CN102382131A - Boron complex of phenolic benzothiazole and benzoxazole and application thereof in electroluminescence devices - Google Patents
Boron complex of phenolic benzothiazole and benzoxazole and application thereof in electroluminescence devices Download PDFInfo
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- CN102382131A CN102382131A CN2011102513041A CN201110251304A CN102382131A CN 102382131 A CN102382131 A CN 102382131A CN 2011102513041 A CN2011102513041 A CN 2011102513041A CN 201110251304 A CN201110251304 A CN 201110251304A CN 102382131 A CN102382131 A CN 102382131A
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- benzothiazole
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Abstract
The invention belongs to the technical field of organic electroluminescence and particularly relates to a boron complex containing phenolic benzothiazole or phenolic benzoxazole derivative ligands and application thereof in electroluminescence devices. The compound is further used for luminous layers of the electroluminescence devices to obtain the high-performance electroluminescence devices of which the emission spectrums contain green ray to red ray areas so that the electroluminescence devices can be used for application fields such as lighting sources, signal lamps, alphanumeric displays, indication boards, optoelectronic couplers, flat panel displays and the like.
Description
Technical field
The invention belongs to technical field of organic electroluminescence, be specifically related to contain the boron complexes and the application of these boron complexes in electroluminescent device of phenylol benzothiazole and phenylol benzoxazoles analog derivative part.
Background technology
People such as Pope have reported the organic electroluminescent phenomenon the earliest in earlier 1960s, and they have observed the blue light that anthracene sends when applying the high pressure of four hectovolts in the anthracene single crystal both sides.But because monocrystalline is difficult to growth, device drive voltage is very high, and (400～2000V), the technology that they adopted does not almost have practical use.Up to 1987; The people such as C.W.Tang of U.S. Kodak company adopt the ultrathin membrane technology with the hole transport effect preferably aromatic amine as hole transmission layer; With the aluminum complex of oxine as luminescent layer; Respectively as anode and negative electrode, prepared luminescent device with tin indium oxide (ITO) film and metal alloy.This device has obtained brightness up to 1000cd/m under the 10V driving voltage
2Green emission, the efficient of device is 1.5lm/W (seeing C.W.Tang and S.A.VanSlyke, Appl. Phys.Lett., 1987,51,913).This breakthrough makes organic electroluminescent research be able to worldwide in depth carry out rapidly.
The people such as C.W.Tang that continue find Alq first
3Have after the good electroluminescent properties, people use oxine and verivate and Al in succession
3+, Zn
2+, Ga
3+, Be
2+Deng having synthesized a series of complex electroluminescent materials, the most of jaundice of these materials green glows, some blue light-emitting (is seen U.S.Pat.No.4,720,432; U.S.Pat.No.4,539,507; U.S.Pat.No.5,151,629; Y. Hamada et al., Jpn.J. Appl.Phys., Part2., 1992,32, L514; M.Matsumura et al., Jpn.J. Appl. Phys., 1996,35,5357; P.E.Burrows et al., J. Appl. Phys., 1996,79,7991).The Sano of Japan Sanyo company etc. are at U.S.Pat.5, have prepared the blue-light device of better performances in 432,014 as luminescent layer with western Buddhist alkali-Zn complex.Hamada of it should be noted that Japanese Sanyo company etc. synthesizes 10-hydroxy benzo quinoline compound, and its electroluminescent properties has surpassed Alq
3(Y.Hamada et al., Chem.Lett., 1993,905).
Nineteen ninety, people such as the Burroughes of univ cambridge uk are that luminescent material has prepared the first high molecule electroluminescent device with polyphenylene ethylene (PPV), and the anode of device and negative electrode are respectively ITO and metallic aluminium; After applying the voltage of 14V, device sends visible light, and maximum quantum yield is 0.05% (to see J.H.Burroughes; D.D.C.Bradley, A.R.Brown et al., Nature; 1990,347,539).
