WO2023231795A1 - Heterocyclic compound and organic light-emitting element comprising same - Google Patents

Heterocyclic compound and organic light-emitting element comprising same Download PDF

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WO2023231795A1
WO2023231795A1 PCT/CN2023/095029 CN2023095029W WO2023231795A1 WO 2023231795 A1 WO2023231795 A1 WO 2023231795A1 CN 2023095029 W CN2023095029 W CN 2023095029W WO 2023231795 A1 WO2023231795 A1 WO 2023231795A1
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unsubstituted
substituted
layer
aryl
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PCT/CN2023/095029
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曹建华
姜卫东
张九敏
边坤
戴雄
邸庆童
何连贞
姜坤
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北京八亿时空液晶科技股份有限公司
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Publication of WO2023231795A1 publication Critical patent/WO2023231795A1/en

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    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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Definitions

  • the present invention relates to the technical field of organic electroluminescent materials, and in particular to a heterocyclic compound and its application in organic light-emitting elements.
  • organic luminescence refers to the phenomenon of emitting light when electric energy is applied to an organic substance; that is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes will be injected from the anode. To the organic layer, electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed. When the excitons transition to the ground state, they emit light and heat.
  • organic electroluminescent display technology has matured, and some products have entered the market.
  • problems that need to be solved during the industrialization process.
  • various organic materials used to make components including their carrier injection and transmission properties, material electroluminescence properties, service life, color purity, matching between various materials and between various electrodes, etc.
  • the problem has not yet been solved; in particular, the luminous efficiency and service life of light-emitting components have not yet met practical requirements, which has greatly restricted the development of organic light-emitting diode (OLED) technology.
  • Metal complex phosphorescent materials that utilize triplet luminescence have high luminous efficiency, and their green and red light materials have met the requirements for use.
  • metal complex phosphorescent materials require phosphorescent materials or hole materials with high triplet energy levels and match. Therefore, the development of phosphorescent materials or hole materials with high triplet energy levels is an urgent need for the current development of OLEDs.
  • the object of the present invention is to provide a heterocyclic compound that can improve the thermal stability of the material and the ability to transport carriers.
  • the organic electroluminescent element prepared by using the compound can significantly reduce the driving voltage and improve the luminous efficiency and lifespan.
  • Another object of the present invention is to provide the application of the compound.
  • the present invention provides the following technical solutions:
  • the present invention provides a heterocyclic compound, the structural formula of which is shown in formula (I):
  • L 1 and L 2 are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
  • X 1 , X 2 , and X 3 are each independently N or CR 3 , and at least one of X 1 , X 2 , and X 3 is N;
  • Y is selected from O, S, CR 4 R 5 , SiR 4 R 5 or NAr 4 ;
  • R 1 , R 2 , R 3 , R 4 and R 5 appear, the same or different ones are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro, carboxyl or their carboxylate, sulfonic acid group or their sulfonate.
  • Acid salt phosphate group or its phosphate, C 1 -C 40 alkyl group, C 1 -C 40 alkoxy group, C 2 -C 40 alkenyl group, C 1 -C 40 alkylthio group, C 1 -C 40 alkyl group Oxygen group, C 3 -C 40 cycloalkyl group, C 1 -C 40 alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, Substituted or unsubstituted C 6 -C 60 arylthio group, substituted or unsubstituted C 6 -C 60 aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 silyl group, substituted or unsubstituted boron A group consisting of a substituted or unsubstituted amino group, a substituted or unsubsti
  • Ar 2 , Ar 3 , and Ar 4 are each independently selected from a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 fused ring aryl group, or a substituted or unsubstituted C 2 - A group consisting of C 60 heterocyclic aryl groups;
  • Ar 1 is selected from the group consisting of groups represented by the following formulas a to h,
  • T 1 and T 2 are directly bonded, or each is independently selected from O, S, NAr, C(R) 2 , or there is no T 1 ;
  • Ar is a substituted or unsubstituted aryl group;
  • R which are the same or different from each other, are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 40 Alkyl, C 1 -C 40 alkoxy, C 2 -C 40 alkenyl, C 1 -C 40 alkylthio, C 1 -C 40 alkoxy, C 3 -C 40 cycloalkyl, C 1 - C 40 alkyl sulfoxide, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60
  • the substituent R is one or more to saturated substitution
  • *- represents the position where L 1 is bonded to the groups represented by formulas a to h.
  • each time R 1 , R 2 , R 3 , R 4 , and R 5 appear they are each independently selected from hydrogen, deuterium, fluorine, nitrile, phenyl, diphenyl, and terphenyl. , naphthyl, phenanthrenyl, triphenylene, carbazole, dibenzofuran or dibenzothiophene group.
  • the Ar 2 , Ar 3 , and Ar 4 are each independently selected from the following groups: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, tetraphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydrogen Pyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimeric indene, isotrimeric indene, spirotrimeric indene, spiroisotrimeric Indene, furan, benzofuran, isobenzofuran, dibenzofuran,
  • the Ar 1 is selected from any one of the groups represented by the following formulas 2 to 33,
  • Ar is phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl, terphenyl, triphenylene, fluorenyl, spirodifluorenyl, dihydrophenanthryl, benzene Furanyl, dibenzofuranyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl or groups derived from combinations of these systems; R, which are the same or different from each other, are selected from hydrogen, deuterium, A group consisting of fluorine, nitrile, methyl, ethyl, phenyl, biphenyl, and fluorenyl. Two or more adjacent R can be arbitrarily joined or fused to form a substituted or unsubstituted ring.
  • the ring formed may or may not contain N, O, S, P, B or C(R) 2 ;
  • the substituent R is one or more to saturated substitution
  • *- represents the site where L 1 is bonded to the group represented by Formula 2 to Formula 33.
  • the Ar 1 is selected from any one of the groups shown below,
  • Ar is phenyl, naphthyl, phenanthrenyl, biphenyl, terphenyl, triphenylene, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, pyridine
  • R which are the same or different from each other, are selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, phenyl, biphenyl, and fluorenyl;
  • the substituent R is one or more to saturated substitution
  • the L 1 and L 2 are each independently selected from the group consisting of the following groups III-1 to III-15:
  • Z 11 and Z 12 are each independently selected from hydrogen, deuterated hydrogen, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate Acid salt, phosphate group or its phosphate, C 1 -C 40 alkyl group, C 2 -C 40 alkenyl group, C 2 -C 40 alkynyl group, C 1 -C 40 alkoxy group, C 3 -C 40 cycloalkane group, C 3 -C 40 cycloalkenyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 aryl sulfide An ether group, or a group consisting of substituted or unsubsti
  • Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 6 -C 60 aryl sulfide group.
  • T 3 represents oxygen atom or sulfur atom
  • substituted or unsubstituted means one selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or its carboxyl group.
  • One or more substituents in the C 60 heterocyclic aryl group may be substituted or unsubstituted, or may be substituted or unsubstituted by a substituent in which two or more substituents among the substituents exemplified above are connected.
  • the compound is selected from the compounds represented by the following formulas CJHM383-CJHM470:
  • the present invention also provides an organic electroluminescent material, the raw material of which includes the above-mentioned heterocyclic compound; the organic electroluminescent material including the compound of the present invention has the ability of carrier transport.
  • the present invention also provides the use of the above-mentioned heterocyclic compound in preparing organic electroluminescent elements.
  • the present invention also provides an organic electroluminescent element, which includes: a first electrode, a second electrode, a capping layer and one or more organic layers placed between the first electrode and the second electrode;
  • the material of at least one layer of the organic layer or capping layer includes the above-mentioned heterocyclic compound.
  • the organic electroluminescent element includes a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may contain further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, excitation layers, etc. sub-blocking layer, electron blocking layer and/or charge generating layer. An intermediate layer having, for example, an exciton blocking function can also be introduced between the two luminescent layers. However, it should be noted that each of these layers does not necessarily have to be present.
  • the organic electroluminescent device described herein may include one light emitting layer, or it may include multiple light emitting layers.
  • a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer.
  • Particularly preferred are systems with three luminescent layers, wherein the three layers can exhibit blue, green and red luminescence. If more than one luminescent layer is present, according to the invention at least one of these layers contains a heterocyclic compound of the invention.
  • the organic electroluminescent element according to the present invention does not include a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, that is, the light-emitting layer and the electron blocking layer or hole transport layer
  • the hole transport layer or the anode is directly adjacent, and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
  • organic electroluminescent components are preferred in which one or more layers are applied by means of a sublimation method, wherein the layer is deposited by vapor deposition in a vacuum sublimation device at an initial pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. Apply the material.
  • the initial pressure may also be even lower, for example below 10 -7 Pa.
  • organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, wherein the material is applied at a pressure of between 10 ⁇ 5 Pa and 1 Pa.
  • a particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
  • organic electroluminescent elements produced from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photothermography, thermal transfer printing, spray printing, etc. Ink printing or nozzle printing to produce one or more layers.
  • Soluble compounds can be obtained, for example, by appropriately substituting compounds represented by formula (I). These methods are also particularly suitable for oligomers, Dendrimers and polymers.
  • hybrid methods are possible, in which one or more layers are applied, for example, from solution and one or more further layers are applied by vapor deposition.
  • the invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, applying at least one layer by means of a sublimation method, and/or characterized in that at least one layer is applied by means of an organic vapor deposition method or by means of carrier gas sublimation. layers, and/or is characterized in that at least one layer is applied by spin coating from solution or by means of printing methods.
  • the invention relates to a heterocyclic compound comprising at least one of the above-indicated heterocyclic compounds of the invention.
  • the compounds may preferably also comprise other compounds.
  • Processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires formulation of the compounds according to the invention.
  • These formulations may be, for example, solutions, dispersions or emulsions.
  • mixtures of two or more solvents may preferably be used.
  • Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, Tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenone, 1,2,3,5-tetramethylbenzene, 1,2, 4,5-Tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, ⁇ -terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohe
  • the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer or an electron blocking layer.
  • the present invention also provides a consumer product, which includes the above-mentioned organic electroluminescent element.
  • the raw materials used in the present invention can be purchased from commercial stores. Any range recorded in the present invention includes the end value and any value between the end value and the end value or any value between the end value. Any subrange formed by.
  • the heterocyclic compound represented by formula (I) provided by the invention has a high triplet energy level, increases the rigidity of the phenanthrene or azaphenanthrene molecule, improves the thermal stability of the material and the ability to transport carriers, and the The compound is used in organic electroluminescent components to significantly reduce driving voltage, improve luminous efficiency and lifespan.
  • FIG. 1 shows a schematic diagram of an organic light-emitting device 100. Illustrations are not necessarily to scale.
  • Device 100 may include substrate 101, anode 102, hole injection layer 103, hole transport layer 104, electron blocking layer 105, light emitting layer 106, hole blocking layer 107, electron transport layer 108, electron injection layer 109, cathode 110 and capping layer (CPL) 111.
  • Device 100 may be fabricated by sequentially depositing the described layers.
  • FIG. 2 shows a schematic diagram of an organic light-emitting device 200 with two light-emitting layers.
  • the device includes a substrate 201, an anode 202, hole injection 203, hole transport layer 204, first light-emitting layer 205, electron transport layer 206, charge generation layer 207, hole injection layer 208, hole transport layer 209, The second light-emitting layer 210, the electron transport layer 211, the electron injection layer 212 and the cathode 213.
  • Device 200 may be prepared by sequentially depositing the described layers.
  • the luminescence peak shapes of the first luminescent layer and the second luminescent layer may be overlapping or cross-overlapping or non-overlapping.
  • materials similar to those described with respect to device 100 may be used.
  • Figure 2 provides an example of how some layers may be added from the structure of device 100.
  • test instruments and methods for performance testing of OLED materials and components in the following examples are as follows:
  • Luminance and chromaticity coordinates tested using spectral scanner PhotoResearch PR-715;
  • X represents I, Br, Cl or OTf; other symbols used are as defined above.
  • the preparation method of compound CJHM387 includes the following steps:
  • the preparation method of compound CJHM399 includes the following steps:
  • the OLED element of this embodiment is a top-emitting light-emitting element, including a substrate 101, an anode layer 102 provided on the substrate 101, a hole injection layer 103 provided on the anode layer 102, The hole transport layer 104 provided on the hole injection layer 103, the electron blocking layer 105 provided on the hole transport layer 104, the organic light emitting layer 106 provided on the electron blocking layer 105, the organic light emitting layer 106 provided on the organic light emitting layer 106.
  • the preparation method of the OLED element includes follow these steps:
  • Formula (I) is the host material and GD03 is the doping material.
  • GD03 is the formula (I). 3% by mass, as the organic light-emitting layer of the element, the film thickness of the organic light-emitting layer obtained by evaporation is
  • An organic electroluminescent element 200 has a structure as shown in Figure 2, which includes a substrate 201, anode 202, hole injection 203, hole transport layer 204, first light emitting layer 205, electron transport layer 206, charge generation layer 207, hole injection layer 208, hole transport layer 209, second light emitting layer 210, electron transport layer 211, electron injection layer 212 and cathode 213.
  • a digital source meter and a luminance meter were used to measure the driving voltage and current efficiency of the organic electroluminescent elements prepared in Example 3 and Comparative Examples 1 and 2, as well as the lifetime of the elements. Specifically, increase the voltage at a rate of 0.1V per second, measure the voltage when the brightness of the organic electroluminescent element reaches 1000cd/ m2 , which is the driving voltage, and measure the current density at this time; the ratio of brightness to current density That is the current efficiency; the LT90% life test is as follows: use a luminance meter to maintain a constant current at a brightness of 1000cd/ m2 , and measure the time for the brightness of the organic electroluminescent element to decay to 900cd/ m2 , in hours.
  • the data listed in Table 3 are relative data compared to Comparative Element 1.
  • the difference between compound HS01 in Comparative Example 1 is that the plane conjugation ability of a single phenanthrene ring is weak, and the transmission of holes and electrons is unbalanced. Its ability to accept holes is stronger than its ability to accept electrons. This is The imbalance of species transmission affects the formation of excitons in the light-emitting layer, resulting in high voltage, low efficiency, and reduced lifetime.
  • the compound of the present invention introduces heteroatoms such as oxygen and sulfur on the basis of the phenanthrene ring, which improves the conjugation ability of the mother core. Therefore, it has excellent performance in molecular film formation and charge transmission, and the charge transmission within the element is more efficient. Balanced, component performance improves.
  • HS02 has a unipolar p-type structure, and its ability to accept holes is stronger than its ability to accept electrons. This imbalance in transmission affects excitons.
  • the formation in the light-emitting layer results in high voltage, low efficiency, and reduced lifespan.
  • the compound of the present invention forms a p-n bipolar structure after introducing a nitrogen-containing heteroaromatic ring, so its performance in molecular film formation and charge transmission is excellent, the charge transmission in the element is more balanced, and the element performance is improved.
  • the heterocyclic compound represented by formula (I) provided by the invention has a high triplet energy level, increases the rigidity of the phenanthrene or azaphenanthrene molecule, improves the thermal stability of the material and the ability to transport carriers, and the The compound is used in organic electroluminescent components to significantly reduce driving voltage, improve luminous efficiency and lifespan.

