CN101525335B - Full-bridge linked triphenylamine compound and application thereof in electroluminescent device - Google Patents
Full-bridge linked triphenylamine compound and application thereof in electroluminescent device Download PDFInfo
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- CN101525335B CN101525335B CN2009100616760A CN200910061676A CN101525335B CN 101525335 B CN101525335 B CN 101525335B CN 2009100616760 A CN2009100616760 A CN 2009100616760A CN 200910061676 A CN200910061676 A CN 200910061676A CN 101525335 B CN101525335 B CN 101525335B
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Abstract
The invention discloses triphenylamine compound with a full-bridge rigid structure and the application of the triphenylamine compound serving as hole transport layer material in electroluminescent device. The general structure of the compound is right formula; wherein, R is hydrogen atoms, phenyl, 4-triphenylamine or 3-(N-p-tert-butyl phenyl) which are same with each other. The triphenylamine compound has high thermal stability, and a synthetic method thereof is simple to be carried out. The compound can be used for preparing the electroluminescent device by a spin coating process, has low cost and extensive use. The electroluminescent device manufactured by triphenylamine compound serving as cavity transport layer material has electroluminescent performances of high efficiency and high brightness and can be widely applied to the organic electroluminescent field.
Description
Technical field
The present invention relates to have the triphenyl amine compound of full-bridge connection rigid structure and in electroluminescent device as the application of hole mobile material, belong to field of organic electroluminescent materials.
Background technology
Prepare with Alq by vacuum deposition method from people's reported first such as the C.W.Tang of Kodak in 1987
3Since the bi-layer devices structure for luminescent material, organic electroluminescent has just obtained people's very big concern.
In order to obtain the device of high-luminous-efficiency, the device of multilayered structure is subjected to paying close attention to widely always.So-called multilayer device generally comprise following which floor: hole injection layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer.Wherein, hole transmission layer generally contains the aromatic amine structure, utilizes the lone-pair electron of nitrogen-atoms to come transporting holes, as hole mobile material 1 the most commonly used, 4-two (1-naphthyl phenyl amine)-biphenyl (NPB).
But the second-order transition temperature of NPB molecule has only 95 ℃, and thermostability is not high, has limited its application in electroluminescent device.In addition, what the NPB molecule adopted when device prepares is vacuum-sublimation film forming manufacture craft, such manufacture craft length consuming time, cost height.
In order to improve the thermostability of traditional hole mobile material, be different from tradition " linear molecule ", Shirota has proposed the notion of " star-shaped molecule ", he with the arylamine molecule be connected on phenyl or triphenylamine around, the molecule that obtains like this is because the space is crowded, molecular weight is also bigger, makes molecular crystal take place than difficult, thereby has improved the thermostability of molecule.
In theory, 1999, Sakaki has proposed the notion of " plane nitrogen ", be the center nitrogen-atoms and when aromatic group has to a certain degree conjugation on every side the hole transmission performance better, but because the phenyl adjacent with nitrogen-atoms is in a kind of state that reverses in traditional arylamine material, cause the conjugacy of molecule to reduce, and the nitrogen positive ion that forms in transmission is sp
2Hydridization, such molecule are reformed can be higher.He foretells if nitrogen-atoms can be in more planar state of a relative phenyl on every side, then can obtain more outstanding hole mobile material.Up to the present such model molecule also is not synthesized out, only rests on theory stage.
Summary of the invention
The objective of the invention is to remedy the deficiencies in the prior art, triphenyl amine compound and application thereof with full-bridge connection rigid structure are provided, described triphenyl amine compound has satisfied the requirement of Sakaki theory, and they are had luminescent properties efficiently as the electroluminescent device that hole mobile material prepares.
