WO2018014405A1 - 发光材料及其制备方法与使用该发光材料的有机发光二极管 - Google Patents
发光材料及其制备方法与使用该发光材料的有机发光二极管 Download PDFInfo
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- WO2018014405A1 WO2018014405A1 PCT/CN2016/095609 CN2016095609W WO2018014405A1 WO 2018014405 A1 WO2018014405 A1 WO 2018014405A1 CN 2016095609 W CN2016095609 W CN 2016095609W WO 2018014405 A1 WO2018014405 A1 WO 2018014405A1
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Definitions
- the present invention relates to the field of display technologies, and in particular, to a luminescent material, a method for fabricating the same, and an organic light emitting diode using the luminescent material.
- OLED organic light-emitting diode
- OLED organic electroluminescent display
- the working temperature has wide adaptability, light volume, fast response, easy to realize color display and large screen display, easy to realize integration with integrated circuit driver, easy to realize flexible display, and the like, and thus has broad application prospects.
- OLED displays use organic light-emitting diodes for illumination, so it is extremely important to improve the efficiency and lifetime of organic light-emitting diodes.
- organic light-emitting diodes have made great progress.
- fluorescent phosphorescence hybridization white light devices with simple structure and high efficiency can be obtained.
- the efficiency of such fluorescent phosphor hybrid devices is largely dependent on the efficiency of the fluorescence, so the development of efficient fluorescent materials remains of great importance.
- luminescent small molecules can be obtained in commercial applications because of their simple preparation steps, stable structure, and purification, so that higher device efficiencies can be obtained.
- the use of small molecules for evaporation or solution processing to prepare multilayer devices has received great attention and has made great progress.
- the efficiency of the device is greatly limited because it usually only uses 25% of singlet excitons.
- the Japanese Adachi team used the thermal activation delayed fluorescence mechanism to make the exciton utilization rate of all organic materials reach 100%, which made the device efficiency of organic fluorescence leap.
- due to the scarcity of such materials expanding the types of such materials is of great significance for future application choices.
- organic small molecule luminescent materials with simple structure and good performance and satisfying commercialization requirements are still very limited, and luminescent materials with low development cost and excellent efficiency are still of great significance.
- the object of the present invention is to provide a luminescent material which has a single structure, a certain molecular weight, a good solubility and a film forming property, and can be applied to a small molecule organic light emitting diode.
- the object of the present invention is also to provide a method for preparing a luminescent material, which has simple steps and a yield. high.
- Another object of the present invention is to provide an organic light emitting diode, wherein the light emitting layer contains the above light emitting material, and has high luminous efficiency and stability.
- the present invention first provides a luminescent material having a structural formula of Wherein Ar 1 and Ar 2 are each selected from the group consisting of aromatic amino groups represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7). ;
- Ar 1 is the same as Ar 2 .
- the luminescent material includes one or more of the compounds P6, P10, P16, P22, P28, P34, and P40;
- the invention also provides a preparation method of a luminescent material, comprising the following steps:
- Step 2 intermediate A luminescent material is obtained by reacting an aromatic amine compound with a Ullmann reaction or Suzuki, and the luminescent material has a structural formula of Wherein Ar 1 and Ar 2 are each selected from the group consisting of aromatic amino groups represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7). ;
- Ar 1 is the same as Ar 2 .
- the luminescent material includes one or more of the compounds P6, P10, P16, P22, P28, P34, and P40;
- the step 1 includes:
- Step 12 First hydrolyzed under alkaline conditions and then acidified to obtain
- the present invention provides an organic light emitting diode comprising a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode stacked in this order from bottom to top on the substrate;
- the luminescent layer includes a luminescent material, and the luminescent material has a structural formula of
- Ar 1 and Ar 2 are each selected from the group consisting of aromatic amino groups represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7). ;
- Ar 1 is the same as Ar 2 .
- the luminescent material includes one or more of the compounds P6, P10, P16, P22, P28, P34, and P40;
- the invention has the beneficial effects that the luminescent material provided by the invention has a single structure, a certain molecular weight, good solubility and film forming property, and stable film morphology; and has a high decomposition temperature and a relatively low sublimation temperature. It is easy to sublimate into a high-purity luminescent material, which can be applied to a small molecule organic light-emitting diode; by changing the linked aromatic amine group, the physical properties can be further improved, and the performance of the photovoltaic device based on the luminescent material can be improved.
- the invention provides a method for preparing a luminescent material, which comprises using bromothiophenol and 2-fluoro-4-bromobenzonitrile as starting materials, and obtaining an intermediate of a luminescent material through a series of simple reactions, and finally passing Ur.
