CN101274916B - Multifunctional bipolar carrier transmission material and application thereof - Google Patents

Multifunctional bipolar carrier transmission material and application thereof Download PDF

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CN101274916B
CN101274916B CN2008100475927A CN200810047592A CN101274916B CN 101274916 B CN101274916 B CN 101274916B CN 2008100475927 A CN2008100475927 A CN 2008100475927A CN 200810047592 A CN200810047592 A CN 200810047592A CN 101274916 B CN101274916 B CN 101274916B
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layer
compound
hole
electroluminescent
carrier transmission
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CN101274916A (en
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杨楚罗
陶友田
秦金贵
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Wuhan University WHU
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Abstract

The invention discloses a compound which contains a triphenylamine unit with hole transport function and an oxdiazole unit with electronic transport function, the structure general formula is as the lower right, wherein Ar is a triphenyl amines compound with hole transport function. The synthesizing method of the multifunction compound of the invention is simple in operation and applicable for wide use. As transmission material of bipolar carrier, the compound of the invention can be applied to making an electroluminescent device in a blue-ray electrofluor optic device, has the advantages of the electroluminescent performance of high efficiency and high brightness and can be widely used in the organic electroluminescent field.

Description

A kind of multifunctional bipolar carrier transmission material and application thereof
Technical field
The present invention relates to field of organic electroluminescent materials, be specifically related to a kind of blue emitting material with bipolar carrier transmission performance and in the application in electroluminescent field.
Background technology
From people's reported first such as the C.W.Tang of Kodak in 1987 prepare by vacuum deposition method with Alq3 be the bi-layer devices structure of luminescent material since, organic electroluminescent has just obtained people's very big concern.
Organic electroluminescent can be divided into fluorescence and phosphorescence electroluminescent.According to spin quantum statistical theory, the formation probability proportion of singlet state exciton and triplet exciton is 1: 3, promptly the singlet state exciton only account for " electron-hole pair " 25%.Therefore, the fluorescence that comes from the radiative transition of singlet state exciton just only accounts for 25% of total input energy, and the electroluminescent of phosphor material just can utilize the energy of whole excitons, thereby has bigger superiority.
Forrest in 1999 and Thompson etc. [M A Baldo, S Lamansky, P.E.Burroes, M EThompson, S.R.Forrest.Appl Phys Let, 1999,75,4.] with green phosphorescent material Ir (ppy) 3With the doped in concentrations profiled of 6wt% 4,4 '-N, in the material of main part of N '-two carbazoles-biphenyl (CBP), and introduced hole barrier layer material 2,9-dimethyl 4,7-phenylbenzene-1,10-phenanthroline (BCP), the maximum external quantum efficiency of the green glow OLED of acquisition reaches 8%, and power efficiency reaches every watt of 31 lumen (lm/W), all substantially exceed the electroluminescent fluorescent luminescent device, cause the extensive concern of people immediately the heavy metal complex luminescent material.
(Y.-J.Su, H.-L.Huang, C.-L.Li, C.-H.Chien, Y.-T.Tao, P.-T.Chou, S.Datta, R.-S.Liu, Adv.Mater, 2003,15,884) such as Y T Tao had reported complexes of red light iridium (piq) in 2003 2Ir (acac) is entrained in the maximum external quantum efficiency of the device for preparing among the main body CBP with it and reaches 9.71%, and external quantum efficiency is that 9.21% o'clock current efficiency and power efficiency is respectively every ampere of 8.22 Kan Tela (cd/A) and 2.34lm/W.
Adopt this Subjective and Objective structure in the present phosphorescence electroluminescent device mostly, soon the phosphorescent emissions material in main substance, to avoid burying in oblivion of concentration quenching and triplet state-triplet state, improves phosphorescent emissions efficient with certain doped in concentrations profiled.
In the three primary colours phosphor material of having reported at present, have only green emitting to reach the commercialization requirement on efficient and purity of color, then there is the contradiction between purity of color and the efficient in red phosphorescence material.Be 4 at present as the maximum of the material of main part report of red phosphorescent, 4 '-N, N '-two carbazoles-biphenyl (CBP), but CBP not too mates with the energy level of hole transmission layer adjacent in the device and causes device performance to descend because of itself easy crystallization.Therefore it is significant to develop the red phosphorescent material of main part with good thermal stability, suitable energy level.And for the blue phosphorescent material, the standard (less than 0.2) that the y value of the chromaticity coordinates of report is generally all set up greater than International Commission on Illumination (CIE).Therefore the blue-fluorescence electroluminescent material of developing high-performance, good color purity remains one of present research focus.