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Abstract

The present invention relates to the technical field of organic electroluminescent materials, and particularly relates to a heterocyclic compound and the use thereof. The structural formula of the compound is as shown in formula (I). The compound of formula (I) has a heteroatom-bonded phenanthrene structure. When used in an organic electroluminescent element, the compound can significantly reduce the driving voltage, improve the luminous efficiency, and prolong the service life.

Description

一种杂环化合物及包含它的有机发光元件A heterocyclic compound and an organic light-emitting element containing the same
交叉引用cross reference
本申请要求2022年5月31日提交的专利名称为“一种杂环化合物及包含它的有机发光元件”的第202210608100.7号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。This application claims priority from Chinese patent application No. 202210608100.7, titled "A heterocyclic compound and an organic light-emitting element containing the same", filed on May 31, 2022, the entire disclosure of which is incorporated herein by reference in its entirety.
技术领域Technical field
本发明涉及有机电致发光材料技术领域，尤其涉及一种杂环化合物及其在有机发光元件中的应用。The present invention relates to the technical field of organic electroluminescent materials, and in particular to a heterocyclic compound and its application in organic light-emitting elements.
背景技术Background technique
一般而言，有机发光现象是指在对有机物质施加电能时发出光的现象；即在阳极与阴极之间配置有机层时，如果在两个电极之间施加电压，则空穴会从阳极注入至有机层，电子会从阴极注入至有机层；当所注入的空穴和电子相遇时，会形成激子，当该激子跃迁至基态时，会发出光和热。Generally speaking, organic luminescence refers to the phenomenon of emitting light when electric energy is applied to an organic substance; that is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes will be injected from the anode. To the organic layer, electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed. When the excitons transition to the ground state, they emit light and heat.
最近几年有机电致发光显示技术已趋于成熟，一些产品已进入市场，但在产业化过程中，仍有许多问题亟待解决。特别是用于制作元件的各种有机材料，其载流子注入和传输性能、材料电发光性能、使用寿命、色纯度、各种材料之间及与各电极之间的匹配等，尚有许多问题还未解决；尤其是发光元件的发光效率和使用寿命还达不到实用化要求，这大大限制了有机发光二极管(OrganicLight-Emitting Diode，简称OLED)技术的发展。而利用三线态发光的金属配合物磷光材料具有高的发光效率，其绿光和红光材料已经达到使用要求，但是金属配合物磷光材料要求具有高三线态能级的磷光材料或空穴材料与之匹配。因此，开发具有高三线态能级的磷光材料或空穴材料是当前OLED发展的迫切需求。In recent years, organic electroluminescent display technology has matured, and some products have entered the market. However, there are still many problems that need to be solved during the industrialization process. In particular, there are many problems in the various organic materials used to make components, including their carrier injection and transmission properties, material electroluminescence properties, service life, color purity, matching between various materials and between various electrodes, etc. The problem has not yet been solved; in particular, the luminous efficiency and service life of light-emitting components have not yet met practical requirements, which has greatly restricted the development of organic light-emitting diode (OLED) technology. Metal complex phosphorescent materials that utilize triplet luminescence have high luminous efficiency, and their green and red light materials have met the requirements for use. However, metal complex phosphorescent materials require phosphorescent materials or hole materials with high triplet energy levels and match. Therefore, the development of phosphorescent materials or hole materials with high triplet energy levels is an urgent need for the current development of OLEDs.
在目前的技术发展下，无论是对于荧光材料还是对于磷光材料，特别是在用于有机电致发光元件中的工作电压、效率和寿命方面和在升华期间的热稳定性方面，都还需要改进。Under the current technological development, both fluorescent materials and phosphorescent materials still need to be improved, especially in terms of operating voltage, efficiency and lifetime used in organic electroluminescent components and thermal stability during sublimation. .
鉴于此，特提出本发明。In view of this, the present invention is proposed.
发明内容Contents of the invention
为了克服如上所述的以往技术问题而进一步提高有机电致发光元件的特性，继续要求对于在有机电致发光元件中可用作磷光材料或空穴材料的更加稳定且有效的物质的开发。In order to overcome the conventional technical problems described above and further improve the characteristics of organic electroluminescent elements, there is a continuing demand for the development of more stable and effective substances that can be used as phosphorescent materials or hole materials in organic electroluminescent elements.
本发明的目的在于提供一种杂环化合物，该化合物可提高材料热稳定性和输送载流子的能力，利用该化合物制备的有机电致发光元件，可显著降低驱动电压、提高发光效率和寿命；本发明的另一目的在于提供该化合物的应用。The object of the present invention is to provide a heterocyclic compound that can improve the thermal stability of the material and the ability to transport carriers. The organic electroluminescent element prepared by using the compound can significantly reduce the driving voltage and improve the luminous efficiency and lifespan. ; Another object of the present invention is to provide the application of the compound.
具体地，本发明提供以下技术方案：Specifically, the present invention provides the following technical solutions:
本发明提供一种杂环化合物，其结构式如式(I)所示：
The present invention provides a heterocyclic compound, the structural formula of which is shown in formula (I):
其中，in,
L1和L2彼此相同或不同，各自独立地选自单键、取代或未取代的C6-C60亚芳基、或者取代或未取代的C2-C60杂亚芳基；L 1 and L 2 are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
X1、X2、X3各自独立地为N或CR3，X1、X2、X3中至少一个为N；X 1 , X 2 , and X 3 are each independently N or CR 3 , and at least one of X 1 , X 2 , and X 3 is N;
Y选自O、S、CR4R5、SiR4R5或NAr4； Y is selected from O, S, CR 4 R 5 , SiR 4 R 5 or NAr 4 ;
R1、R2、R3、R4、R5出现时，相同或不同的选自由氢、氘、氟、羟基、腈基、硝基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C40烷基、C1-C40烷氧基、C2-C40烯基、C1-C40烷硫基、C1-C40烷氧基、C3-C40环烷基、C1-C40烷基亚砜基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫基、取代或未取代的C6-C60芳基亚砜基、取代或未取代的C3-C40甲硅烷基、取代或未取代的硼基、取代或未取代的胺基、取代或未取代的芳基膦基、取代或未取代的氧化膦基、或者取代或未取代的C2-C60杂环芳基组成的群组；When R 1 , R 2 , R 3 , R 4 and R 5 appear, the same or different ones are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro, carboxyl or their carboxylate, sulfonic acid group or their sulfonate. Acid salt, phosphate group or its phosphate, C 1 -C 40 alkyl group, C 1 -C 40 alkoxy group, C 2 -C 40 alkenyl group, C 1 -C 40 alkylthio group, C 1 -C 40 alkyl group Oxygen group, C 3 -C 40 cycloalkyl group, C 1 -C 40 alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, Substituted or unsubstituted C 6 -C 60 arylthio group, substituted or unsubstituted C 6 -C 60 aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 silyl group, substituted or unsubstituted boron A group consisting of a substituted or unsubstituted amino group, a substituted or unsubstituted arylphosphine group, a substituted or unsubstituted phosphine oxide group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group;
Ar2、Ar3、Ar4各自独立地选自由取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、或者取代或未取代的C2-C60杂环芳基组成的群组；Ar 2 , Ar 3 , and Ar 4 are each independently selected from a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 fused ring aryl group, or a substituted or unsubstituted C 2 - A group consisting of C 60 heterocyclic aryl groups;
Ar1选自以下式a至式h所示基团组成的群组，
Ar 1 is selected from the group consisting of groups represented by the following formulas a to h,
式a至式h中，T1、T2为直接键合、或各自独立地选自O、S、NAr、C(R)2、或者没有T1；Ar为取代或未取代的芳基；R彼此相同或不同的选自由氢、氘、氟、羟基、腈基、硝基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C40烷基、C1-C40烷氧基、C2-C40烯基、C1-C40烷硫基、C1-C40烷氧基、C3-C40环烷基、C1-C40烷基亚砜基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫基、取代或未取代的C6-C60芳基亚砜基、取代或未取代的C3-C40甲硅烷基、取代或未取代的硼基、取代或未取代的胺基、取代或未取代的芳基膦基、取代或未取代的氧化膦基、或者取代或未取代的C2-C60杂环芳基组成的群组，两个或多个相邻的R可以任意的接合或稠合形成取代或未取代的环，在形成的环中含有或不含有N、O、S、P、B或C(R)2；In formulas a to h, T 1 and T 2 are directly bonded, or each is independently selected from O, S, NAr, C(R) 2 , or there is no T 1 ; Ar is a substituted or unsubstituted aryl group; R, which are the same or different from each other, are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 40 Alkyl, C 1 -C 40 alkoxy, C 2 -C 40 alkenyl, C 1 -C 40 alkylthio, C 1 -C 40 alkoxy, C 3 -C 40 cycloalkyl, C 1 - C 40 alkyl sulfoxide, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 aryloxy, substituted or unsubstituted C 6 -C 60 arylthio, substituted Or unsubstituted C 6 -C 60 aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 silyl group, substituted or unsubstituted boron group, substituted or unsubstituted amine group, substituted or unsubstituted A group consisting of an arylphosphine group, a substituted or unsubstituted phosphine oxide group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group. Two or more adjacent R can be arbitrarily joined or fused. Forming a substituted or unsubstituted ring with or without N, O, S, P, B or C(R) 2 in the formed ring;
取代基R为一个或多个至饱和取代；The substituent R is one or more to saturated substitution;
*-表示L1与式a至式h所示基团结合的部位。*- represents the position where L 1 is bonded to the groups represented by formulas a to h.
作为优选，所述R1、R2、R3、R4、R5在每次出现时，各自独立地选自由氢、氘、氟、腈基、苯基、二联苯基、三联苯基、萘基、菲基、三亚苯基、咔唑、二苯并呋喃或二苯并噻吩组成的群组。Preferably, each time R 1 , R 2 , R 3 , R 4 , and R 5 appear, they are each independently selected from hydrogen, deuterium, fluorine, nitrile, phenyl, diphenyl, and terphenyl. , naphthyl, phenanthrenyl, triphenylene, carbazole, dibenzofuran or dibenzothiophene group.
作为优选，所述Ar2、Ar3、Ar4各自独立地选自如下物质的基团：苯、萘、蒽、苯并蒽、菲、芘、苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、四联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5，6]喹啉、苯并[6，7]喹啉、苯并[7，8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1，2-噻唑、1，3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1，5-二氮杂蒽、2，7-二氮杂芘、2，3-二氮杂芘、1，6-二氮杂芘、1，8-二氮杂芘、4，5-二氮杂芘，4，5，9，10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1，2，3-三唑、1，2，4-三唑、苯并三唑、1，2，3-噁二唑、1，2，4-噁二唑、1，2，5-噁二唑、1，3，4-噁二唑、1，2，3-噻二唑、1，2，4-噻二唑、1，2，5-噻二唑、1，3，4-噻二唑、1，3，5-三嗪、1，2，4-三嗪、1，2，3-三嗪、四唑、1，2，4，5-四嗪、1，2，3，4-四嗪、1，2，3，5-四嗪、嘌呤、蝶啶、吲嗪、喹唑啉和苯并噻二唑或者衍生自这些体系的组合的基团。Preferably, the Ar 2 , Ar 3 , and Ar 4 are each independently selected from the following groups: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, tetraphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydrogen Pyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimeric indene, isotrimeric indene, spirotrimeric indene, spiroisotrimeric Indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline , isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyridine Azole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanzimidazole, pyridimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthraceneoxazole Azole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazabenzophenanthrene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline Phenoline, 1,5-diazapyrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5 - Diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorine ring, naphthyridine, azacarbazole, benzocarboline, Carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine , 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole or groups derived from combinations of these systems .
作为优选，所述Ar1选自以下式2至式33所示基团的任意一个，

Preferably, the Ar 1 is selected from any one of the groups represented by the following formulas 2 to 33,

式2至式33中，Ar为苯基、萘基、蒽基、菲基、芘基、联苯基、三联苯基、三亚苯基、芴基、螺二芴基、二氢菲基、苯并呋喃基、二苯并呋喃基、苯并噻吩基、二苯并噻吩基、咔唑基、吡啶基或者衍生自这些体系的组合的基团；R彼此相同或不同的选自由氢、氘、氟、腈基、甲基、乙基、苯基、联苯基、芴基组成的群组，两个或多个相邻的R可以任意的接合或稠合形成取代或未取代的环，在形成的环中含有或不含有N、O、S、P、B或C(R)2；In formulas 2 to 33, Ar is phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl, terphenyl, triphenylene, fluorenyl, spirodifluorenyl, dihydrophenanthryl, benzene Furanyl, dibenzofuranyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl or groups derived from combinations of these systems; R, which are the same or different from each other, are selected from hydrogen, deuterium, A group consisting of fluorine, nitrile, methyl, ethyl, phenyl, biphenyl, and fluorenyl. Two or more adjacent R can be arbitrarily joined or fused to form a substituted or unsubstituted ring. The ring formed may or may not contain N, O, S, P, B or C(R) 2 ;
取代基R为一个或多个至饱和取代；The substituent R is one or more to saturated substitution;
*-表示L1与式2至式33所示基团结合的部位。*- represents the site where L 1 is bonded to the group represented by Formula 2 to Formula 33.
根据本发明的实施例，所述Ar1选自以下所示基团中的任意一个，

According to an embodiment of the present invention, the Ar 1 is selected from any one of the groups shown below,