- the mannon reaction or the Suzuki reaction gives a luminescent material, and the steps are simple and the yield is high.
- the invention provides an organic light emitting diode, wherein the light emitting layer comprises the above light emitting material, and has high luminous efficiency and stability.
- FIG. 1 is a flow chart of a method for preparing a luminescent material of the present invention
- Figure 2 is a graph showing the absorption emission spectrum of the compound P6 in a toluene solution
- Figure 3 is a room temperature fluorescence emission spectrum of a compound P6 in a tetrahydrofuran solution
- FIG. 5 is a schematic structural view of an organic light emitting diode according to the present invention.
- FIG. 6 is a graph showing voltage-current density/luminance of an organic light emitting diode containing a compound P6;
- Fig. 8 is a graph showing the electroluminescence spectrum of an organic light emitting diode containing the compound P6.
- the invention firstly provides a luminescent material having the structural formula Wherein Ar 1 and Ar 2 are each selected from the group consisting of aromatic amino groups represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7). ;
- Ar 1 is the same as Ar 2 .
- the luminescent material includes one or more of the compounds P6, P10, P16, P22, P28, P34, and P40;
- the luminescent material has the advantages of single structure, determined molecular weight, good solubility and film forming property, and stable film morphology; high decomposition temperature and relatively low sublimation temperature, and easy sublimation into high-purity luminescent materials, applicable For small molecule organic light-emitting diodes; by changing the attached aromatic amine groups, the physical properties can be further improved, and the performance of the photovoltaic device based on the luminescent material can be improved.
- the present invention also provides a method for preparing the above luminescent material, comprising the following steps:
- the step 1 includes:
- step 11 The specific implementation steps of the step 11 are:
- Step 12 First hydrolyzed under alkaline conditions and then acidified to obtain
- step 12 The specific implementation steps of the step 12 are:
- step 13 The specific implementation steps of the step 13 are:
- step 14 The specific implementation steps of the step 14 are:
- Step 2 intermediate A luminescent material is obtained by a Ullmann reaction or a Suzuki reaction with an aromatic amine compound, and the luminescent material has a structural formula of Wherein Ar 1 and Ar 2 are each selected from the group consisting of aromatic amino groups represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7). ;
- Ar 1 is the same as Ar 2 .
- the luminescent material includes one or more of the compounds P6, P10, P16, P22, P28, P34, and P40;
- the aromatic amine compound comprises carbazole, diphenylamine, 9,9-dimethyl acridine, p-carbazole boronate, p-phenyloxazolium borate, p-three.
- Example 1 Intermediate Compound P6 is obtained by reaction with carbazole by Ullmann.
- FIG. 2 is a graph showing the absorption emission spectrum of the compound P6 in a toluene solution
- FIG. 3 is a room temperature fluorescence emission spectrum of the compound P6 in a tetrahydrofuran solution
- FIG. 4 is a 77K low-temperature phosphorescence spectrum of the compound P6 in a tetrahydrofuran solution.
- 3,6-2Cz-TOXO is an abbreviation for the compound P6.
- the compound P6 has good luminescent properties.
- Example 2 Intermediate Compound P10 was obtained by a Ullmann reaction with 9,9-dimethylacridine.
- the synthetic route of the compound P10 is as follows:
- Example 3 Intermediate Compound P16 is obtained by a Ullmann reaction with diphenylamine.
- Example 4 Intermediate Compound P22 is obtained by reaction with p-carbazole phenyl boronate via Suzuki.
- Example 5 Intermediate Compound P28 is obtained by reaction with p-phenyloxazole boronate via Suzuki.
- Example 6 Intermediate Compound P34 is obtained by reaction with p-triphenylamine borate through Suzuki.
- Example 7 Intermediate Compound P40 is obtained by reaction with p-phenylphenothiazine-S,S-dioxaborate via Suzuki.
- the preparation method of the above luminescent material uses m-bromothiophenol and 2-fluoro-4-bromobenzonitrile as starting materials, and obtains an intermediate of a luminescent material through a series of simple reactions, and finally passes a Ullmann reaction or a Suzuki reaction.
- the luminescent material is obtained, the steps are simple, and the yield is high.
- the present invention further provides an organic light emitting diode including the above luminescent material, comprising a substrate 10, an anode 20 and a hole injection layer stacked in this order from bottom to top on the substrate 10. 30, hole transport layer 40, light emitting layer 50, electron transport layer 60, electron injection layer 70, and cathode 80;
- the luminescent layer 50 includes a luminescent material, and the luminescent material has a structural formula of
- Ar 1 and Ar 2 are each selected from the group consisting of aromatic amino groups represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), and formula (7). ;
- Ar 1 is the same as Ar 2 .
