CN106946870B - A kind of preparation method and applications of OLED material - Google Patents

A kind of preparation method and applications of OLED material Download PDF

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CN106946870B
CN106946870B CN201710081294.9A CN201710081294A CN106946870B CN 106946870 B CN106946870 B CN 106946870B CN 201710081294 A CN201710081294 A CN 201710081294A CN 106946870 B CN106946870 B CN 106946870B
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oled
organic electroluminescence
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layer
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CN106946870A (en
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张成新
李庆
盛磊
孙晟源
邢宗仁
慈振华
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Valiant Co Ltd
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Abstract

The present invention relates to a kind of preparation method and applications of OLED material, the OLED material has molecular structure shown in meeting formula (1),Wherein, X is SO in formula2Or C (CN)2；The aryl amine or the heteroatomic aryl group containing N, O, S that two Ar are independently selected from hydrogen-based or carbon atom number 6-60, OLED material provided by the invention have the characteristics that thermal stability it is good, it is intermolecular be not easy to crystallize, be not easy to assemble, good film-forming property, preparation process is simple, as emitting layer material, applied to field of organic electroluminescence, there are good photoelectric properties.

Description

A kind of preparation method and applications of OLED material
Technical field
The invention belongs to field of organic electroluminescence, and in particular to a kind of preparation method and applications of OLED material.
Background technique
Since 1987, and organic electroluminescence device (Organic Light-Emitting Diodes, referred to as OLEDs) it is increasingly becoming the generally acknowledged next-generation flat panel display of industry.OLEDs belongs to selfluminous element, when charge (electronics and Hole) be injected between anode and cathode organic film when, electrons and holes are compounded to form exciton and transfer energy to hair Optical molecule, and then excite electronics from ground state transition to excitation state, excited energy shines by Radiation-induced deactivation.OLEDs has Self-luminous, driving voltage is low, frivolous, the wide visual angle that shines, fast response time, flexible folding, low energy consumption, it is raw to carry out large area The advantages that production, thus show in information and have broad application prospects with solid-state lighting field.
However, traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, device it is interior Quantum efficiency is lower (up to 25%).External quantum efficiency is generally lower than 5%, and also there is a big difference with the efficiency of phosphorescent devices. Although phosphor material can be efficiently used and be electrically excited since the strong SO coupling in heavy atom center enhances intersystem crossing The singlet exciton and Triplet exciton of formation, make the internal quantum efficiency of device up to 100%.But there are prices for phosphor material Valuableness, stability of material is poor, and device efficiency tumbles the problems such as serious and limits it in the application of OLEDs.Hot activation delay is glimmering Light (TADF) material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such material Material generally has small poor (the △ E of singlet-tripletST), triplet excitons can be transformed into list by anti-intersystem crossing Line state excitonic luminescence.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation, the interior quantum of device Efficiency can achieve 100%.Meanwhile material structure is controllable, and property is stablized, and it is cheap to be not necessarily to precious metal, in the field OLEDs Have a extensive future.
Although theoretically 100% exciton utilization rate may be implemented in TADF material, following problem there are in fact: (1) Design the T of molecule1And S1State has strong CT feature, very small S1-T1State energy gap, although can be realized by TADF process High T1→S1State exciton conversion ratio, but also result in low S1State radiation transistion rate, consequently it is difficult to have both (or realizing simultaneously) High exciton utilization rate and high fluorescent radiation efficiency；(2) even if having used doping device to mitigate T exciton concentration quenching effect, greatly Efficiency roll-off is serious at higher current densities for the device of most TADF materials.
For current OLED shows the actual demand of Lighting Industry, the development of OLED material is also far from enough at present, falls Afterwards in the requirement of panel manufacturing enterprise, therefore develops high-performance emitting layer material and be particularly important.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method and applications of OLED material, with dibenzo The compound and its application on organic electroluminescence device that thiepin derivative and dibenzocycloheptene malononitrile are parent nucleus. The present invention is based on the aryl substituted diphenylamine of TADF mechanism and thiepin derivative and dibenzocycloheptene malononitrile are parent nucleus class It closes object to be applied on Organic Light Emitting Diode as emitting layer material, there are good photoelectric properties, can satisfy panel manufacture The requirement of enterprise.