The people such as Forrest of Princeton university in 1998 discover; Use the organic luminescent device of general organic materials or employing optical dye doping techniques preparation; Because receive the quantum mechanics transition rule constraint of spin conservation, its maximum luminous internal quantum efficiency is 25%.They are doped in phosphorescent coloring octaethylporphyrin platinum (PtOEP) in the main body luminescent material, and preparing external quantum efficiency is 4%, and internal quantum efficiency reaches 23% luminescent device; Thereby opened up the electroluminescent frontier of phosphorescence and (seen M.A.Baldo; D.F.O ' Brien et al., Nature, 1998; 395,151).
The exploitation of novel material is to promote the essential means that electroluminescent technology is constantly progressive and get into the practicability stage.In recent years, people have dropped into huge financial resources and energy to the exploitation of novel material, and the material of a large amount of excellent propertys makes organic electroluminescent obtain some breakthroughs (to see U.S.Pat.No.5,150,006; 5,141,671; 5,073,446; 5,061,569; 5,059,862; 5,059,861; 5,047,687; 4,950,950; 5,104,740; 5,227,252; 5,256,945; 5,069,975; 5,122,711; 5,554,450; 5,683,823; 5,593,788; 5,645,948; 5,451,343; 5,623,080; 5,395,862).The present invention is intended to develop new electroluminescent material, the material that relates to have be easy to prepare, advantage with low cost, and have electroluminescent properties preferably.
Summary of the invention
The object of the present invention is to provide four kinds of new boron complexes luminescent materials (compound 1-4) that contain phenylol benzothiazole or phenylol benzoxazoles analog derivative part, and be applied to prepare in the high performance organic electroluminescence device.
The synthetic route of compound 1-4 is shown in the following figure.Compound 1-4 is that solvent normal-temperature reaction spend the night make with new steaming THF by containing substituted phenylol benzothiazole of carbazyl, hexichol amido or dimethylin or phenylol benzoxazoles class part and triphenyl-boron under nitrogen protection respectively, and concrete experiment condition is seen embodiment.
Compound of the present invention can be used as luminescent layer and prepares electroluminescent device, and the device architecture of employing is as shown in Figure 1.Device architecture comprises successively: attached to the ITO on the transparent glass as anode, NPB (N; N '-two (1-naphthyl)-N; N '-phenylbenzene-1,1 '-biphenyl-4,4 '-diamines) as hole transmission layer, one or more boron complexes of the present invention as luminescent layer, TPBi (1; 3,5-three (1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene) is as hole blocking layer, Alq
3(oxine aluminium) or Bebq
2(10-hydroxy benzo quinoline beryllium) as electron transfer layer, LiF as electron injecting layer, metal A l as negative electrode.
Hole and electronics inject from anode and negative electrode respectively, in hole transmission layer and electron transfer layer, transmit respectively, and finally inject luminescent layer, and wherein a part of hole and electronics are captured pairing each other, form exciton.Exciton is got back to ground state through radiative transition, just has light to send.These electroluminescent devices can be used for Application Areass such as lighting source, SL, aplhanumeric visual display, direction board, photoelectronic coupler, flat-panel monitor.Through electroluminescent spectrum, brightness, the test of current/voltage characteristic analytical procedure.
Description of drawings
Fig. 1: use material prepn according to the invention the electroluminescent device structural representation;
Fig. 2: the electroluminescent device spectrogram of using material prepn according to the invention.
As shown in Figure 1; Each component names is: attached to the ito anode on the transparent glass 1, NPB (N, N '-two (1-naphthyl)-N, N '-phenylbenzene-1; 1 '-biphenyl-4; 4 '-diamines) and hole transmission layer 2, the luminescent layer 3 that comprises boron complexes according to the invention, TPBi (1,3,5-three (1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene) hole blocking layer 4, Alq
3(oxine aluminium) or Bebq
2(10-hydroxy benzo quinoline beryllium) electron transfer layer 5, LiF electron injecting layer, metal A l negative electrode 7.