- the luminescent material includes one or more of the compounds P6, P10, P16, P22, P28, P34, and P40;
- the light emitting material is 1%.
- the light emitting layer 50 may emit red light, yellow light, green light, or blue light.
- the material of the anode 20 includes a transparent metal oxide, and the transparent metal oxide is preferably indium tin oxide (ITO).
- ITO indium tin oxide
- the material of the hole injection layer 30 includes 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN)
- HAT-CN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
- the material of the hole transport layer 40 includes 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), the 1,1-bis[(di-4) -tolylamino)phenyl]cyclohexane has the structural formula
- the light emitting layer 50 further includes 4,4′-bis(N-carbazole)-1,1′-biphenyl (CBP), and the 4,4′-bis(N-carbazole)-1 , the structural formula of 1'-biphenyl is
- the material of the electron transport layer 60 includes 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TmPyPB), the 1,3,5-tri[(3- The structural formula of pyridyl)-3-phenyl]benzene is
- the material of the electron injection layer 70 includes lithium fluoride (LiF).
- the material of the cathode 80 includes aluminum (Al).
- the anode 20 has a thickness of 95 nm
- the hole injection layer 30 has a thickness of 5 nm
- the hole transport layer 40 has a thickness of 20 nm
- the light-emitting layer 50 has a thickness of 35 nm
- the electron transport The thickness of the layer 60 is 55 nm
- the thickness of the electron injecting layer 70 is 1 nm
- the thickness of the cathode 80 is greater than 80 nm.
- the preparation process of the organic light emitting diode is as follows: the indium tin oxide transparent conductive glass is ultrasonically treated in a cleaning agent, and then washed with deionized water, degreased by ultrasonic in a mixed solvent of acetone/ethanol, and then in a clean environment.
- FIG. 6 is a graph showing voltage-current density/luminance of an organic light emitting diode containing a light-emitting material P6
- FIG. 7 is a graph showing brightness-current efficiency/power efficiency of an organic light-emitting diode containing a light-emitting material P6
- CBP: 1 wt% P6 indicates that the light-emitting layer material of the organic light-emitting diode includes 4,4'-bis(N-carbazole)-1,1'-biphenyl (CBP) and luminescence.
- the material P6, and the specific gravity of the luminescent material P6 in the luminescent layer material is 1% by weight.
- the organic light emitting diode containing the luminescent material P6 has good luminescent properties and luminous efficiency.
- the luminescent material provided by the invention has a single structure, a certain molecular weight, good solubility and film forming property, and stable film morphology; high decomposition temperature and relatively low sublimation temperature, and easy Sublimation into a high-purity luminescent material, which can be applied to a small molecule organic light-emitting diode; by changing the attached aromatic amine group, the physical properties can be further improved, and the performance of the photovoltaic device based on the luminescent material can be improved.
- the invention provides a method for preparing a luminescent material, which comprises using bromothiophenol and 2-fluoro-4-bromobenzonitrile as starting materials, and obtaining an intermediate of a luminescent material through a series of simple reactions, and finally passing Ur.
- the mannon reaction or the Suzuki reaction gives a luminescent material, and the steps are simple and the yield is high.
- the invention provides an organic light emitting diode, wherein the light emitting layer comprises the above light emitting material, and has high luminous efficiency and stability.
