股份有限公司 | Phosphorescent light body material and preparation method thereof and organic electroluminescence device |
| CN103102877B (en) * | 2012-11-14 | 2015-04-15 | 吉林奥来德光电材料股份有限公司 | Silicon-containing organic luminescent material as well as preparation method and application of organic luminescent material |
| CN104017177A (en) * | 2013-02-28 | 2014-09-03 | 海洋王照明科技股份有限公司 | Polymer containing tetraphenyl silicon and phenothiazine units as well as preparation method and application thereof |
| CN103242358B (en) * | 2013-05-15 | 2015-11-25 | 京东方科技集团股份有限公司 | Siliceous dianthranide derivative and its preparation method and application and organic electroluminescence device |
| CN110698654B (en) * | 2018-07-10 | 2021-04-02 | 中国科学院长春应用化学研究所 | Hyperbranched conjugated polyelectrolyte based on trimeric indole, preparation method and application thereof |
| KR102281249B1 (en) * | 2018-08-22 | 2021-07-22 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
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Non-Patent Citations (4)
| Title |
|---|
| Dehua Hu et al.Silane coupling di-carbazoles with high triplet energy as host materials for highly efficient blue phosphorescent devices.《J. Mater. Chem.》.2009,(第9期),6143-6148. |
| Silane coupling di-carbazoles with high triplet energy as host materials for highly efficient blue phosphorescent devices;Dehua Hu et al;《J. Mater. Chem.》;20090706(第9期);6143-6148 * |
| 两种新型咔唑衍生物的合成及其光电性能;刘望博等;《合成化学》;20101020;第18卷(第5期);543-546 * |
| 刘望博等.两种新型咔唑衍生物的合成及其光电性能.《合成化学》.2010,第18卷(第5期),543-546. |
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