其中，Ar为苯基、萘基、菲基、联苯基、三联苯基、三亚苯基、芴基、螺二芴基、二苯并呋喃基、二苯并噻吩基、咔唑基、吡啶基或者衍生自这些体系的组合的基团；R彼此相同或不同的选自由氢、氘、氟、腈基、甲基、乙基、苯基、联苯基、芴基组成的群组；Among them, Ar is phenyl, naphthyl, phenanthrenyl, biphenyl, terphenyl, triphenylene, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, pyridine A group or a group derived from a combination of these systems; R, which are the same or different from each other, are selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, phenyl, biphenyl, and fluorenyl;
取代基R为一个或多个至饱和取代；The substituent R is one or more to saturated substitution;
*-表示L1与所示基团结合的部位。*-Indicates the site where L 1 is combined with the indicated group.
作为优选，上述化合物中，所述L1、L2各自独立地选自由以下III-1～III-15所示基团组成的群组：
Preferably, in the above compound, the L 1 and L 2 are each independently selected from the group consisting of the following groups III-1 to III-15:
其中，in,
Z11、Z12各自独立地选自由氢、氘氢、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C40烷基、C2-C40烯基、C2-C40炔基、C1-C40烷氧基、C3-C40环烷烃基、C3-C40环烯烃基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基组成的群组；Z 11 and Z 12 are each independently selected from hydrogen, deuterated hydrogen, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate Acid salt, phosphate group or its phosphate, C 1 -C 40 alkyl group, C 2 -C 40 alkenyl group, C 2 -C 40 alkynyl group, C 1 -C 40 alkoxy group, C 3 -C 40 cycloalkane group, C 3 -C 40 cycloalkenyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 aryl sulfide An ether group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
Z13表示取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基中的一种或多种；Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 6 -C 60 aryl sulfide group. One or more C 2 -C 60 heterocyclic aryl groups;
y1表示1-4的整数；y2表示1-6的整数；y3表示1-3的整数；y4表示1-5的整数；y1 represents an integer from 1 to 4; y2 represents an integer from 1 to 6; y3 represents an integer from 1 to 3; y4 represents an integer from 1 to 5;
T3表示氧原子或硫原子； T 3 represents oxygen atom or sulfur atom;
表示取代基与主体结构的连接键。 Indicates the bond between the substituent and the main structure.
本发明中，“取代或未取代的”这一用语是指，被选自氢、氘、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C60烷基、C2-C60烯基、C2-C60炔基、C1-C60烷氧基、C3-C60环烷基、C3-C60环烯基、C6-C60芳基、C6-C60芳氧基、C6-C60芳硫醚基和C2-C60杂环芳基中的1个以上的取代基取代或未取代，或者被上述例示的取代基中的2个以上的取代基连接而成的取代基取代或未取代。In the present invention, the term "substituted or unsubstituted" means one selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or its carboxyl group. Acid salt, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 60 alkyl group, C 2 -C 60 alkenyl group, C 2 -C 60 alkynyl group, C 1 -C 60 alkoxy group, C 3 -C 60 cycloalkyl group, C 3 -C 60 cycloalkenyl group, C 6 -C 60 aryl group, C 6 -C 60 aryloxy group, C 6 -C 60 aryl sulfide group and C 2 - One or more substituents in the C 60 heterocyclic aryl group may be substituted or unsubstituted, or may be substituted or unsubstituted by a substituent in which two or more substituents among the substituents exemplified above are connected.
作为优选，所述化合物选自如下式CJHM383-CJHM470所示的化合物：




Preferably, the compound is selected from the compounds represented by the following formulas CJHM383-CJHM470:




本发明还提供一种有机电致发光材料，其原料包括以上所述的杂环化合物；包括本发明的化合物的有机电致发光材料具有载流子传输的能力。The present invention also provides an organic electroluminescent material, the raw material of which includes the above-mentioned heterocyclic compound; the organic electroluminescent material including the compound of the present invention has the ability of carrier transport.
本发明还提供以上所述的杂环化合物在制备有机电致发光元件中的应用。The present invention also provides the use of the above-mentioned heterocyclic compound in preparing organic electroluminescent elements.
本发明还提供一种有机电致发光元件，其包括：第一电极、第二电极、封盖层和置于所述第一电极、所述第二电极之间的一层以上的有机层；所述有机层或封盖层中的至少一层的材料包括以上所述的杂环化合物。The present invention also provides an organic electroluminescent element, which includes: a first electrode, a second electrode, a capping layer and one or more organic layers placed between the first electrode and the second electrode; The material of at least one layer of the organic layer or capping layer includes the above-mentioned heterocyclic compound.
所述有机电致发光元件包含阴极、阳极和至少一个发光层。除了这些层之外，它还可以包含其它的层，例如在每种情况下，包含一个或多个空穴注入层、空穴传输层、空穴阻挡层、电子传输层、电子注入层、激子阻挡层、电子阻挡层和/或电荷产生层。具有例如激子阻挡功能的中间层同样可引入两个发光层之间。然而，应当指出，这些层中的每个并非必须都存在。此处所述有机电致发光装置可包含一个发光层，或者它可包含多个发光层。即，将能够发光的多种发光化合物用于所述发光层中。特别优选具有三个发光层的体系，其中所述三个层可显示蓝色、绿色和红色发光。如果存在多于一个的发光层，则根据本发明，这些层中的至少一个层包含本发明的杂环化合物。The organic electroluminescent element includes a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may contain further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, excitation layers, etc. sub-blocking layer, electron blocking layer and/or charge generating layer. An intermediate layer having, for example, an exciton blocking function can also be introduced between the two luminescent layers. However, it should be noted that each of these layers does not necessarily have to be present. The organic electroluminescent device described herein may include one light emitting layer, or it may include multiple light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three luminescent layers, wherein the three layers can exhibit blue, green and red luminescence. If more than one luminescent layer is present, according to the invention at least one of these layers contains a heterocyclic compound of the invention.
进一步地，根据本发明的有机电致发光元件不包含单独的空穴注入层和/或空穴传输层和/或空穴阻挡层和/或电子传输层，即发光层与电子阻挡层或空穴传输层或阳极直接相邻，和/或发光层与电子传输层或电子注入层或阴极直接相邻。Further, the organic electroluminescent element according to the present invention does not include a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, that is, the light-emitting layer and the electron blocking layer or hole transport layer The hole transport layer or the anode is directly adjacent, and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or the cathode.
在根据本发明的有机电致发光元件的其它层中，特别是在空穴注入和空穴传输层中以及在电子注入和电子传输层中，所有材料可以按照根据现有技术通常所使用的方式来使用。本领域普通技术人员因此将能够在不付出创造性劳动的情况下与根据本发明的发光层组合使用关于有机电致发光元件所知的所有材料。In the other layers of the organic electroluminescent element according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner commonly used according to the prior art. to use. A person skilled in the art will therefore be able to use, without inventive effort, all materials known for organic electroluminescent components in combination with the luminescent layer according to the invention.
此外优选如下的有机电致发光元件，借助于升华方法施加一个或多个层，其中在真空升华装置中在低于10-5Pa、优选低于10-6Pa的初压下通过气相沉积来施加所述材料。然而，所述初压还可能甚至更低，例如低于10-7Pa。Furthermore, organic electroluminescent components are preferred in which one or more layers are applied by means of a sublimation method, wherein the layer is deposited by vapor deposition in a vacuum sublimation device at an initial pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. Apply the material. However, the initial pressure may also be even lower, for example below 10 -7 Pa.
同样优选如下的有机电致发光元件，借助于有机气相沉积方法或借助于载气升华来施加一个或多个层，其中，在10-5Pa至1Pa之间的压力下施加所述材料。该方法的特别的例子是有机蒸气喷印方法，其中所述材料通过喷嘴直接施加，并且因此是结构化的。Also preferred are organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, wherein the material is applied at a pressure of between 10 −5 Pa and 1 Pa. A particular example of this method is the organic vapor jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
此外优选如下的有机电致发光元件，从溶液中，例如通过旋涂，或借助于任何所希望的印刷方法例如丝网印刷、柔性版印刷、平版印刷、光引发热成像、热转印、喷墨印刷或喷嘴印刷，来产生一个或多个层。可溶性化合物，例如通过适当的取代式(I)所示的化合物获得可溶性化合物。这些方法也特别适于低聚物、 树枝状大分子和聚合物。此外可行的是混合方法，其中例如从溶液中施加一个或多个层并且通过气相沉积施加一个或多个另外的层。Furthermore, preference is given to organic electroluminescent elements produced from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photothermography, thermal transfer printing, spray printing, etc. Ink printing or nozzle printing to produce one or more layers. Soluble compounds can be obtained, for example, by appropriately substituting compounds represented by formula (I). These methods are also particularly suitable for oligomers, Dendrimers and polymers. Furthermore, hybrid methods are possible, in which one or more layers are applied, for example, from solution and one or more further layers are applied by vapor deposition.
这些方法是本领域普通技术人员通常已知的，并且他们可以在不付出创造性劳动的情况下将其应用于包含根据本发明的化合物的有机电致发光元件。These methods are generally known to those skilled in the art, and they can apply them to organic electroluminescent elements containing the compounds according to the invention without exerting creative effort.
因此，本发明还涉及制造根据本发明的有机电致发光元件的方法，借助于升华方法来施加至少一个层，和/或特征在于借助于有机气相沉积方法或借助于载气升华来施加至少一个层，和/或特征在于从溶液中通过旋涂或借助于印刷方法来施加至少一个层。The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, applying at least one layer by means of a sublimation method, and/or characterized in that at least one layer is applied by means of an organic vapor deposition method or by means of carrier gas sublimation. layers, and/or is characterized in that at least one layer is applied by spin coating from solution or by means of printing methods.
此外，本发明涉及包含至少一种上文指出的本发明的杂环化合物。如上文关于有机电致发光元件指出的相同优选情况适用于所述本发明的化合物。特别是，所述化合物此外还可优选包含其它化合物。从液相处理根据本发明的化合物，例如通过旋涂或通过印刷方法进行处理，需要根据本发明的化合物的制剂。这些制剂可以例如是溶液、分散体或乳液。出于这个目的，可优选使用两种或更多种溶剂的混合物。合适并且优选的溶剂例如是甲苯、苯甲醚、邻二甲苯、间二甲苯或对二甲苯、苯甲酸甲酯、均三甲苯、萘满、邻二甲氧基苯、四氢呋喃、甲基四氢呋喃、四氢吡喃、氯苯、二噁烷、苯氧基甲苯，特别是3-苯氧基甲苯、(-)-葑酮、1，2，3，5-四甲基苯、1，2，4，5-四甲基苯、1-甲基萘、2-甲基苯并噻唑、2-苯氧基乙醇、2-吡咯烷酮、3-甲基苯甲醚、4-甲基苯甲醚、3，4-二甲基苯甲醚、3，5-二甲基苯甲醚、苯乙酮、α-萜品醇、苯并噻唑、苯甲酸丁酯、异丙苯、环己醇、环己酮、环己基苯、十氢化萘、十二烷基苯、苯甲酸乙酯、茚满、苯甲酸甲酯、1-甲基吡咯烷酮、对甲基异丙基苯、苯乙醚、1，4-二异丙基苯、二苄醚、二乙二醇丁基甲基醚、三乙二醇丁基甲基醚、二乙二醇二丁基醚、三乙二醇二甲基醚、二乙二醇单丁基醚、三丙二醇二甲基醚、四乙二醇二甲基醚、2-异丙基萘、戊苯、己苯、庚苯、辛苯、1，1-双(3，4-二甲基苯基)乙烷，或这些溶剂的混合物。Furthermore, the invention relates to a heterocyclic compound comprising at least one of the above-indicated heterocyclic compounds of the invention. The same preferences as noted above with respect to organic electroluminescent elements apply to the compounds of the invention. In particular, the compounds may preferably also comprise other compounds. Processing the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires formulation of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, Tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenone, 1,2,3,5-tetramethylbenzene, 1,2, 4,5-Tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanol, Hexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indan, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenylethyl ether, 1,4 -Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol mono Butyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-di methylphenyl)ethane, or mixtures of these solvents.
作为优选，所述有机层包括空穴注入层、空穴传输层、空穴阻挡层、发光层、电子传输层、电子注入层或电子阻挡层。Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer or an electron blocking layer.
本发明同时提供一种消费型产品，其包括以上所述的有机电致发光元件。The present invention also provides a consumer product, which includes the above-mentioned organic electroluminescent element.
另外，如无特殊说明，本发明中所用原料均可通过市售商购获得，本发明所记载的任何范围包括端值以及端值之间的任何数值以及端值或者端值之间的任意数值所构成的任意子范围。In addition, unless otherwise specified, the raw materials used in the present invention can be purchased from commercial stores. Any range recorded in the present invention includes the end value and any value between the end value and the end value or any value between the end value. Any subrange formed by.
本发明所取得的有益效果：Beneficial effects achieved by the present invention:
本发明提供的式(I)所示杂环化合物，具有高的三线态能级，增大了菲或氮杂菲分子的刚性，提高了材料热稳定性和输送载流子的能力，将该化合物应用在有机电致发光元件中，可显著降低驱动电压、提高发光效率和寿命。The heterocyclic compound represented by formula (I) provided by the invention has a high triplet energy level, increases the rigidity of the phenanthrene or azaphenanthrene molecule, improves the thermal stability of the material and the ability to transport carriers, and the The compound is used in organic electroluminescent components to significantly reduce driving voltage, improve luminous efficiency and lifespan.
附图说明Description of the drawings
图1展示有机发光装置100示意图。图示不一定按比例绘制。装置100可包含衬底101、阳极102、空穴注入层103、空穴传输层104、电子阻挡层105、发光层106、空穴阻挡层107、电子传输层108、电子注入层109、阴极110以及封盖层(CPL)111。装置100可通过依序沉积所描述的层来制造。FIG. 1 shows a schematic diagram of an organic light-emitting device 100. Illustrations are not necessarily to scale. Device 100 may include substrate 101, anode 102, hole injection layer 103, hole transport layer 104, electron blocking layer 105, light emitting layer 106, hole blocking layer 107, electron transport layer 108, electron injection layer 109, cathode 110 and capping layer (CPL) 111. Device 100 may be fabricated by sequentially depositing the described layers.
图2展示两个发光层的有机发光装置200示意图。所述装置包含衬底201、阳极202、空穴注入203、空穴传输层204、第一发光层205、电子传输层206、电荷产生层207、空穴注入层208、空穴传输层209、第二发光层210、电子传输层211、电子注入层212以及阴极213。可通过依序沉积所描述的层来制备装置200。因为最常见的OLED装置具有一个发光层，而装置200具有第一发光层和第二发光层，第一发光层和第二发光层的发光峰形可以是重叠的或交叉重叠的或非重叠的。在装置200的对应层中，可使用与关于装置100所描述的材料类似的材料。图2提供可如何从装置100的结构增加一些层的一个实例。FIG. 2 shows a schematic diagram of an organic light-emitting device 200 with two light-emitting layers. The device includes a substrate 201, an anode 202, hole injection 203, hole transport layer 204, first light-emitting layer 205, electron transport layer 206, charge generation layer 207, hole injection layer 208, hole transport layer 209, The second light-emitting layer 210, the electron transport layer 211, the electron injection layer 212 and the cathode 213. Device 200 may be prepared by sequentially depositing the described layers. Because the most common OLED device has one luminescent layer, and the device 200 has a first luminescent layer and a second luminescent layer, the luminescence peak shapes of the first luminescent layer and the second luminescent layer may be overlapping or cross-overlapping or non-overlapping. . In corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Figure 2 provides an example of how some layers may be added from the structure of device 100.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。The following examples are used to illustrate the invention but are not intended to limit the scope of the invention.
在本发明的描述中，除非另有说明，“多个”的含义是两个或两个以上；术语“上”、“下”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。 In the description of the present invention, unless otherwise stated, the meaning of "plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. is based on the orientation or position shown in the drawings. The positional relationship is only for the convenience of describing the present invention and simplifying the description. It does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention.
以下实施例中所使用的实验方法如无特殊说明，均为常规方法。以下实施例中所用的实验原料和相关设备等，如无特殊说明，均可从商业途径得到，所述百分比如无特殊说明，均为质量百分比。The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental raw materials and related equipment used in the following examples can all be obtained from commercial sources unless otherwise specified. The percentages mentioned are all mass percentages unless otherwise specified.
下述实施例对OLED材料及元件进行性能测试的测试仪器及方法如下：The test instruments and methods for performance testing of OLED materials and components in the following examples are as follows:
OLED元件性能检测条件：OLED component performance testing conditions:
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；Luminance and chromaticity coordinates: tested using spectral scanner PhotoResearch PR-715;
电流密度和起亮电压：使用数字源表Keithley 2420测试；Current density and lighting voltage: tested using digital source meter Keithley 2420;
功率效率：使用NEWPORT 1931-C测试。Power efficiency: tested using NEWPORT 1931-C.
实施例Example
化合物式(I)的合成路线如下：
The synthetic route of compound formula (I) is as follows:
其中，X表示I、Br、Cl或OTf；其它所用符号如上文中所定义。Among them, X represents I, Br, Cl or OTf; other symbols used are as defined above.
实施例1Example 1
化合物CJHM387的制备方法，包括如下步骤：The preparation method of compound CJHM387 includes the following steps:
第一步：中间体Int-1的制备
Step 1: Preparation of intermediate Int-1
20.0mmol的SM-1(反应物1)溶解于60mL的冰醋酸中，在氮气保护下，加入15.4mmol的碘酸钾、26.2mmol的碘化钾，升温至回流搅拌反应2小时，降到室温，过滤，滤饼用水洗、饱和亚硫酸氢钠水溶液洗，硅胶柱分离纯化，得到白色固体Int-1，收率91％。20.0 mmol of SM-1 (reactant 1) was dissolved in 60 mL of glacial acetic acid. Under nitrogen protection, 15.4 mmol of potassium iodate and 26.2 mmol of potassium iodide were added. The temperature was raised to reflux and the reaction was stirred for 2 hours, then cooled to room temperature and filtered. , the filter cake was washed with water and saturated sodium bisulfite aqueous solution, and separated and purified on a silica gel column to obtain white solid Int-1 with a yield of 91%.
第二步：中间体Int-2的制备
Step 2: Preparation of intermediate Int-2
10.0mmol的Int-1溶解于60mL的甲苯中，在氮气保护下，加入11.0mmol的9-苯基咔唑-3-硼酸(反应物2)、24.0mmol的无水碳酸钠、0.01mmol的Pd(PPh3)4催化剂，再加入30mL的乙醇和30mL的水，升温至回流搅拌反应5小时，降到室温，加入50mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到黄色固体Int-2，收率82％。10.0 mmol of Int-1 was dissolved in 60 mL of toluene. Under nitrogen protection, 11.0 mmol of 9-phenylcarbazole-3-boronic acid (reactant 2), 24.0 mmol of anhydrous sodium carbonate, and 0.01 mmol of Pd were added. (PPh 3 ) 4 catalyst, then add 30 mL of ethanol and 30 mL of water, heat to reflux and stir for 5 hours, then cool to room temperature, add 50 mL of water to dilute, extract with ethyl acetate, collect the organic phase, dry, filter, and filtrate Concentrate to dryness under reduced pressure and use silica gel column for separation and purification to obtain yellow solid Int-2 with a yield of 82%.
第三步：中间体Int-3的制备
Step 3: Preparation of intermediate Int-3
在氮气保护下，20.0mmol的Int-1溶于60mL的THF，降温至-78℃，滴加入9.6mL的2.5M正丁基 锂正己烷溶液，搅拌反应30分钟，滴加入30.0mmol的硼酸三甲酯，升至室温搅拌反应1小时，加入100mL的IN稀盐酸水溶液，用EA萃取，有机相干燥，过滤，减压浓缩干，用正己烷分散过滤，得到黄色固体Int-3，收率：83％。Under nitrogen protection, 20.0 mmol of Int-1 was dissolved in 60 mL of THF, cooled to -78°C, and 9.6 mL of 2.5 M n-butyl was added dropwise. Lithium n-hexane solution, stir and react for 30 minutes, add 30.0 mmol of trimethyl borate dropwise, raise to room temperature and stir for 1 hour, add 100 mL of IN dilute hydrochloric acid aqueous solution, extract with EA, dry the organic phase, filter, and concentrate to dryness under reduced pressure , use n-hexane dispersion filtration to obtain yellow solid Int-3, yield: 83%.
第四步：化合物CJHM387的制备
Step 4: Preparation of compound CJHM387
在氮气保护下，12.0mmol的中间体Int-3、10.0mmol的2-氯-4，6-二苯基-1，3，5-三嗪(反应物3)、36.0mmol的六水合磷酸钾和40mL的甲苯混合，再加入0.01mmol的Pd132催化剂、20mL的乙醇和20mL的水，升温至回流搅拌反应12小时，降到室温，加入50mL的水稀释，用二氯甲烷萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到黄色固体CJHM387，收率85％，MS(MALDI-TOF)：m/z＝665.2345[M+H]+；1HNMR(δ、CDCl3)：8.53(1H，s)；8.36～8.32(4H，m)；8.15～8.13(2H，d)；8.07～8.05(2H，d)；7.98～7.90(3H，m)；7.76～7.75(1H，d)；7.69～7.66(2H，d)；7.64～7.55(3H，m)；7.53～7.48(8H，m)；7.36～7.32(1H，m)；7.16～7.14(1H，m)。Under nitrogen protection, 12.0 mmol of intermediate Int-3, 10.0 mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine (reactant 3), 36.0 mmol of potassium phosphate hexahydrate Mix with 40 mL of toluene, then add 0.01 mmol of Pd132 catalyst, 20 mL of ethanol and 20 mL of water, raise the temperature to reflux and stir for 12 hours, then cool to room temperature, add 50 mL of water to dilute, extract with dichloromethane, and collect the organic phase. Dry, filter, and concentrate the filtrate to dryness under reduced pressure. Use a silica gel column for separation and purification to obtain yellow solid CJHM387 with a yield of 85%. MS (MALDI-TOF): m/z=665.2345[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.53 (1H, s); 8.36～8.32 (4H, m); 8.15～8.13 (2H, d); 8.07～8.05 (2H, d); 7.98～7.90 (3H, m); 7.76～7.75 (1H, d); 7.69～7.66 (2H, d); 7.64～7.55 (3H, m); 7.53～7.48 (8H, m); 7.36～7.32 (1H, m); 7.16～7.14 (1H, m) .
参照上述的合成方法，制备以下表1所示化合物：Referring to the above synthetic method, prepare the compounds shown in Table 1 below:
表1