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Abstract
一种发光材料及其制备方法与使用该发光材料的有机发光二极管。该发光材料结构单一，分子量确定，具有较好的溶解性及成膜性，且薄膜形态稳定；具有很高的分解温度和比较低的升华温度，容易升华成高纯度的发光材料，可应用于小分子有机发光二极管。所述发光材料的制备方法，以间溴苯酚与2-氟-4-溴苄腈为起始原料，通过一系列的简单反应得到发光材料的中间体，最后通过乌尔曼反应或铃木反应得到发光材料，步骤简单，产率高。所述有机发光二极管，发光层含有上述发光材料，具有较高的发光率与稳定性。
Description
本发明涉及显示技术领域，尤其涉及一种发光材料及其制备方法与使用该发光材料的有机发光二极管。
有机发光二极管(OLED，Organic Light-Emitting Diode)显示器，也称为有机电致发光显示器，是一种新兴的平板显示装置，由于其具有制备工艺简单、成本低、功耗低、发光亮度高、工作温度适应范围广、体积轻薄、响应速度快，而且易于实现彩色显示和大屏幕显示、易于实现和集成电路驱动器相匹配、易于实现柔性显示等优点，因而具有广阔的应用前景。
OLED显示器利用有机发光二极管进行发光，因此改善有机发光二极管的效率和寿命显得极为重要。至今，有机发光二极管已经取得了长足的进展，通过荧光磷光杂化，可以获得器件结构简单且效率很高的白光器件。而这种荧光磷光杂化器件的效率很大程度上依赖于荧光的效率，因此发展高效的荧光材料依然具有举足轻重的意义。
相比于聚合物而言，发光小分子由于制备步骤简便，结构稳定，能够纯化，因而可以获得更高的器件效率，从而可得到商业化应用。利用小分子进行蒸镀或者溶液加工，制备多层器件的方法已经受到了极大关注，并且取得了巨大的进展。但是基于传统的有机荧光材料由于通常只能利用25％的单线态激子，因此器件的效率受到极大的限制。而近期，由日本人Adachi课题组利用热活化延迟荧光机理，使全有机材料的激子利用率也可以达到100％，使得有机荧光的器件效率实现了飞跃。然而由于这类材料种类稀少，因而拓展这类材料的种类对未来的应用选择具有很重要的意义。至今为止，结构简单、且兼具良好性能、满足商业化需求的有机小分子发光材料依旧十分有限，开发成本低廉且效率优异的发光材料依然具有举足轻重的意义。
发明内容
本发明的目的在于提供一种发光材料，结构单一，分子量确定，具有较好的溶解性及成膜性，可应用于小分子有机发光二极管。
本发明的目的还在于提供一种发光材料的制备方法，步骤简单，产率
高。
本发明的目的还在于提供一种有机发光二极管，发光层含有上述发光材料，具有较高的发光效率与稳定性。
为实现上述目的，本发明首先提供一种发光材料，结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
Ar1与Ar2相同。
所述发光材料包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；
所述化合物P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
本发明还提供一种发光材料的制备方法，包括如下步骤：
步骤1、制备中间体
步骤2、中间体
与芳香胺化合物通过乌尔曼反应或
铃木反应得到发光材料，所述发光材料的结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
Ar1与Ar2相同。
所述发光材料包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；
所述化合物P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
所述步骤1包括：
步骤11、间溴苯硫酚与2-氟-4-溴苄腈反应得到
步骤12、
先在碱性条件下水解，再酸化，得到
步骤13、
发生脱水缩合反应，得到
和
步骤14、
与过氧化氢反应得到中间体
本发明提供一种有机发光二极管，包括基板、在基板上从下到上依次层叠设置的阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层、及阴极；
所述发光层包括发光材料，所述发光材料的结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
Ar1与Ar2相同。
所述发光材料包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；
所述化合物P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
本发明的有益效果：本发明提供的一种发光材料，结构单一，分子量确定，具有较好的溶解性及成膜性，且薄膜形态稳定；具有很高的分解温度和比较低的升华温度，容易升华成高纯度的发光材料，可应用于小分子有机发光二极管；通过改变连接的芳香胺基团，可进一步改善其物理特性，提升基于该发光材料的光电器件的性能。本发明提供的一种发光材料的制备方法，以间溴苯硫酚与2-氟-4-溴苄腈为起始原料，通过一系列的简单反应得到发光材料的中间体，最后通过乌尔曼反应或铃木反应得到发光材料，步骤简单，产率高。本发明提供的一种有机发光二极管，发光层含有上述发光材料，具有较高的发光效率与稳定性。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为本发明的发光材料的制备方法的流程图；