Bipolar carrier transmission material has electronics and hole transport performance concurrently, can balancing device in the injection of current carrier and transmission, simplification device architecture, thereby be subjected to paying close attention to widely.In recent years, the material of main part about the bipolar carrier transmission also has report.(Lee, Jiun-Haw such as Lee for example; Tsai, Hsin-Hun; Leung, Man-Kit; Yang, Chih-Chiang; Chao, Chun-Chieh.Applied Physics Letters, 2007,90,243501), with Ir (ppy) 3Doped in concentrations profiled with 9wt% has in the oxadiazole human subject material 2,2 '-two of bipolar transmission-[5-phenyl-2-(1,3,4)-oxadiazole base]-biphenyl, and the current efficiency of device is every square metre of (cd/m of 1000 Kan Tela in brightness 2) time be 24cd/A, be slightly less than device based on CBP.(Mei-Yi Lai such as Lai, Chih-HsinChen, Wei-Sheng Huang, Jiann T.Lin, Tung-Huei Ke, Li-Yin Chen, Ming-HanTsai, Chung-Chih Wu.Angew.Chem.Int.Ed.2008,47,581) bipolar carrier transmission material based on triphenylamine and benzoglyoxaline of report.As the luminescent layer of non-adulterated blue-fluorescence device, obtaining maximum current efficient is 2.8cd/A, and as the single layer device of the material of main part preparation of orange phosphorescence, maximum external quantum efficiency is 7.8%.The bipolar carrier transmission material of being reported at present all is the main body as green and orange phosphorescence, and yet there are no report as the main body of red phosphorescent.
The triphenylamine units that will have the hole transport performance among the present invention is connected in a different manner with the oxadiazole unit with electronic transmission performance, prepared the compound that a class has bipolar carrier transmission performance.With they luminescent layer materials as electrochromic fluorescent devices, prepared blue-light device maximum current efficient reaches 4cd/A, and this performance in the present non-adulterated blue-fluorescence device of reporting is very outstanding.In addition with them as red phosphorescence material (piq) 2The main body of Ir (acac), the ruddiness device emission peak of preparation is positioned at 630nm, maximum current efficient reaches 11.3cd/A, maximum power efficiency 8.21m/W, maximum external quantum efficiency 14.2%, this performance is higher than the device based on CBP far away, is that single-shot photosphere device effect is one of best so far.
We utilize this type compound both can be used for efficient blue-light-emitting simultaneously, can prepare single-shot photosphere, single adulterated white electroluminescence device as the main body of high efficiency red phosphorescence again.
Summary of the invention
The object of the present invention is to provide a kind of compound and application thereof with bipolar carrier transmission performance, described compound has preferable performance and effect as luminescent layer material preparation electrochromic fluorescent devices.
Compound with bipolar carrier transmission performance described in the invention had not only contained the triphenylamine units of hole transport performance but also had contained the oxadiazole unit of electronic transmission performance, and general structure is as follows:
Figure G2008100475927D00031
In the formula,
Figure G2008100475927D00032
Be that Ar is 4-triphenylamine phenyl, 2-triphenylamine phenyl or 3-triphenylamine phenyl.
Electroluminescent device of the present invention, comprise glass, attached to Conducting Glass layer on glass, the hole injection layer that closes with the Conducting Glass laminating, hole transmission layer with the hole injection layer applying, luminescent layer with the hole transmission layer applying, with the hole blocking layer of luminescent layer applying, with the electron transfer layer of hole blocking layer applying, with the cathode layer of electron transfer layer applying.Wherein the luminescent layer of fluorescent device is made up of the described material of formula (1), the luminescent layer of red phosphorescent device and white light parts is a material of main part with the described compound of formula (1), dopant material is the common complex of iridium with cyclic metal complexes, as the Ir that glows (piq) 2(acac).
Bipolar carrier transmission material material of the present invention is applied to can obtain maximum current efficient 4cd/A in the blue light electroluminescent fluorescent optical device.The present invention is with Ir (piq) 2(acac) be the ruddiness electro phosphorescent device of object preparation, chromaticity coordinates CIE is (0.68,0.32), and high-high brightness reaches 24416 (cd/m 2), maximum luminous efficiency can reach 11.3cd/A, and maximum power efficiency reaches 8.2lm/W, and maximum external quantum efficiency reaches 14.2%, is that performance is one of best in the identical purity of color red phosphorescent device.The chromaticity coordinates of prepared simple white light parts when driving voltage 11V is (0.37,0.31), maximum current efficient 7.9cd/A.
Description of drawings
Fig. 1 electroluminescent device structural representation of the present invention;
The emmission spectrum of Fig. 2 electroluminescent device of the present invention.
Embodiment
The present invention is further illustrated below by specific embodiment, and its purpose is to help better to understand content of the present invention, but the protection domain that these specific embodiments do not limit the present invention in any way.
The used raw material of the present embodiment is a known compound, can buy on market, or available methods known in the art is synthetic.
Embodiment 1
2,5-two (4-4 '-the triphenylamine phenyl)-1,3, the preparation of 4-oxadiazole (being abbreviated as Host1)