Table 1





实施例2Example 2
化合物CJHM399的制备方法，包括以下步骤：The preparation method of compound CJHM399 includes the following steps:
第一步：化合物Int-4的制备
Step One: Preparation of Compound Int-4
20.0mmol的Int-1溶解于80mL干燥的二甲苯中，在氮气保护下，加入20.0mmol的咔唑、60.0mmol的无水碳酸钾、0.2mmol的碘化亚铜和0.6mmol的N，N’-二甲基乙二胺，升温至回流搅拌反应15小时，降到室温，过滤，滤饼用二氯甲烷洗，滤液减压浓缩干，用硅胶柱分离纯化，得到白色固体Int-4，收率75％。20.0mmol of Int-1 was dissolved in 80mL of dry xylene. Under nitrogen protection, 20.0mmol of carbazole, 60.0mmol of anhydrous potassium carbonate, 0.2mmol of copper iodide and 0.6mmol of N, N' were added. -Dimethylethylenediamine, raise the temperature to reflux and stir the reaction for 15 hours, lower to room temperature, filter, wash the filter cake with dichloromethane, concentrate the filtrate to dryness under reduced pressure, separate and purify with a silica gel column, obtain white solid Int-4, collect The rate is 75%.
第二步：化合物Int-5的制备
Step 2: Preparation of compound Int-5
参照实施例1第三步的合成方法，仅将实施例1第三步的Int-2替换为Int-4，制备得到白色固体Int-5，收率78％。Referring to the synthesis method in the third step of Example 1, only Int-2 in the third step of Example 1 was replaced with Int-4, and a white solid Int-5 was prepared with a yield of 78%.
第三步：化合物CJHM399的制备
Step 3: Preparation of compound CJHM399
参照实施例1第四步的合成方法，仅将实施例1第四步的Int-3替换为Int-5，将2-氯-4，6-二苯基-1，3，5-三嗪替换为2-联苯基-4-氯-6-苯基-1，3，5-三嗪，用硅胶柱分离纯化，得到黄色固体CJHM399，收率78％，MS(MALDI-TOF)：m/z＝665.2355[M+H]+；1HNMR(δ、CDCl3)：8.54(1H，s)；8.38～8.35(3H，m)；8.18～8.14(2H，m)；8.05～8.02(2H，m)；7.95～7.91(3H，m)；7.76～7.68(5H，m)；7.58～7.54(2H，m)；7.52～7.45(6H，m)；7.43～7.35(2H，m)；7.18～7.14(2H，m)。参照上述的合成方法，制备以下表2所示化合物：Referring to the synthesis method in the fourth step of Example 1, only Int-3 in the fourth step of Example 1 is replaced with Int-5, and 2-chloro-4,6-diphenyl-1,3,5-triazine is Replaced with 2-biphenyl-4-chloro-6-phenyl-1,3,5-triazine, separated and purified using silica gel column to obtain yellow solid CJHM399, yield 78%, MS (MALDI-TOF): m /z=665.2355[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.54 (1H, s); 8.38～8.35 (3H, m); 8.18～8.14 (2H, m); 8.05～8.02 (2H , m); 7.95～7.91 (3H, m); 7.76～7.68 (5H, m); 7.58～7.54 (2H, m); 7.52～7.45 (6H, m); 7.43～7.35 (2H, m); 7.18 ~7.14 (2H, m). Referring to the above synthetic method, prepare the compounds shown in Table 2 below:
表2

Table 2

实施例3Example 3
一种OLED元件，如图1所示，本实施例的OLED元件为顶发射光元件，包括基板101、设于基板101上的阳极层102、设于阳极层102上的空穴注入层103、设于空穴注入层103上的空穴传输层104、设于空穴传输层104上的电子阻挡层105、设于电子阻挡层105上的有机发光层106、设于有机发光层106上的电子传输层107、设于电子传输层107上的电子注入层108、设于电子注入层108上的阴极层109以及设于阴极109上的封盖层110，所述的OLED元件的制备方法包括如下步骤：An OLED element, as shown in Figure 1, the OLED element of this embodiment is a top-emitting light-emitting element, including a substrate 101, an anode layer 102 provided on the substrate 101, a hole injection layer 103 provided on the anode layer 102, The hole transport layer 104 provided on the hole injection layer 103, the electron blocking layer 105 provided on the hole transport layer 104, the organic light emitting layer 106 provided on the electron blocking layer 105, the organic light emitting layer 106 provided on the organic light emitting layer 106. The electron transport layer 107, the electron injection layer 108 provided on the electron transport layer 107, the cathode layer 109 provided on the electron injection layer 108, and the capping layer 110 provided on the cathode 109. The preparation method of the OLED element includes Follow these steps:
1)将涂布了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。1) Ultrasonicate the glass substrate coated with the ITO conductive layer in a cleaning agent for 30 minutes, rinse in deionized water, ultrasonicate in an acetone/ethanol mixed solvent for 30 minutes, and bake in a clean environment until completely dry. Use a UV cleaner for 10 minutes and bombard the surface with a low-energy cation beam.
2)把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10-5～9×10-3Pa，在上述阳极层膜上蒸镀金属银作为阳极层，蒸镀膜厚为继续分别蒸镀化合物2-TNATA和F4TCNQ作为空穴注入层，其中，F4TCNQ为2-TNATA质量的3％，蒸镀膜厚为 2) Place the above-processed ITO glass substrate in a vacuum chamber, evacuate to 1×10 -5 ~ 9×10 -3 Pa, evaporate metallic silver on the above-mentioned anode layer as an anode layer, and evaporate the thickness of the film for Continue to evaporate the compounds 2-TNATA and F4TCNQ as hole injection layers respectively. Among them, F4TCNQ is 3% of the mass of 2-TNATA, and the evaporated film thickness is
3)在上述空穴注入层上继续蒸镀化合物HTM101为空穴传输层，蒸镀膜厚为 3) Continue to evaporate the compound HTM101 on the above hole injection layer as a hole transport layer, and the evaporation film thickness is
4)在上述空穴注入层上继续蒸镀化合物EBL为电子阻挡层，蒸镀膜厚为 4) Continue to evaporate compound EBL as an electron blocking layer on the above hole injection layer, and the evaporated film thickness is
5)在电子阻挡层上继续蒸镀本发明的化合物式(I)为主体材料和GD03为掺杂材料，GD03为式(I) 质量的3％，作为元件的有机发光层，蒸镀所得有机发光层的膜厚为 5) Continue to evaporate the compound of the present invention on the electron blocking layer. Formula (I) is the host material and GD03 is the doping material. GD03 is the formula (I). 3% by mass, as the organic light-emitting layer of the element, the film thickness of the organic light-emitting layer obtained by evaporation is
6)在有机发光层上继续蒸镀一层LiQ和ET01作为元件的电子传输层，其中，ET01为LiQ质量的50％，蒸镀膜厚为 6) Continue to evaporate a layer of LiQ and ET01 on the organic light-emitting layer as the electron transport layer of the element, where ET01 is 50% of the mass of LiQ, and the evaporated film thickness is
7)在电子传输层之上继续蒸镀一层LiF为电子注入层，蒸镀膜厚为 7) Continue to evaporate a layer of LiF on top of the electron transport layer as the electron injection layer. The evaporated film thickness is
8)在电子注入层之上蒸镀金属镁和银作为元件的透明阴极层，镁和银的质量比为1∶10，蒸镀膜厚为 8) Evaporate metal magnesium and silver on the electron injection layer as the transparent cathode layer of the element. The mass ratio of magnesium and silver is 1:10, and the thickness of the evaporated film is
9)在透明阴极层之上再蒸镀一层NPD作为元件的CPL层，蒸镀膜厚为得到本发明提供的OLED元件。9) On the transparent cathode layer, evaporate another layer of NPD as the CPL layer of the component. The evaporated film thickness is The OLED element provided by the invention is obtained.
上述实施例3中使用的化合物结构如下：
The structure of the compound used in the above Example 3 is as follows:
实施例4Example 4
一种有机电致发光元件200，其结构如图2所示，其包含衬底201、阳极202、空穴注入203、空穴传输层204、第一发光层205、电子传输层206、电荷产生层207、空穴注入层208、空穴传输层209、第二发光层210、电子传输层211、电子注入层212以及阴极213。An organic electroluminescent element 200 has a structure as shown in Figure 2, which includes a substrate 201, anode 202, hole injection 203, hole transport layer 204, first light emitting layer 205, electron transport layer 206, charge generation layer 207, hole injection layer 208, hole transport layer 209, second light emitting layer 210, electron transport layer 211, electron injection layer 212 and cathode 213.
对比例1Comparative example 1
按照与实施例3相同的步骤，将步骤5)中的化合物(式I)替换为HS01，得到对比元件1；
Follow the same steps as Example 3, replace the compound (Formula I) in step 5) with HS01 to obtain Comparative Element 1;
对比例2Comparative example 2
按照与实施例3相同的步骤，将步骤5)中的化合物(式I)替换为HS02，得到对比元件2；
Follow the same steps as Example 3, replace the compound (Formula I) in step 5) with HS02 to obtain Comparative Element 2;
对上述过程制备的有机电致发光元件进行如下性能测试：The organic electroluminescent elements prepared by the above process were subjected to the following performance tests:
在同样亮度下，使用数字源表及亮度计测定实施例3及对比例1、2中制备得到的有机电致发光元件的驱动电压和电流效率以及元件的寿命。具体而言，以每秒0.1V的速率提升电压，测定当有机电致发光元件的亮度达到1000cd/m2时的电压即驱动电压，同时测出此时的电流密度；亮度与电流密度的比值即为电流效率；LT90％寿命测试如下：使用亮度计在1000cd/m2亮度下，保持恒定的电流，测量有机电致发光元件的亮度衰减为900cd/m2的时间，单位为小时。表3中列出的数据是相较于对比元件1的相对数据。Under the same brightness, a digital source meter and a luminance meter were used to measure the driving voltage and current efficiency of the organic electroluminescent elements prepared in Example 3 and Comparative Examples 1 and 2, as well as the lifetime of the elements. Specifically, increase the voltage at a rate of 0.1V per second, measure the voltage when the brightness of the organic electroluminescent element reaches 1000cd/ m2 , which is the driving voltage, and measure the current density at this time; the ratio of brightness to current density That is the current efficiency; the LT90% life test is as follows: use a luminance meter to maintain a constant current at a brightness of 1000cd/ m2 , and measure the time for the brightness of the organic electroluminescent element to decay to 900cd/ m2 , in hours. The data listed in Table 3 are relative data compared to Comparative Element 1.
表3