The technical scheme to solve the above technical problems is that a kind of OLED material, including with meeting formula (1) institute The molecular structure shown,
Wherein, X is SO in formula2OrTwo Ar are independently selected from the aryl amine of hydrogen-based or carbon atom number 6-60 or contain N, the heteroatomic aryl group of O, S.
Based on the above technical solution, the present invention can also be improved as follows.
Further, described two Ar are identical or not identical, and wherein Ar part-structure is as follows:
In any one, E be chemical bond connection site.
The present invention provides a kind of preparation method of OLED material, includes the following steps, raw material A is reacted to obtain with raw material C Product I, as shown in reaction equation 2；Or react raw material B with raw material C to obtain product II, as shown in reaction equation 3；Or by raw material D with Raw material E reacts to obtain product I, as shown in reaction equation 4；Or react raw material F with raw material E to obtain product II, such as 5 institute of reaction equation Show；
Wherein, reaction equation 2 is into reaction equation 5, X SO2Or C (CN)2, arylamine of the Ar selected from hydrogen-based or carbon atom number 6-60 Base or the heteroatomic aryl group containing N, O, S, two Ar in product I are identical or not identical.
A kind of purposes of the above-mentioned OLED material of the present invention as organic electroluminescent LED material.
The present invention also provides a kind of OLED materials to prepare the application in organic electroluminescence device, the organic electroluminescence hair Luminescent layer in optical device contains above-mentioned OLED material.
Further, the organic electroluminescence device is OLED device.
Following compounds C01-C46 is the representative structure for meeting spirit of that invention and principle, it should be understood that following chemical combination Object structure is intended merely to more fully understand the present invention, is not limitation of the present invention.
The beneficial effects of the present invention are: the present invention provides one kind with dibenzo thiepin derivative and dibenzocycloheptene Malononitrile is electroluminescent organic material and its application of parent nucleus, and provides the preparation method of such material, with material work For the organic electroluminescence device of emitting layer material material production, preferable efficiency is illustrated, it is characterized in that:
1. the compounds of this invention using dibenzo thiepin derivative and dibenzocycloheptene malononitrile as parent nucleus, has molecule Between be not easy to crystallize, be not easy to assemble, have the characteristics that good filming；It is mostly rigid radical in molecule, there is good thermostabilization Property；With suitable HOMO and lumo energy, electron cloud, which efficiently separates, can be achieved lesser S1-T1State energy gap can effectively improve height Exciton utilization rate and high fluorescent radiation efficiency reduce the efficiency roll-off under high current density, reduce device voltage, have good Photoelectric characteristic.
2. OLED material of the present invention can be applied to the production of OLED luminescent device, and can obtain good device performance, OLED material as OLED luminescent device emitting layer material in use, production device have good photoelectric properties, this hair The bright compound has good application effect in OLED luminescent device, has good industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of organic electroluminescence device prepared by the present invention.
In attached drawing, parts list represented by the reference numerals are as follows:
101, ITO Conducting Glass, 102, hole transmission layer, 103, luminescent layer, 104, exciton barrier-layer, 105, electronics Transport layer, 106, electron injecting layer, 107, cathode layer.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.
The present invention will also provide OLED material as luminescent material and be used for the application example of field of organic electroluminescence, especially The application example of the luminescent layer for organic electroluminescence device, the implementation process with as a result, being intended merely to preferably solve The present invention is released, is not limitation of the present invention.
Prepared organic electroluminescence device includes ITO Conducting Glass (anode), the hole transport being sequentially overlapped Layer (NPB-TCTA-CzSi), luminescent layer (electroluminescent organic material of the present invention), exciton barrier-layer (DPEPO), electronics Transport layer (TPBI), electron injecting layer (LiF) and cathode layer (Al), as shown in Figure 1.All functional layers are all made of vacuum evaporation work Skill is made.The molecular structural formula of used some organic compounds is as follows in such device, and wherein T1 is in comparative example 1 Luminescent material.