图2为化合物P6在甲苯溶液中的吸收发射光谱图；
图3为化合物P6在四氢呋喃溶液中的室温荧光发射光谱图；
图4为化合物P6在四氢呋喃溶液中的77K低温磷光发射光谱图；
图5为本发明的有机发光二极管的结构示意图；
图6为含有化合物P6的有机发光二极管的电压-电流密度/亮度关系曲线图；
图7为含有化合物P6的有机发光二极管的亮度-电流效率/功率效率关系曲线图；
图8为含有化合物P6的有机发光二极管的电致发光光谱图。
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
本发明首先提供一种发光材料，其结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
优选的，Ar1与Ar2相同。
具体的，所述发光材料包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；
所述化合物P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
上述发光材料，结构单一，分子量确定，具有较好的溶解性及成膜性，且薄膜形态稳定；具有很高的分解温度和比较低的升华温度，容易升华成高纯度的发光材料，可应用于小分子有机发光二极管；通过改变连接的芳香胺基团，可进一步改善其物理特性，提升基于该发光材料的光电器件的性能。
请参阅图1，本发明还提供一种上述发光材料的制备方法，包括如下步骤：
步骤1、制备中间体
所述中间体
的合成路线为：
具体的，所述步骤1包括：
步骤11、间溴苯硫酚与2-氟-4-溴苄腈反应得到
所述步骤11的具体实施步骤为：
于250ml三口烧瓶中将0.73g(30mmol)NaH缓慢加入到溶解有4.7g(25mmol)间溴苯硫酚的20ml干燥二甲基甲酰胺(DMF)中,然后向其中滴加溶解有5g(25mmol)2-氟-4-溴苄腈的20ml干燥二甲基甲酰胺中。在氮气保护下，加热回流反应20h，反应结束后降至室温，将反应液倒入50ml1M的NaOH溶液中，二氯甲烷(DCM)萃取，减压出掉溶剂，过硅胶柱，得到白色固体5.2g，即为化合物b1。分子式：C13H7Br2NS；MS:366.87；元素分析：C,42.31；H,1.91；Br,43.30；N,3.80；S,8.69。
步骤12、
先在碱性条件下水解，再酸化，得到
所述步骤12的具体实施步骤为：
于250ml三口烧瓶中加入80ml去离子水、15g KOH、及80ml乙醇，将5.2g化合物b1加入到反应瓶中，氮气保护下回流过夜。反应完冷却至室温，将反应液加入到100ml 6M的盐酸中，冰浴析出白色固体抽滤，干燥
得到白色固体5.1g，即为化合物b2。分子式：C13H8Br2O2S；MS：385.86；元素分析：C,40.23；H,2.08；Br,41.18；O,8.25；S,8.26。
步骤13、
发生脱水缩合反应，得到
和
所述步骤13的具体实施步骤为：
在500ml单口烧瓶中加入2.75g(10mmol)化合物b2，加入500ml氯仿作为溶剂，滴加3.2g(20mmol，2equ)三氟乙酸酐，室温搅拌10min，加冰浴冷却10min，然后加入0.5g三氟化硼乙醚，去掉冰浴室温反应12h。反应完，加亚硫酸钠饱和水溶液，淬灭多余的三氟乙酸酐，分液，减压蒸馏除掉溶剂，过柱分别得到
产率分别为36％和45％。
步骤14、
与过氧化氢反应得到中间体
所述步骤14的具体实施步骤为：
于250ml三口烧瓶中加入5g(13.59mmol)
50mL二氯甲烷、20mL醋酸、3mL(5equ)过氧化氢。在80℃下反应8小时，反应完降温，用水洗去多余过氧化氢后萃取。过柱得到4.34g的中间体
产率为88％；分子式：C13H6Br2O3S；M/Z＝399.84；理论值：402.06；元素分析：401.84(100.0％),399.84(50.0％),403.84(48.1％),402.84(15.0％),404.84(7.8％),400.84(7.5％),403.83(4.4％),405.83(2.2％)。
步骤2、中间体
与芳香胺化合物通过乌尔曼反应或
铃木(Suzuki)反应得到发光材料，所述发光材料的结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
优选的，Ar1与Ar2相同。
具体的，所述发光材料包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；
所述化合物P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
具体的，所述步骤2中，所述芳香胺化合物包括咔唑、二苯胺、9,9-二甲基吖啶、对咔唑苯硼酸酯、对苯基咔唑硼酸酯、对三苯胺硼酸酯、及对苯基吩噻嗪-S,S-二氧硼酸酯中的一种或多种；
所述咔唑的结构式为
所述二苯胺的结构式为
所述9,9-二甲基吖啶的结构式为
所述对咔唑苯硼酸酯的结构式为
所述对苯基咔唑硼酸酯的结构式为
所述对三苯胺硼酸酯的结构式为