The present invention is said to have a triphenyl amine compound of full-bridge connection rigid structure, its structure as the formula (1):
Wherein R is mutually the same phenyl, 4-triphen amido or 3-(N-is to tert-butyl-phenyl) carbazyl, also is that R is mutually the same
Or
The said hole mobile material of the present invention with triphenyl amine compound of full-bridge connection rigid structure as electroluminescent device.
Electroluminescent device of the present invention comprises successively the cathode layer of fitting, luminescent layer, hole transmission layer and attached to Conducting Glass layer on glass, and wherein the material that uses of hole transmission layer is the described compound of formula (1).
The triphenylamine units bridging that will have the hole transport performance among the present invention gets up to have formed full-bridge and connects structure, compare with the triphenylamine units that does not have bridging or part bridging, triphenyl amine compound molecular rigidity of the present invention is bigger, thermostability is higher, and the molecular conjugation skeleton is the plane more, make center nitrogen-atoms and phenyl ring conjugation ability reinforcement on every side, help the transmission in hole, satisfied the requirement of Sakaki theory, with they hole mobile materials as electroluminescent device, thermostability to device has significantly raising, can obtain electroluminescent properties efficiently.The present invention prepared based on Alq
3The green device high-high brightness reach 39051cd/m
2, maximum current efficient obviously is better than the 4.29cd/A of traditional NPB up to 6.48cd/A.Simultaneously, this class material of the present invention can adopt spin coating proceeding when the preparation electroluminescent device, compare with vacuum-sublimation film forming manufacture craft, and cost is lower.
Description of drawings
One of Fig. 1 hole mobile material of the present invention 2,6,10-three (3-(N-is to tert-butyl-phenyl) carbazyl)-4,8, the ultraviolet-visible absorption spectroscopy figure of 12-three (di-p-tolyl methylene radical) bridged triphenyl amine solution;
One of Fig. 2 hole mobile material of the present invention 2,6,10-three (3-(N-is to tert-butyl-phenyl) carbazyl)-4,8, the photoluminescence figure of 12-three (di-p-tolyl methylene radical) bridged triphenyl amine solution;
Fig. 3 electroluminescent device structural representation of the present invention;
The emmission spectrum of Fig. 4 electroluminescent device of the present invention.
Embodiment
The present invention is further illustrated below by specific embodiment, and its purpose is to help to understand content of the present invention better, but the protection domain that these specific embodiments do not limit the present invention in any way.
The used raw material of the embodiment of the invention is a known compound, can buy on market, or available methods known in the art is synthetic.
Embodiment 1
4,8, the preparation of 12-three (di-p-tolyl methylene radical) bridged triphenyl amine (being abbreviated as HTM1)
3.87g para-bromo toluene (22.6mmol) is dissolved in the 30ml absolute ether in Shiran gram (Schlenk) pipe.9.3ml (2.45M 22.8mmol) splashes in the Schlenk pipe under-10 ℃ of conditions n-BuLi, drips off back low-temp reaction 1h.0.90 g 2,2 ', 2 "-triphenylamine tricarboxylic acid methyl esters (2.15mmol) is dissolved in and splashes into the Schlenk pipe behind the absolute anhydrous THF of 20ml, reaction 3h.Reaction finishes the rare NH in back
4Cl solution carries out cancellation.Extracted with diethyl ether.Tell organic phase, wash anhydrous Na with water three times
2SO
4Dry.Be spin-dried for organic solvent, the thick product that obtains is dissolved in 30ml glacial acetic acid, reflux.The careful dense HCl of 3ml, the reaction 3h of splashing into.Reaction finishes back solution and pours in the 200ml frozen water.The 20ml chloroform extracts respectively three times, gets red solution.Be spin-dried for thick product sherwood oil behind the chloroform: methylene dichloride=2: 1 (volume ratio) is crossed post and is separated, and gets white solid 1.48g, productive rate 84%.Warp
1H NMR,
13C NMR, MS characterize, and confirm that this white solid is HTM1.