The preparation of 1 compound C03 of embodiment
Under nitrogen protection, raw material A -1 (2.0g, 5mmol), raw material B-1 (2.30g, 11mmol) and 120mL toluene are added Enter in 250mL there-necked flask, then puts into catalyst acetic acid palladium (0.011g, 0.05mmol), catalyst ligand tri-tert-butylphosphine four Borofluoride (0.026g, 0.1mmol), acid binding agent sodium tert-butoxide (1.44g, 15mmol).It is small that system is warming up to back flow reaction 8 When, 50mL water quenching reaction is added after being naturally cooling to 20~25 DEG C, liquid separation removes solvent and obtains crude product toluene crystallization 2.43g object C03, yield 78.1%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C44H38N2O2S, theoretical value 658.2654, test value 658.2651.Elemental analysis (C44H38N2O2S), theoretical value C:80.21, H:5.81, N:4.25, O:4.86, S:4.87, measured value C:80.22, H:5.80, N:4.26, O:4.86, S:4.86.
The preparation of 2 compound C12 of embodiment
Under nitrogen protection, by raw material A -2 (1.24g, 2.5mmol), raw material B-2 (1.86g, 5.5mmol), 80mL toluene It is added in 250mL there-necked flask with 20mL water, then puts into catalyst tetrakis triphenylphosphine palladium (0.029g, 0.025mmol), tie up acid Agent potassium carbonate (1.04g, 7.5mmol).System is warming up to back flow reaction 8 hours, is naturally cooling to 20~25 DEG C, and liquid separation removes Crude product toluene crystallization is obtained 1.43g object C40, yield 78.7% by solvent.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H34N2O2S, theoretical value 726.2341, test value 726.2340.Elemental analysis (C50H34N2O2S), theoretical value C:82.62, H:4.71, N:3.85, O:4.40, S:4.41, measured value C:82.62, H:4.71, N:3.85, O:4.40, S:4.41.
The preparation of 3 compound C15 of embodiment
Preparation method of the synthetic method referring to C03, total recovery 76.8%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C42H26N4O2, theoretical value 618.2056, test value 618.2058.Elemental analysis (C42H26N4O2), theoretical value C:81.54, H:4.24, N:9.06, O:5.17, measured value C:81.54, H:4.23, N:9.07, O:5.17.
The preparation of 4 compound C18 of embodiment
Preparation method of the synthetic method referring to C12, total recovery 72.2%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C60H46N4, theoretical value 822.3722, test value 822.3711.Elemental analysis (C60H46N4), theoretical value C:87.56, H:5.63, N:6.81, measured value C:87.55, H:5.64, N: 6.81。
The preparation of 5 compound C21 of embodiment
Preparation method of the synthetic method referring to C03, total recovery 71.6%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C50H34N4, theoretical value 690.2783, test value 690.2782.Elemental analysis (C50H34N4), theoretical value C:86.93, H:4.24, N:8.11, measured value C:86.94, H:4.23, N: 8.11。
The preparation of 6 compound C29 of embodiment
Preparation method of the synthetic method referring to C03, total recovery 78.5%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C42H26N4, theoretical value 586.2157, test value 586.2158.Elemental analysis (C42H26N4), theoretical value C:85.98, H:4.47, N:9.55, measured value C:85.97, H:4.47, N: 9.56。
The preparation of 7 compound C33 of embodiment
Preparation method of the synthetic method referring to C03, total recovery 78.3%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C54H33N4, theoretical value 751.2736, test value 751.2732.Elemental analysis (C54H33N4), theoretical value C:86.26, H:4.42, N:9.31, measured value C:86.27, H:4.42, N: 9.31。
The preparation of 8 compound C45 of embodiment
Preparation method of the synthetic method referring to C03, total recovery 77.9%.
High resolution mass spectrum, the source ESI, positive ion mode, molecular formula C34H35NO2S, theoretical value 521.2388, test value 521.2339.Elemental analysis (C34H35NO2S), theoretical value C:78.27, H:6.76, N:2.68, O:6.13, S:6.15, measured value C:78.27, H:6.76, N:2.68, O:6.13, S:6.15.
Organic electroluminescence device embodiment:
The present invention chooses compound C33, compound C45 and makes organic electroluminescence device, and luminescent material T1 is selected to make It for comparative example, is described below with reference to Fig. 1, organic electroluminescence device sequentially consists of as ITO Conducting Glass (101), hole transmission layer (102), luminescent layer (103) exciton barrier-layer (104), electron transfer layer (105), electron injecting layer (106) and cathode layer (107).It should be appreciated that device implementation process with as a result, be intended merely to preferably explain the present invention, not Limitation of the present invention.