Its characteristic of the electroluminescent device of The compounds of this invention is following: compound 1 emission peak position is 544nm, cut-in voltage 4.5V, and high-high brightness is 9181cd/m
2, maximum current efficient is 3.1cd/A, maximum power efficiency is 1.8lm/W; Compound 2 emission peak positions are 560nm, cut-in voltage 3.0V, and high-high brightness is 31220cd/m
2, maximum current efficient is 5.5cd/A, maximum power efficiency is 4.8lm/W; Compound 3 emission peak positions are 612nm, cut-in voltage 4.5V, and high-high brightness is 14010cd/m
2, maximum current efficient is 4.5cd/A, maximum power efficiency is 3.1lm/W; Compound 4 emission peak positions are 652nm, cut-in voltage 4.0V, and high-high brightness is 4662cd/m
2, maximum current efficient is 0.59cd/A, maximum power efficiency is 0.47lm/W.Wherein compound 2 high-high brightness can reach 31220cd/m
2Be the highest electroluminescent brightness of the boron complexes of report up to now, compound 3 can reach the performance level in doped ruddiness device of typical ruddiness dopant material DCJTB as non-adulterated its device performance of red light-emitting material.Electroluminescent spectrum is as shown in Figure 2.
Embodiment
Embodiment 1: compound 1 synthetic:
(100mg 0.26mmol) is dissolved in 30ml and newly steams among the THF, slowly splashes into triphenyl-boron (94mg with part 2-[4-morpholinodithio-4-carbazyl phenol; 0.39mmol) THF solution, stirred overnight at room temperature is drained back distillation with solvent; Obtain yellow-green colour solid (75mg, productive rate 52%).Nucleus magnetic hydrogen spectrum
1H NMR (CDCl
3, ppm): δ 8.15 (d, J=8.0Hz, 2H), 7.87 (d, J=8.0Hz, 1H), 7.72 (d, J=2.5Hz, 1H), 7.62 (dd, J=8.5Hz, 2.5Hz, 1H), 7.45-7.27 (m, 20H).The molion quality that mass spectroscopy is confirmed is: 556.6, and (calculated value is: 556.2); Theoretical constituent content (%) C
37H
25BN
2OS:C, 79.86; H, 4.53; N, 5.03; S, 5.76; Actual measurement constituent content (%): C, 79.56; H, 4.42; N, 5.02; S, 5.65.Above-mentioned analytical results shows, the product of the product of acquisition for estimating.
Embodiment 2: compound 2 synthetic:
(180mg 0.48mmol) newly steams among the THF in 30ml, slowly splashes into triphenyl-boron (173mg with part 2-benzoxazoles-4-hexichol amino-phenol; 0.71mmol) THF solution, stirred overnight at room temperature is drained back distillation with solvent; Obtain orange solids (120mg, productive rate 46%).Nucleus magnetic hydrogen spectrum
1H NMR (CDCl
3, ppm): δ 7.58 (d, J=8.0Hz, 1H), 7.54 (d, J=3.0Hz, 1H); 7.46-7.44 (m, 4H), 7.39 (t, J=7.5Hz, 1H), 7.35 (dd, J=9.0Hz; 2.5Hz, 1H), and 7.27-7.24 (m, 11H), 7.14 (d, J=9.0Hz; 1H), 7.08 (d, J=8.0Hz, 4H), 7.02-6.99 (m, 3H).The molion quality that mass spectroscopy is confirmed is: 542.2, and (calculated value is: 542.2); Theoretical constituent content (%) C
37H
27BN
2O
2: C, 81.93; H, 5.02; N, 5.16; Actual measurement constituent content (%): C, 81.81; H, 4.93; N, 5.15.Above-mentioned analytical results shows, the product of the product of acquisition for estimating.