所述对苯基吩噻嗪-S,S-二氧硼酸酯的结构式为
以下结合具体实施例，详细说明所述步骤2的具体实施方法。
实施例1：中间体
与咔唑通过乌尔曼反应得到化合物P6。
所述化合物P6的合成路线如下：
所述实施例1的具体实施步骤为：
在氮气保护下，向三口烧瓶中加入100ml甲苯、0.72g(2mmol)中间体
0.67g(4mmol)咔唑，在搅拌下加入0.3g叔丁基醇钠，再加入20mg三(二亚苄基丙酮)二钯(Pd2(dba)3)，再加入0.3ml 10％三叔丁基膦正己烷溶液，加热回流，反应过夜。降温，用二氯甲烷萃取有机相，旋干，过柱。得白色固体产物0.77g，产率67％。分子式：C37H22N2O3S；M/Z＝574.14；理论值：574.14(100.0％),575.14(40.4％),576.14(9.2％),576.13(4.5％),577.13(1.8％),575.13(1.5％),577.15(1.0％)；元素分析：C,77.33；H,3.86；N,4.87；O,8.35；S,5.58。
图2为化合物P6在甲苯溶液中的吸收发射光谱图；图3为化合物P6在四氢呋喃溶液中的室温荧光发射光谱图；图4为化合物P6在四氢呋喃溶液中的77K低温磷光发射光谱图。图2、图3、及图4中，3,6-2Cz-TOXO为化合物P6的简称，从图2、图3、及图4中可以看出，化合物P6具有良好的发光性能。
实施例2：中间体
与9,9-二甲基吖啶通过乌尔曼反应得到化合物P10。
所述化合物P10的合成路线如下：
所述实施例2的具体实施步骤为：
在氮气保护下，向三口烧瓶中加入100ml甲苯、0.72g(2mmol)中间体
0.84g(4mmol)9,9-二甲基吖啶，在搅拌下加入0.3g叔丁基醇钠，再加入20mg三(二亚苄基丙酮)二钯(Pd2(dba)3)，再加入0.3ml10％三叔丁基膦正己烷溶液，加热回流，反应过夜。降温，用二氯甲烷萃取有机相，旋干，过柱。得到白色固体0.78g，产率62％。分子式：C43H34N2O3S；M/Z＝658.23；理论值：658.23(100.0％),659.23(48.2％),660.24(10.8％),660.22(4.5％),661.23(2.2％),661.24(2.0％),660.23(1.3％)；元素分析：C,78.39；H,5.20；N,4.25；O,7.29；S,4.87。
实施例3：中间体
与二苯胺通过乌尔曼反应得到化合物P16。
所述化合物P16的合成路线如下：
所述实施例3的具体实施步骤为：
在氮气保护下，向三口烧瓶中加入100ml甲苯、0.72g(2mmol)中间体
0.84g(4mmol)二苯胺，在搅拌下加入0.3g叔丁基醇钠，再加入20mg三(二亚苄基丙酮)二钯(Pd2(dba)3)，再加入0.3ml 10％三叔丁基膦正己烷溶液，加热回流，反应过夜。降温，用二氯甲烷萃取有机相，旋干，过柱。得白色固体产物0.69g，产率60％。分子式：C37H26N2O3S；M/Z＝578.17；理论值：578.17(100.0％),579.17(41.2％),580.17(9.1％),580.16(4.5％),581.17(2.2％),581.18(1.0％)；元素分析：C,76.79；H,4.53；N,4.84；O,8.29；S,5.54。
实施例4：中间体
与对咔唑苯硼酸酯通过铃木反应得到化合物P22。
所述化合物P22的合成路线如下：
所述实施例4的具体实施步骤为：
在氮气气氛下，往250ml烧瓶中加入96ml甲苯、32ml乙醇、16ml 2M的碳酸钾水溶液、0.72g(2mmol)中间体
2.06g(1.2equ)对咔唑苯硼酸酯，室温搅拌，然后加入100mg三苯基磷钯(催化剂)，96℃回流24小时。冷却至室温，二氯甲烷萃取，无水硫酸镁干燥。得白色固体产物1.22g，产率84％。分子式：C49H30N2O3S；M/Z＝726.20；理论值：726.20(100.0％),727.20(54.3％),728.20(15.2％),728.19(4.5％),729.21(2.7％),729.20(2.6％)；元素分析：C,80.97；H,4.16；N,3.85；O,6.60；S,4.41。
实施例5：中间体
与对苯基咔唑硼酸酯通过铃木反应得到化合物P28。
所述化合物P28的合成路线如下：
所述实施例5的具体实施步骤为：
在氮气气氛下，往250ml烧瓶中加入96ml甲苯、32ml乙醇、16ml 2M的碳酸钾水溶液、0.72g(2mmol)中间体
2.32g(1.2equ)对苯基咔唑硼酸酯，室温搅拌，然后加入100mg三苯基磷钯(催化剂)，96℃回流24小时。冷却至室温，二氯甲烷萃取，无水硫酸镁干燥。分离得白色固体1.23g，产率85％。分子式：C49H30N2O3S；M/Z＝726.20；理论值：726.20(100.0％),727.20(54.3％),728.20(15.2％),728.19(4.5％),729.21(2.7％),729.20(2.6％)；元素分析：C,80.97；H,4.16；N,3.85；O,6.60；S,4.41。
实施例6：中间体
与对三苯胺硼酸酯通过铃木反应得到化合物P34。
所述化合物P34的合成路线如下：
所述实施例6的具体实施步骤为：
在氮气气氛下，往250ml烧瓶中加入96ml甲苯、32ml乙醇、16ml 2M的碳酸钾水溶液、0.72g(2mmol)中间体