Application of the 9 compound C33 of embodiment in organic electroluminescence device
The present embodiment prepares organic electroluminescence device one by the following method:
A) it cleans ITO (tin indium oxide) glass: cleaning each 30 points of ito glass with deionized water, acetone, EtOH Sonicate respectively Then clock is handled 5 minutes in plasma cleaner；
B) successively vacuum evaporation hole transmission layer NPB (30nm), TCTA (20nm), CzSi on anode ito glass (10nm), evaporation rate 0.1nm/s；
C) the vacuum evaporation luminescent layer on hole transmission layer, 10%wt compound C33 (preparation of embodiment 1): DPEPO, Evaporation rate 0.1nm/s, vapor deposition total film thickness are 20nm
D) on luminescent layer, total film thickness is deposited in the vacuum evaporation DPEPO as exciton resistance layer, evaporation rate 0.1nm/s For 10nm；
E) on exciton barrier-layer, TPBI of the vacuum evaporation as electron transfer layer, with a thickness of 30nm；
F) on electron transfer layer, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm；
G) on electron injecting layer, vacuum evaporation cathode Al, with a thickness of 100nm.
The structure of device is ITO/NPB (30nm), TCTA (20nm), CzSi (10nm)/DPEPO:10%wt compound C33 (20nm)/DPEPO (10nm)/TPBI (30nm)/LiF (1nm)/Al (100nm), during vacuum evaporation, pressure < 4.0 × 10- 4Pa, using compound C33 as the luminescent material of device one, the test result of obtained device is shown in Table 1.
Embodiment 10: application of the compound C45 in organic electroluminescence device
Organic electroluminescence device is made according to method same as Example 9, difference is to use C45 as luminescent layer Luminescent material replace as in the embodiment 1 of luminescent layer luminescent material synthesis compound C33.The test result of obtained device is shown in Shown in table 1.
Comparative example 1: organic electroluminescence device is made according to method same as Example 9, difference is to make using T1 The C33 synthesized in the embodiment 1 as luminescent layer luminescent material is replaced by the luminescent material of luminescent layer.The test knot of obtained device Fruit is shown in Table 1.
1 device photoelectric tables of data of table
As known from Table 1, there is preferable current efficiency and power efficiency with the luminescent device that OLED material of the invention makes. As blue light emitting device, there is lesser CIE y value.
Choose compound C03, compound C12, compound C15, compound C18, compound C21, compound C29 production with The mutually isostructural organic electroluminescence device of embodiment 9, difference are only that the luminescent material type of luminescent layer.Device performance test The results are shown in Table 2.
2 device photoelectric tables of data of table
As known from Table 2, in 1000cd/m2Under brightness, the present invention uses TADF material as the device performance of luminescent dye Stablize, current efficiency and power efficiency with higher.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (5)

1. a kind of OLED material, which is characterized in that including with molecular structure shown in meeting formula (1),
Wherein, X is SO in formula2OrWherein Ar structure is as follows:
In any one, E be chemical bond connection site.
2. a kind of a kind of preparation method of OLED material as described in claim 1, which is characterized in that include the following steps, it will be former Material A reacts to obtain type I compound with raw material C, as shown in reaction equation 2；Or react to obtain type I compound with raw material E by raw material D, As shown in reaction equation 4；
Wherein, in reaction equation 2 and reaction equation 4, X SO2OrAr is selected from group as described in claim 1.
3. a kind of purposes of OLED material a kind of as described in claim 1 as organic electroluminescent LED material.
4. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes luminescent layer, described to shine Layer contains OLED material described in claim 1.
5. a kind of organic electroluminescence device according to claim 4, which is characterized in that the organic electroluminescence device is OLED device.
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WO2016029137A1 (en) * 2014-08-22 2016-02-25 Arizona Board Of Regents On Behalf Of Arizona State University Organic light-emitting diodes with fluorescent and phosphorescent emitters
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CN102257097A (en) * 2008-12-18 2011-11-23 东友精细化工有限公司 Asymmetrical aryl amine derivative for organic electroluminescence devices, method for preparing same, organic thin film for organic electroluminescence devices and organic electroluminescence device using same
WO2016029137A1 (en) * 2014-08-22 2016-02-25 Arizona Board Of Regents On Behalf Of Arizona State University Organic light-emitting diodes with fluorescent and phosphorescent emitters
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