Embodiment 3: compound 3 synthetic:
With part 2-[4-morpholinodithio-4-two. (100mg 0.25mmol) newly steams among the THF in 30ml anilino phenol, slowly splashes into triphenyl-boron (92mg; 0.38mmol) THF solution, stirred overnight at room temperature is drained back distillation with solvent; Obtain orange red solid (59mg, productive rate 42%).Nucleus magnetic hydrogen spectrum
1HNMR (CDCl
3, ppm): δ 7.79 (d, J=8.0Hz, 1H), 7.39-7.36 (m, 5H), 7.30-7.23 (m, 14H), 7.11-7.06 (m, 5H), 7.00 (t, J=7.5Hz, 2H).The molion quality that mass spectroscopy is confirmed is: 558.6, and (calculated value is: 558.2); Theoretical constituent content (%) C
37H
27BN
2OS:C, 79.57; H, 4.87; N, 5.02; S, 5.74; Actual measurement constituent content (%): C, 79.28; H, 4.70; N, 4.95; S, 5.64.Above-mentioned analytical results shows, the product of the product of acquisition for estimating.
Embodiment 4: compound 4 synthetic:
(153mg 0.57mmol) newly steams among the THF in 30ml, slowly splashes into triphenyl-boron (206mg with part 2-[4-morpholinodithio-4-dimethylin phenol; 0.86mmol) THF solution, stirred overnight at room temperature is drained back distillation with solvent; Obtain red solid (100mg, productive rate 40%).Nucleus magnetic hydrogen spectrum
1H NMR (CDCl
3, ppm): δ 7.84 (d, J=8.0Hz, 1H), 7.40-7.36 (m, 5H), 7.24-7.20 (m, 8H), 7.13 (d, J=9.0Hz, 1H), 7.08 (dd, J=9.0Hz, 2.5Hz, 1H), 6.71 (d, J=3.0Hz, 1H), 2.88 (s, 6H).The molion quality that mass spectroscopy is confirmed is: 434.4, and (calculated value is: 434.2); Theoretical constituent content (%) C
27H
23BN
2OS:C, 74.66; H, 5.34; N, 6.45; S, 7.38; Actual measurement constituent content (%): C, 74,74; H, 5.28; N, 6.50; S, 7.33.Above-mentioned analytical results shows, the product of the product of acquisition for estimating.
Embodiment 5: luminescent device [ITO/NPB/ compound 1/Alq
3/ LiF/Al]
(thickness does being coated with on the glass substrate of ito anode successively vapor deposition hole transmission layer NPB
), the compound 1 of luminescent layer embodiment 1 preparation
Electron transfer layer Alq
3 
Electronics injecting material LiF
The Al negative electrode
In evaporate process, keep-up pressure is 5 * 10
-6Pa.This device emission peak position is 544nm, cut-in voltage 4.5V, and high-high brightness is 9181cd/m
2, maximum current efficient is 3.1cd/A, maximum power efficiency is 1.8lm/W.
Embodiment 6: luminescent device [ITO/NPB/ compound 2/Alq
3/ LiF/Al]
(thickness does being coated with on the glass substrate of ito anode successively vapor deposition hole transmission layer NPB
), the compound 2 of luminescent layer embodiment 2 preparations
Electron transfer layer Alq
3 Electronics injecting material LiF
The Al negative electrode
In evaporate process, keep-up pressure is 5 * 10
-6Pa.This device emission peak position is 560nm, cut-in voltage 3.0V, and high-high brightness is 31220cd/m
2, maximum current efficient is 5.5cd/A, maximum power efficiency is 4.8lm/W.