table 3


由表3可知，本发明的化合物制备的元件在相同的亮度下，驱动电压相较HS01低，电流效率提高明显，最高达到对比元件的1.2倍之多，而且元件的LT90％寿命有较大的改善。It can be seen from Table 3 that at the same brightness, the driving voltage of the components prepared by the compound of the present invention is lower than that of HS01, and the current efficiency is significantly improved, up to 1.2 times that of the comparative components, and the LT90% life of the components is greatly improved. improve.
对比例1中的化合物HS01与本发明的化合物相比，区别在于单一菲环平面共轭能力弱，对空穴和电子的传输不平衡，其接受空穴的能力强于接受电子的能力，这种传输的不平衡影响了激子在发光层中的形成，导致电压高、效率偏低，且寿命下降。而本发明的化合物在菲环的基础上引入氧、硫等杂原子，提高了母核的共轭能力，所以其在分子成膜及电荷的传输上性能均较优异，元件内电荷的传输更加平衡，元件性能提高。Compared with the compound of the present invention, the difference between compound HS01 in Comparative Example 1 is that the plane conjugation ability of a single phenanthrene ring is weak, and the transmission of holes and electrons is unbalanced. Its ability to accept holes is stronger than its ability to accept electrons. This is The imbalance of species transmission affects the formation of excitons in the light-emitting layer, resulting in high voltage, low efficiency, and reduced lifetime. The compound of the present invention introduces heteroatoms such as oxygen and sulfur on the basis of the phenanthrene ring, which improves the conjugation ability of the mother core. Therefore, it has excellent performance in molecular film formation and charge transmission, and the charge transmission within the element is more efficient. Balanced, component performance improves.
对比例2中的化合物HS02与本发明的化合物相比，区别在HS02为单极性的p型结构，其接受空穴的能力强于接受电子的能力，这种传输的不平衡影响了激子在发光层中的形成，导致电压高、效率偏低，且寿命下降。而本发明的化合物在引入含氮的杂芳环后形成p-n型双极性结构，所以其在分子成膜及电荷的传输上性能均较优异，元件内电荷的传输更加平衡，元件性能提高。Comparing the compound HS02 in Comparative Example 2 with the compound of the present invention, the difference is that HS02 has a unipolar p-type structure, and its ability to accept holes is stronger than its ability to accept electrons. This imbalance in transmission affects excitons. The formation in the light-emitting layer results in high voltage, low efficiency, and reduced lifespan. The compound of the present invention forms a p-n bipolar structure after introducing a nitrogen-containing heteroaromatic ring, so its performance in molecular film formation and charge transmission is excellent, the charge transmission in the element is more balanced, and the element performance is improved.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.
工业实用性Industrial applicability
本发明提供的式(I)所示杂环化合物，具有高的三线态能级，增大了菲或氮杂菲分子的刚性，提高了材料热稳定性和输送载流子的能力，将该化合物应用在有机电致发光元件中，可显著降低驱动电压、提高发光效率和寿命。 The heterocyclic compound represented by formula (I) provided by the invention has a high triplet energy level, increases the rigidity of the phenanthrene or azaphenanthrene molecule, improves the thermal stability of the material and the ability to transport carriers, and the The compound is used in organic electroluminescent components to significantly reduce driving voltage, improve luminous efficiency and lifespan.

Claims (10)