2.32g(1.2equ)对
三苯胺硼酸酯，室温搅拌，然后加入100mg三苯基磷钯(催化剂)，96℃回流24小时。冷却至室温，二氯甲烷萃取，无水硫酸镁干燥。得白色固体产物1.21g，产率83％。分子式：C49H34N2O3S；M/Z＝730.23；理论值：730.23(100.0％),731.23(54.7％),732.24(14.0％),732.22(4.5％),733.24(2.8％),733.23(2.5％),732.23(1.4％)；元素分析：C,80.52；H,4.69；N,3.83；O,6.57；S,4.39。
实施例7：中间体
与对苯基吩噻嗪-S,S-二氧硼酸酯通过铃木反应得到化合物P40。
所述化合物P40的合成路线如下：
所述实施例7的具体实施步骤为：
在氮气气氛下，往250ml烧瓶中加入96ml甲苯、32ml乙醇、16ml 2M的碳酸钾水溶液、0.72g(2mmol)中间体
2.06g(1.2equ)对苯基吩噻嗪-S,S-二氧硼酸酯，室温搅拌，然后加入100mg三苯基磷钯(催化剂)，96℃回流24小时。冷却至室温，二氯甲烷萃取，无水硫酸镁干燥。得白色固体产物1.45g，产率85％。分子式：C49H30N2O7S3；M/Z＝854.12；理论值：854.12(100.0％),855.12(56.1％),856.13(15.5％),856.12(15.3％),857.12(7.5％),857.13(3.7％),858.12(2.3％)；元素分析：C,68.84；H,3.54；N,3.28；O,13.10；S,11.25。
上述发光材料的制备方法，以间溴苯硫酚与2-氟-4-溴苄腈为起始原料，通过一系列的简单反应得到发光材料的中间体，最后通过乌尔曼反应或铃木反应得到发光材料，步骤简单，产率高。
请参阅图5，本发明还提供一种含有上述发光材料的有机发光二极管，包括基板10、在基板10上从下到上依次层叠设置的阳极20、空穴注入层
30、空穴传输层40、发光层50、电子传输层60、电子注入层70、及阴极80；
所述发光层50包括发光材料，所述发光材料的结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
优选的，Ar1与Ar2相同。
具体的，所述发光材料包括包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；
所述化合物P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
优选的，所述发光层50的材料中，所述发光材料
的质量百分比为1％。
具体的，所述发光层50可以发红光、黄光、绿光、或者蓝光。
具体的，所述阳极20的材料包括透明金属氧化物，所述透明金属氧化物优选为氧化铟锡(ITO)。
具体的，所述空穴注入层30的材料包括2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂三亚苯(HAT-CN)，所述2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂三亚苯的结构式为
具体的，所述空穴传输层40的材料包括1,1-双[(二-4-甲苯基氨基)苯基]环己烷(TAPC)，所述1,1-双[(二-4-甲苯基氨基)苯基]环己烷的结构式为
具体的，所述发光层50还包括4,4'-双(N-咔唑)-1,1'-联苯(CBP)，所述4,4'-双(N-咔唑)-1,1'-联苯的结构式为
具体的，所述电子传输层60的材料包括1,3,5-三[(3-吡啶基)-3-苯基]苯(TmPyPB)，所述1,3,5-三[(3-吡啶基)-3-苯基]苯的结构式为
具体的，所述电子注入层70的材料包括氟化锂(LiF)。
具体的，所述阴极80的材料包括铝(Al)。
优选的，所述阳极20的厚度为95nm，所述空穴注入层30的厚度为5nm，所述空穴传输层40的厚度为20nm，所述发光层50的厚度为35nm，所述电子传输层60的厚度为55nm，所述电子注入层70的厚度为1nm，所述阴极80的厚度大于80nm。
所述有机发光二极管的制备过程如下：将氧化铟锡透明导电玻璃在清洗剂中进行超声处理，再用去离子水清洗，在丙酮/乙醇的混合溶剂中利用超声除油，之后在洁净的环境下烘烤至完全除去水分，然后用紫外光和臭氧进行清洗，并用低能阳离子轰击得到阳极20，将带有阳极20的透明导电玻璃置于真空腔内，抽真空至1×10-5～9×10-3Pa，然后在所述阳极20上依次蒸镀空穴注入层30、空穴传输层40、数层发光层50、电子传输层60、电子注入层70与阴极80，最终得到本实施例的有机发光二极管。
图6为含有发光材料P6的有机发光二极管的电压-电流密度/亮度关系曲线图；图7为含有发光材料P6的有机发光二极管的亮度-电流效率/功率效率关系曲线图；图8为含有发光材料P6的有机发光二极管的电致发光光谱图。图6、图7、及图8中，CBP：1wt％P6表示有机发光二极管的发光层材料包括4,4'-双(N-咔唑)-1,1'-联苯(CBP)与发光材料P6，且发光材料P6在发光层材料中的比重为1wt％，从图6、图7、及图8中可以看出，含有发光材料P6的有机发光二极管具有良好的发光性能和发光效率。