Embodiment 7: luminescent device [ITO/NPB/ compound 3/TPBi/Bebq
2/ LiF/Al] (thickness does being coated with on the glass substrate of ito anode successively vapor deposition hole transmission layer NPB
), the compound 3 of luminescent layer embodiment 3 preparations
Hole blocking layer TPBi
Electron transfer layer Bebq
2 
Electronics injecting material LiF
The Al negative electrode
In evaporate process, keep-up pressure is 5 * 10
-6Pa.This device emission peak position is 612nm, cut-in voltage 4.5V, and high-high brightness is 14010cd/m
2, maximum current efficient is 4.5cd/A, maximum power efficiency is 3.1lm/W.
Embodiment 8: luminescent device [ITO/NPB/ compound 4/Alq
3/ LiF/Al]
(thickness does being coated with on the glass substrate of ito anode successively vapor deposition hole transmission layer NPB
), the compound 4 of luminescent layer embodiment 4 preparations
Electron transfer layer Alq
3 Electronics injecting material LiF
The Al negative electrode
In evaporate process, keep-up pressure is 5 * 10
-6Pa.This device emission peak position is 652nm, cut-in voltage 4.0V, and high-high brightness is 4662cd/m
2, maximum current efficient is 0.59cd/A, maximum power efficiency is 0.47lm/W.
Claims (4)
1. boron complexes that contains phenylol benzothiazole or phenylol benzoxazoles analog derivative part, its structural formula is as follows:
2. the described a kind of application of boron complexes in the preparation electroluminescent device that contains phenylol benzothiazole or phenylol benzoxazoles analog derivative part of claim 1.
3. a kind of application of boron complexes in the preparation electroluminescent device that contains phenylol benzothiazole or phenylol benzoxazoles analog derivative part as claimed in claim 2 is characterized in that: the luminescent layer that is used as electroluminescent device.
4. like claim 2 or the 3 described a kind of application of boron complexes in the preparation electroluminescent device that contain phenylol benzothiazole or phenylol benzoxazoles analog derivative part, it is characterized in that: be used to prepare lighting source, SL, aplhanumeric visual display, direction board, photoelectronic coupler or flat-panel monitor.
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| JP2019023186A (en) * | 2017-07-21 | 2019-02-14 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Organometallic compound, and organic light emitting element containing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654442A (en) * | 2009-09-11 | 2010-02-24 | 大连理工大学 | 2-(2'-hydroxyphenyl) benzothiazole chelated zinc derivative as well as preparation method and application thereof |
| CN102050798A (en) * | 2010-12-07 | 2011-05-11 | 吉林大学 | 2-(2'-hydroxylphenyl)-benzothiazole derivative luminescent materials |
| US20110108819A1 (en) * | 2008-08-18 | 2011-05-12 | Poopathy Kathirgamanathan | Compounds having electron transport properties, their preparation and use |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110108819A1 (en) * | 2008-08-18 | 2011-05-12 | Poopathy Kathirgamanathan | Compounds having electron transport properties, their preparation and use |
| CN101654442A (en) * | 2009-09-11 | 2010-02-24 | 大连理工大学 | 2-(2'-hydroxyphenyl) benzothiazole chelated zinc derivative as well as preparation method and application thereof |
| CN102050798A (en) * | 2010-12-07 | 2011-05-11 | 吉林大学 | 2-(2'-hydroxylphenyl)-benzothiazole derivative luminescent materials |
Non-Patent Citations (2)
| Title |
|---|
| 《Inorganic chemistry》 20090625 Zuolun Zhang et al. Luminescent Boron-Contained Ladder-Type pi-Conjugated Compounds 7230-7236 1-4 第48卷, 第15期 * |
| ZUOLUN ZHANG ET AL.: "Luminescent Boron-Contained Ladder-Type π-Conjugated Compounds", 《INORGANIC CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019023186A (en) * | 2017-07-21 | 2019-02-14 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Organometallic compound, and organic light emitting element containing the same |
| JP7224125B2 (en) | 2017-07-21 | 2023-02-17 | 三星ディスプレイ株式會社 | Organometallic compound and organic light-emitting device containing the same |
| US11925104B2 (en) | 2017-07-21 | 2024-03-05 | Samsung Display Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
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