1HNMR(300MHz，CDCl
3，δ)：6.93(t，J＝6.6Hz，3H)，6.83-6.81(m，18H)，6.63(d，J＝8.1Hz，12H)，2.27(s，18H)；
13C?NMR(75MHz，CDCl
3，δ)：143.58，135.41，135.35，130.29，128.86，128.25，128.20，122.45，55.38，21.14.Anal.Calcd.for?C
63H
51N(％)：C，92.04；H，6.25；N，1.70.Found：C，92.21；H，6.20；N，1.65.MS(EI)m/z：821.9[M
+].
2,6,10-triphenyl-4,8, the preparation of 12-three (di-p-tolyl methylene radical) bridged triphenyl amine (being abbreviated as HTM2)
1.00g (1.22mmol) 4,8,12-three (di-p-tolyl methylene radical) bridged triphenyl amine is dissolved in the 20ml chloroform in the 50ml round-bottomed flask.Add 0.68g NBS (3.82mmol).Stirring at room reaction 12h.Reaction washes organic phase with water three times after finishing.Anhydrous Na
2SO
4Dry.Use sherwood oil: methylene dichloride=3: 1 (volume ratio) is crossed post and is separated.Get white solid 2,6,10-three bromo-4,8,12-three (di-p-tolyl methylene radical) bridged triphenyl amine 1.22g, productive rate 95%.
1H?NMR(300MHz，CDCl
3，δ)：6.91(s，6H)，6.86(d，J＝8.1Hz，12H)，6.55(d，J＝8.1Hz，12H)，2.30(s，18H)；
13C?NMR(75MHz，CDCl
3，δ)：141.809，136.132，134.261，130.772，130.701，130.001，128.697，116.098，55.293，21.124.Anal.Calcd.for?C
63H
48Br
3N(％)：C，71.47；H，4.57；N，1.32.Found：C，71.23；H，4.40；N，1.35；MALDI-TOF-MS：m/z?1059.2(M
+).
2,6,10-three bromo-4,8,12-three (di-p-tolyl methylene radical) bridged triphenyl amine (600mg, 0.57mmol), phenylo boric acid (276mg, 2.26mmol), Pd (PPh
3)
4(1.81g, 17.1mmol) and salt of wormwood (1.81g 17.1mmol) is dissolved in 40ml toluene and 9ml distilled water in the Schlenk bottle.Back flow reaction 2d.CHCl
3Extraction, anhydrous sodium sulfate drying, be spin-dried for solvent after, use sherwood oil: methylene dichloride=3: 1 (volume ratio) is crossed the post separation.Get white solid 506mg, productive rate 85%.Warp
1H NMR,
13C NMR, MS characterize, and confirm that this white solid is HTM2.
1H?NMR(300MHz，CDCl
3，δ)：7.27-7.14(m，21H)，6.87(d，J＝8.1Hz，12H)，6.74(d；J＝8.1Hz，12H)，2.29(s，18H)；
13C?NMR(300MHz，CDCl
3，δ)：143.246，140.855，135.529，134.742，130.332，129.445，128.829，128.443，126.753，55.771，21.211.Anal.Calcd.for?C
81H
63N(％)：C，92.62；H，6.05；N，1.33.Found：C，92.46.15；H，6.27；N，1.24.Ms?MALDI-TOFm/z1049.8[M
+].
2,6,10-three (4-triphen amido)-4,8, the preparation of 12-three (di-p-tolyl methylene radical) bridged triphenyl amine (being abbreviated as HTM3)
Adopt way similar to Example 2 can make HTM3.
1H?NMR(300MHz，CDCl
3，δ)：7.18-7.15(m，18H)，7.05-6.91(m，30H)，6.78(d，J＝7.2Hz，12H)，6.65(d，J＝7.2Hz，12H)，2.21(s，18H).Anal.Calcd.for?C
117H
90N
4(％)：C，90.54；H，5.85；N，3.61.Found：C，91.01；H，6.16；N，3.36；MALDI-TOF-MS：m/z?1551.5(M
+).