  1. 一种杂环化合物，其特征在于，其结构式如式(I)所示：
    A heterocyclic compound, characterized in that its structural formula is shown in formula (I):
    其中，in,
    L1和L2彼此相同或不同，各自独立地选自单键、取代或未取代的C6-C60亚芳基、或者取代或未取代的C2-C60杂亚芳基；L 1 and L 2 are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
    X1、X2、X3各自独立地为N或CR3，X1、X2、X3中至少一个为N；X 1 , X 2 , and X 3 are each independently N or CR 3 , and at least one of X 1 , X 2 , and X 3 is N;
    Y选自O、S、CR4R5、SiR4R5或NAr4；Y is selected from O, S, CR 4 R 5 , SiR 4 R 5 or NAr 4 ;
    R1、R2、R3、R4、R5出现时，相同或不同的选自由氢、氘、氟、羟基、腈基、硝基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C40烷基、C1-C40烷氧基、C2-C40烯基、C1-C40烷硫基、C1-C40烷氧基、C3-C40环烷基、C1-C40烷基亚砜基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫基、取代或未取代的C6-C60芳基亚砜基、取代或未取代的C3-C40甲硅烷基、取代或未取代的硼基、取代或未取代的胺基、取代或未取代的芳基膦基、取代或未取代的氧化膦基、或者取代或未取代的C2-C60杂环芳基组成的群组；When R 1 , R 2 , R 3 , R 4 and R 5 appear, the same or different ones are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro, carboxyl or their carboxylate, sulfonic acid group or their sulfonate. Acid salt, phosphate group or its phosphate, C 1 -C 40 alkyl group, C 1 -C 40 alkoxy group, C 2 -C 40 alkenyl group, C 1 -C 40 alkylthio group, C 1 -C 40 alkyl group Oxygen group, C 3 -C 40 cycloalkyl group, C 1 -C 40 alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, Substituted or unsubstituted C 6 -C 60 arylthio group, substituted or unsubstituted C 6 -C 60 aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 silyl group, substituted or unsubstituted boron A group consisting of a substituted or unsubstituted amino group, a substituted or unsubstituted arylphosphine group, a substituted or unsubstituted phosphine oxide group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group;
    Ar2、Ar3、Ar4各自独立地选自由取代或未取代的C6-C60芳基、取代或未取代的C6-C60稠环芳基、或者取代或未取代的C2-C60杂环芳基组成的群组；Ar 2 , Ar 3 , and Ar 4 are each independently selected from a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 fused ring aryl group, or a substituted or unsubstituted C 2 - A group consisting of C 60 heterocyclic aryl groups;
    Ar1选自以下式a至式h所示基团组成的群组，
    Ar 1 is selected from the group consisting of groups represented by the following formulas a to h,
    式a至式h中，T1、T2为直接键合、或各自独立地选自O、S、NAr、C(R)2、或者没有T1；Ar为取代或未取代的芳基；R彼此相同或不同的选自由氢、氘、氟、羟基、腈基、硝基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C40烷基、C1-C40烷氧基、C2-C40烯基、C1-C40烷硫基、C1-C40烷氧基、C3-C40环烷基、C1-C40烷基亚砜基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫基、取代或未取代的C6-C60芳基亚砜基、取代或未取代的C3-C40甲硅烷基、取代或未取代的硼基、取代或未取代的胺基、取代或未取代的芳基膦基、取代或未取代的氧化膦基、或者取代或未取代的C2-C60杂环芳基组成的群组，两个或多个相邻的R可以任意的接合或稠合形成取代或未取代的环，在形成的环中含有或不含有N、O、S、P、B或C(R)2；In formulas a to h, T 1 and T 2 are directly bonded, or each is independently selected from O, S, NAr, C(R) 2 , or there is no T 1 ; Ar is a substituted or unsubstituted aryl group; R, which are the same or different from each other, are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile group, nitro group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate, phosphate group or its phosphate, C 1 -C 40 Alkyl, C 1 -C 40 alkoxy, C 2 -C 40 alkenyl, C 1 -C 40 alkylthio, C 1 -C 40 alkoxy, C 3 -C 40 cycloalkyl, C 1 - C 40 alkyl sulfoxide, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 aryloxy, substituted or unsubstituted C 6 -C 60 arylthio, substituted Or unsubstituted C 6 -C 60 aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 silyl group, substituted or unsubstituted boron group, substituted or unsubstituted amine group, substituted or unsubstituted A group consisting of an arylphosphine group, a substituted or unsubstituted phosphine oxide group, or a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group. Two or more adjacent R can be arbitrarily joined or fused. Forming a substituted or unsubstituted ring with or without N, O, S, P, B or C(R) 2 in the formed ring;
    取代基R为一个或多个至饱和取代；The substituent R is one or more to saturated substitution;
    *-表示L1与式a至式h所示基团结合的部位。*- represents the position where L 1 is bonded to the groups represented by formulas a to h.
  2. 根据权利要求1所述的杂环化合物，其特征在于，所述R1、R2、R3、R4、R5在每次出现时，各自独立地选自由氢、氘、氟、腈基、苯基、二联苯基、三联苯基、萘基、菲基、三亚苯基、咔唑、二苯并呋喃或二苯并噻吩组成的群组；The heterocyclic compound according to claim 1, characterized in that, each time R 1 , R 2 , R 3 , R 4 , and R 5 appear, they are each independently selected from hydrogen, deuterium, fluorine, and nitrile. , phenyl, diphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylene, carbazole, dibenzofuran or dibenzothiophene group;
    Ar2、Ar3、Ar4各自独立地选自如下物质的基团：苯、萘、蒽、苯并蒽、菲、芘、苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、四联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异 三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5，6]喹啉、苯并[6，7]喹啉、苯并[7，8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1，2-噻唑、1，3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1，5-二氮杂蒽、2，7-二氮杂芘、2，3-二氮杂芘、1，6-二氮杂芘、1，8-二氮杂芘、4，5-二氮杂芘，4，5，9，10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1，2，3-三唑、1，2，4-三唑、苯并三唑、1，2，3-噁二唑、1，2，4-噁二唑、1，2，5-噁二唑、1，3，4-噁二唑、1，2，3-噻二唑、1，2，4-噻二唑、1，2，5-噻二唑、1，3，4-噻二唑、1，3，5-三嗪、1，2，4-三嗪、1，2，3-三嗪、四唑、1，2，4，5-四嗪、1，2，3，4-四嗪、1，2，3，5-四嗪、嘌呤、蝶啶、吲嗪、喹唑啉和苯并噻二唑或者衍生自这些体系的组合的基团；Ar 2 , Ar 3 , and Ar 4 are each independently selected from the following groups: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, aiphenyl, terphenyl, tetraphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydrogen Pyrene, cis or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, trimer indene, isotrimeric indene, spiro trimer indene, spiroiso Tripolyindene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, Quinoline, isoquinoline, acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine , pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanzimidazole, pyridimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthracene Oxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazabenzophenanthrene, benzopyridazine, pyrimidine, benzopyrimidine, Quinoxaline, 1,5-diazapyrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4 , 5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorine ring, naphthyridine, azacarbazole, benzocarb Phenoline, carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole Azole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole Azole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5- Tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole or derived from combinations of these systems group;
    Ar1选自以下式2至式33所示基团的任意一个，
    Ar 1 is selected from any one of the groups represented by the following formulas 2 to 33,
    式2至式33中，Ar为苯基、萘基、蒽基、菲基、芘基、联苯基、三联苯基、三亚苯基、芴基、螺二 芴基、二氢菲基、苯并呋喃基、二苯并呋喃基、苯并噻吩基、二苯并噻吩基、咔唑基、吡啶基或者衍生自这些体系的组合的基团；R彼此相同或不同的选自由氢、氘、氟、腈基、甲基、乙基、苯基、联苯基、芴基组成的群组，两个或多个相邻的R可以任意的接合或稠合形成取代或未取代的环，在形成的环中含有或不含有N、O、S、P、B或C(R)2；In Formula 2 to Formula 33, Ar is phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, biphenyl, terphenyl, triphenylene, fluorenyl, spirobi Fluorenyl, dihydrophenanthyl, benzofuryl, dibenzofuranyl, benzothienyl, dibenzothienyl, carbazolyl, pyridyl or groups derived from combinations of these systems; R are identical to each other Or different groups selected from hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, phenyl, biphenyl, fluorenyl, two or more adjacent R can be arbitrarily joined or fused Forming a substituted or unsubstituted ring with or without N, O, S, P, B or C(R) 2 in the formed ring;
    取代基R为一个或多个至饱和取代；The substituent R is one or more to saturated substitution;
    *-表示L1与式2至式33所示基团结合的部位。*- represents the site where L 1 is bonded to the group represented by Formula 2 to Formula 33.
  3. 根据权利要求1所述的杂环化合物，其特征在于，所述Ar1选自以下所示基团中的任意一个，
    The heterocyclic compound according to claim 1, characterized in that said Ar 1 is selected from any one of the groups shown below,
    其中，Ar为苯基、萘基、菲基、联苯基、三联苯基、三亚苯基、芴基、螺二芴基、二苯并呋喃基、二苯并噻吩基、咔唑基、吡啶基或者衍生自这些体系的组合的基团；R彼此相同或不同的选自由氢、氘、氟、腈基、甲基、乙基、苯基、联苯基、芴基组成的群组；Among them, Ar is phenyl, naphthyl, phenanthrenyl, biphenyl, terphenyl, triphenylene, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, pyridine A group or a group derived from a combination of these systems; R, which are the same or different from each other, are selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, methyl, ethyl, phenyl, biphenyl, and fluorenyl;
    取代基R为一个或多个至饱和取代；The substituent R is one or more to saturated substitution;
    *-表示L1与所示基团结合的部位。*-Indicates the site where L 1 is combined with the indicated group.
  4. 根据权利要求1所述的杂环化合物，其特征在于，所述L1、L2各自独立地选自由以下III-1～III-15所示基团组成的群组：

    The heterocyclic compound according to claim 1, wherein L 1 and L 2 are each independently selected from the group consisting of the following groups III-1 to III-15:

    其中，in,
    Z11、Z12各自独立地选自由氢、氘氢、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C1-C40烷基、C2-C40烯基、C2-C40炔基、C1-C40烷氧基、C3-C40环烷烃基、C3-C40环烯烃基、取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基组成的群组；Z 11 and Z 12 are each independently selected from hydrogen, deuterated hydrogen, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidine group, hydrazine group, hydrazone group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate Acid salt, phosphate group or its phosphate, C 1 -C 40 alkyl group, C 2 -C 40 alkenyl group, C 2 -C 40 alkynyl group, C 1 -C 40 alkoxy group, C 3 -C 40 cycloalkane group, C 3 -C 40 cycloalkenyl group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 aryl sulfide An ether group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
    Z13表示取代或未取代的C6-C60芳基、取代或未取代的C6-C60芳氧基、取代或未取代的C6-C60芳硫醚基、或者取代或未取代的C2-C60杂环芳基中的一种或多种；Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 aryl sulfide group, or a substituted or unsubstituted C 6 -C 60 aryl sulfide group. One or more C 2 -C 60 heterocyclic aryl groups;
    y1表示1-4的整数；y2表示1-6的整数；y3表示1-3的整数；y4表示1-5的整数；y1 represents an integer from 1 to 4; y2 represents an integer from 1 to 6; y3 represents an integer from 1 to 3; y4 represents an integer from 1 to 5;
    T3表示氧原子或硫原子；T 3 represents oxygen atom or sulfur atom;
    表示取代基与主体结构的连接键。 Indicates the bond between the substituent and the main structure.
  5. 根据权利要求1-4中任一项所述的杂环化合物，其特征在于，所述杂环化合物选自如下式CJHM383-CJHM470所示的化合物：




    The heterocyclic compound according to any one of claims 1-4, characterized in that the heterocyclic compound is selected from the compounds represented by the following formulas CJHM383-CJHM470:




  6. 一种有机电致发光材料，其特征在于，其原料包括权利要求1-5中任一项所述的杂环化合物。An organic electroluminescent material, characterized in that its raw materials include the heterocyclic compound according to any one of claims 1-5.
  7. 权利要求1-5中任一项所述的杂环化合物在制备有机电致发光元件中的应用。Use of the heterocyclic compound according to any one of claims 1 to 5 in the preparation of organic electroluminescent elements.
  8. 一种有机电致发光元件，其特征在于，其包括：第一电极、第二电极、封盖层和置于所述第一电极、所述第二电极之间的一层以上的有机层；所述有机层或封盖层中的至少一层的材料包括权利要求1-5中任一项所述的杂环化合物。An organic electroluminescent element, characterized in that it includes: a first electrode, a second electrode, a capping layer and one or more organic layers placed between the first electrode and the second electrode; The material of at least one layer of the organic layer or capping layer includes the heterocyclic compound of any one of claims 1-5.
  9. 根据权利要求8所述的有机电致发光元件，其特征在于，所述有机层包括空穴注入层、空穴传输层、空穴阻挡层、发光层、电子传输层、电子注入层或电子阻挡层。The organic electroluminescent element according to claim 8, characterized in that the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer or an electron blocking layer. layer.
  10. 一种消费型产品，其特征在于，其包括权利要求8所述的有机电致发光元件。 A consumer product, characterized in that it includes the organic electroluminescent element according to claim 8.
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