综上所述，本发明提供的一种发光材料，结构单一，分子量确定，具有较好的溶解性及成膜性，且薄膜形态稳定；具有很高的分解温度和比较低的升华温度，容易升华成高纯度的发光材料，可应用于小分子有机发光二极管；通过改变连接的芳香胺基团，可进一步改善其物理特性，提升基于该发光材料的光电器件的性能。本发明提供的一种发光材料的制备方法，以间溴苯硫酚与2-氟-4-溴苄腈为起始原料，通过一系列的简单反应得到发光材料的中间体，最后通过乌尔曼反应或铃木反应得到发光材料，步骤简单，产率高。本发明提供的一种有机发光二极管，发光层含有上述发光材料，具有较高的发光效率与稳定性。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。
Claims (10)
- 一种发光材料，结构通式为其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
- 如权利要求1所述的发光材料，其中，Ar1与Ar2相同。
- 如权利要求2所述的发光材料，包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；所述化合物P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
- 一种发光材料的制备方法，包括如下步骤：步骤1、制备中间体
步骤2、中间体与芳香胺化合物通过乌尔曼反应或铃木反应得到发光材料，所述发光材料的结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
- 如权利要求4所述的发光材料的制备方法，其中，Ar1与Ar2相同。
- 如权利要求5所述的发光材料的制备方法，其中，所述发光材料包括P6、P10、P16、P22、P28、P34、及P40中的一种或多种；所述P6、P10、P16、P22、P28、P34、及P40的结构式分别如下：
- 如权利要求4所述的发光材料的制备方法，其中，所述步骤1包括：步骤11、间溴苯硫酚与2-氟-4-溴苄腈反应得到
步骤12、先在碱性条件下水解，再酸化，得到
步骤13、发生脱水缩合反应，得到
和
步骤14、与过氧化氢反应得到中间体
- 一种有机发光二极管，包括基板、在基板上从下到上依次层叠设置的阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层、及阴极；所述发光层包括发光材料，所述发光材料的结构通式为
其中，Ar1、Ar2分别选自式(1)、式(2)、式(3)、式(4)、式(5)、式(6)、式(7)所示的芳香氨基团；
- 如权利要求8所述的有机发光二极管，其中，Ar1与Ar2相同。
- 如权利要求9所述的有机发光二极管，其中，所述发光材料包括化合物P6、P10、P16、P22、P28、P34、及P40中的一种或多种；所述P6、P10、P16、P22、P28、P34、及化合物P40的结构式分别如下：
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| CN103189368A (zh) * | 2010-11-08 | 2013-07-03 | 佳能株式会社 | 噻吨酮化合物和具有该噻吨酮化合物的有机发光元件 |
| CN103804346A (zh) * | 2012-11-08 | 2014-05-21 | 中国科学院理化技术研究所 | 氧化硫杂蒽酮类衍生物、制备方法及其应用 |
| CN104756275A (zh) * | 2012-10-31 | 2015-07-01 | 默克专利有限公司 | 电子器件 |
| CN104761547A (zh) * | 2015-03-26 | 2015-07-08 | 深圳市华星光电技术有限公司 | 噻吨酮-芳香胺化合物及应用该化合物的有机发光器件 |
| KR20160064644A (ko) * | 2014-11-28 | 2016-06-08 | 주식회사 엘지화학 | 신규한 화합물, 이의 제조방법 및 이를 포함하는 유기 태양전지 |
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| CN103189368A (zh) * | 2010-11-08 | 2013-07-03 | 佳能株式会社 | 噻吨酮化合物和具有该噻吨酮化合物的有机发光元件 |
| CN104756275A (zh) * | 2012-10-31 | 2015-07-01 | 默克专利有限公司 | 电子器件 |
| CN103804346A (zh) * | 2012-11-08 | 2014-05-21 | 中国科学院理化技术研究所 | 氧化硫杂蒽酮类衍生物、制备方法及其应用 |
| KR20160064644A (ko) * | 2014-11-28 | 2016-06-08 | 주식회사 엘지화학 | 신규한 화합물, 이의 제조방법 및 이를 포함하는 유기 태양전지 |
| CN104761547A (zh) * | 2015-03-26 | 2015-07-08 | 深圳市华星光电技术有限公司 | 噻吨酮-芳香胺化合物及应用该化合物的有机发光器件 |
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