Figure G2008100475927D00041
With 0.38 gram 2,5-two-(4-bromophenyl)-1,3; 4-oxadiazole and 0.6 gram triphenylamine-4-boric acid; a little four triphenyl phosphorus palladium, 1.06 gram yellow soda ash, 10 milliliters of tetrahydrofuran (THF)s; 2 ml waters add in 50 ml flasks; argon shield refluxed 24 hours, cooling back dichloromethane extraction, dried over anhydrous sodium carbonate organic phase; filter, be spin-dried for.With methylene dichloride: the sherwood oil volume ratio is to cross post at 1: 1 to get product 0.49 gram.Light yellow solid, productive rate 70%. 1H-NMR(CDCl 3，300MHz)δ[ppm]：8.18(t，4H)，8.02(d，2H)，7.71(m，6H)，7.53(d，4H)，7.29(m，12H)，7.20(d，4H)，7.06(t，4H)，MS(EA)：m/e?708.6(M +)。
Embodiment 2
2,5-two (2-4 '-the triphenylamine phenyl)-1,3, the preparation of 4-oxadiazole (being abbreviated as Host2)
Figure G2008100475927D00042
With 0.38 gram 2,5-two-(2-bromophenyl)-1,3; 4-oxadiazole and 0.60 gram triphenylamine-4-boric acid; a little four triphenyl phosphorus palladium, 0.56 gram potassium hydroxide, 10 milliliters of tetrahydrofuran (THF)s; 2 ml waters add in 50 ml flasks; argon shield refluxed 24 hours, cooling back dichloromethane extraction, dried over anhydrous sodium carbonate organic phase; filter, be spin-dried for.With methylene dichloride: the sherwood oil volume ratio is to cross post at 1: 1 to get product 0.60 gram.White solid, productive rate 85%.。 1H-NMR(CDCl 3，300MHz)δ[ppm]7.86(d，2H)，8.27(m?2H)，7.58(t，2H)，7.48(t，4H)，7.16(t，8H)，3.97(d?20H).MS(EA)：m/e?708.2(M +)。
Embodiment 3
2,5-two (3-4 '-the triphenylamine phenyl)-1,3, the preparation of 4-oxadiazole (being abbreviated as Host3)
Figure G2008100475927D00051
Adopt way similar to Example 1 can make 2,5-two (3-4 '-the triphenylamine phenyl)-1,3, the 4-oxadiazole.Productive rate 65%. 1H-NMR(CDCl 3，300MHz)δ[ppm]8.35(s，2H)，8.09(d，2H)，7.75(d，2H)，7.57(m，6H)，7.28(m，8H)，7.17，(m，12H)，7.06，(t，4H).MS(EA)：m/e?708(M +)
Embodiment 4
The preparation of electro phosphorescent device
As shown in Figure 1, bipolar carrier transmission material of the present invention can comprise glass and conductive glass (ITO) substrate layer 1, hole injection layer 2 (molybdic oxide MoO as the electroluminescent device of luminescent layer 3), hole transmission layer 3 (4,4 '-two (how basic N-phenyl-N-is)-biphenyl NPB), luminescent layer 4 (the present invention have the compound of bipolar carrier transmission performance or with it as the material of main part phosphorescent complexes that mixes), and hole blocking layer 5 (2,9-dimethyl 4,7-phenylbenzene-1,10-phenanthroline BCP), electron transfer layer 6 (three-oxine aluminium Alq3), cathode layer 7 (lithium fluoride/aluminium).
Electroluminescent device can be made by means known in the art, as presses reference (Adv.Mater.2003,15,277.) disclosed method and make.Concrete grammar is: under high vacuum condition, and evaporation MoO successively on through conductive glass (ITO) substrate that cleans 3, NPB, luminescent layer, the BCP of 10nm, the Alq3 of 30nm, the LiF of 1nm and the Al of 120nm.Make as shown in Figure 1 device with this method, various concrete device architectures are as follows:
Device 1 (D1):
ITO/MoO 3(10nm)/NPB(80nm)/Host1(20nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/Al(120nm)
Device 2 (D2):
ITO/MoO 3(10nm)/NPB(80nm)/Host2(20nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/Al(120nm)
Device 3 (D3):
ITO/MoO 3(10nm)/NPB(80nm)/Hostl：Ir(piq)2(acac)(6wt％，20nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/Al(120nm)
Device 4 (D4):
ITO/MoO 3(10nm)/NPB(80nm)/Host2：Ir(piq)2(acac)(6wt％，20nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/Al(120nm)
Device 5 (D5):
ITO/MoO 3(10nm)/NPB(80nm)/Host3：Ir(piq)2(acac)(6wt％，20nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/Al(120nm)
Device 6 (D6):
ITO/NPB(40nm)/Host1：Ir(piq)2(acac)(0.1wt％，30nm)/BCP(10nm)/Alq3(30nm)/LiF(1nm)/Al(120nm)
Electric current-the brightness of device-voltage characteristic is to be finished by the Keithley source measuring system that has corrected silicon photoelectric diode (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter), electroluminescent spectrum is by the French JY SPEX CCD3000 of company spectrometer measurement, and all measurements are all finished in atmosphere at room temperature.
The performance data of device sees the following form:
Device 1 and 2 is all launched blue light, and the maximum current efficient that is obtained is respectively 3.9 and 3.1cd/A, and performance is outstanding in the non-doped, blue fluorescent device of being reported so far.Device 3～5 is all launched saturated ruddiness with the material of main part of compound of the present invention as luminescent layer, and wherein device 4 maximum external quantum efficiencys are higher than the result (Adv.Mater, 2003,15,884) of documents far away up to 14.2%.Be that the electroluminescent phosphorescence performance is one of best when having identical purity of color so far.Device 6 emission white lights, maximum current efficient 7.9cd/A, chromaticity coordinates CIE are (0.37,0.31), very near the standard of setting up (0.33,0.33) of International Commission on Illumination.Therefore, compare with other materials, multifunctional material of the present invention was owing to both contained the triphenylamine units of tool hole transport performance, contain tool electronic transmission performance De oxadiazole unit again, the balance that helps current carrier in the device, obtain electroluminescent properties efficiently, helped developing high-level efficiency, the simple full-color display of device architecture.