2,6,10-three (3-(N-is to tert-butyl-phenyl) carbazyl)-4,8, the preparation of 12-three (di-p-tolyl methylene radical) bridged triphenyl amine (being abbreviated as HTM4)
Adopt way similar to Example 2 can make HTM4.
1H NMR (300MHz, CDCl
3, δ): 7.99 (d, J=8.1Hz, 3H), 7.52 (d, J=8.1Hz, 9H), 7.37-7.26 (m, 24H), 6.83-6.76 (m, 27H), 2.25 (s, 18H), 1.341 (s, 27H) .Anal.Calcd.for C
129H
108N
4(%): C, 90.38; H, 6.35; N, 3.27.Found:C, 90.71; H, 6.63; N, 2.94.MALDI-TOF-MS:m/z 1713.6 (M
+). Fig. 1 and Fig. 2 are respectively 2,6,10-three (3-(N-is to the tert-butyl-phenyl carbazyl))-4,8, the ultraviolet-visible absorption spectroscopy figure and the photoluminescence figure of 12-three (di-p-tolyl methylene radical) bridged triphenyl amine solution.
Embodiment 5
As shown in Figure 3, the electroluminescent device of triphenyl amine compound preparation of the present invention, comprise successively the cathode layer 4 of fitting, luminescent layer 3, hole transmission layer 2 and attached to Conducting Glass layer 1 on glass, also be that cathode layer and luminescent layer are fitted, luminescent layer and hole transmission layer are fitted, and hole transmission layer and Conducting Glass laminating close; Wherein, the material of Conducting Glass layer 1 can be ITO, and the material of hole transmission layer 2 is a triphenyl amine compound of the present invention, and the material of luminescent layer 3 can be oxine aluminium, and the material of cathode layer 4 can be 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 40nm hole transmission layer, the Alq of evaporation 50nm successively in first spin coating on conductive glass (ITO) substrate that process is cleaned
3, the LiF of 1nm and the Al of 120nm.Make as shown in Figure 3 device with this method, the structure of various devices is as follows:
Device 1 (D1):
ITO/HTM3(40nm)/Alq
3(50nm)/LiF(1nm)/Al(120nm)
Device 2 (D2):
ITO/HTM4(40nm)/Alq
3(50nm)/LiF(1nm)/Al(120nm)
Device 3 (D3):
ITO/NPB(40nm)/Alq
3(50nm)/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 each device sees the following form:
| Device | Maximum brightness cd/m 2 | Maximum current efficient cd/A | Luminescent spectrum |
| Device 1 | 39051? | 4.51? | -? |
| |
24496? | 6.48? | Fig. 4 |
| |
39058? | 4.29? | -? |
Claims (3)
1. have the triphenyl amine compound of full-bridge connection rigid structure, its general structure is:
2. the described application of claim 1 with triphenyl amine compound of full-bridge connection rigid structure as hole mobile material in the electroluminescent device.
3. the electroluminescent device of the described triphenyl amine compound preparation of a claim 1, comprise successively the cathode layer of fitting, luminescent layer, hole transmission layer and attached to Conducting Glass layer on glass, it is characterized in that: the material of hole transmission layer is a full-bridge linked triphenylamine compound as claimed in claim 1.
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| CN106800556A (en) * | 2017-01-13 | 2017-06-06 | 南京信息工程大学 | A kind of structure of three-dimensional triphen amine hole mobile material, synthesis and application |
| CN109810106A (en) * | 2018-12-30 | 2019-05-28 | 瑞声科技（南京）有限公司 | A kind of light emitting composition and luminescent layer and electroluminescent device comprising the light emitting composition |
| CN111362940A (en) * | 2020-03-19 | 2020-07-03 | 苏州大学 | Triphenylamine derivative and application thereof in organic electroluminescent device |
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