Claims (4)

1. contain the triphenylamine units with hole transport and have the unitary compound of Dian Chuan Shu oxadiazole, its general structure is:
Figure F2008100475927C00011
Wherein,
Ar is simultaneously
2. the described compound of claim 1 is as the application of bipolar carrier transmission material.
3. electroluminescent device, comprise glass, attached to Conducting Glass layer on glass, the hole injection layer that closes with the Conducting Glass laminating, hole transmission layer with the hole injection layer applying, with the luminescent layer of hole transmission layer applying, with the hole blocking layer of luminescent layer applying, with the electron transfer layer of hole blocking layer applying, with the cathode layer that electron transfer layer is fitted, it is characterized in that: described luminescent layer contains the described compound of claim 1.
4. electroluminescent device according to claim 3 is characterized in that: luminescent layer is made up of material of main part and dopant material, and the material of main part of luminescent layer is a compound as claimed in claim 1.
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CN101463251B (en) * 2008-12-31 2012-08-01 武汉大学 Electro-phosphorescent main body material with bipolar carrier transmission performance and use thereof
US8604689B2 (en) * 2010-11-11 2013-12-10 Nitto Denko Corporation Hybrid composite emissive construct and light-emitting devices using the same
US9853220B2 (en) 2011-09-12 2017-12-26 Nitto Denko Corporation Efficient organic light-emitting diodes and fabrication of the same
CN103183711B (en) * 2011-12-28 2016-04-20 昆山维信诺显示技术有限公司 A kind of two-triaryl amine replaces phosphine oxygen base Benzophenanthrene compound, intermediate and preparation method and application
CN104017564A (en) * 2013-02-28 2014-09-03 海洋王照明科技股份有限公司 Bipolar blue-phosphorescence material, preparation method thereof and organic electroluminescent device
CN104119290A (en) * 2013-04-25 2014-10-29 海洋王照明科技股份有限公司 Organic semiconductor material, preparation method thereof and electroluminescent device

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