WO2020108422A1 - Diarylamine-substituted 9,9'-spirobifluorene compound and application thereof in oled device - Google Patents

Diarylamine-substituted 9,9'-spirobifluorene compound and application thereof in oled device Download PDF

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WO2020108422A1
WO2020108422A1 PCT/CN2019/120526 CN2019120526W WO2020108422A1 WO 2020108422 A1 WO2020108422 A1 WO 2020108422A1 CN 2019120526 W CN2019120526 W CN 2019120526W WO 2020108422 A1 WO2020108422 A1 WO 2020108422A1
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substituted
unsubstituted
oled device
compound
organic compound
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钱晓春
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常州强力电子新材料股份有限公司
常州强力昱镭光电材料有限公司
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Priority to KR1020217019960A priority Critical patent/KR20210118818A/en
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Definitions

  • the invention belongs to the technical field of organic chemistry and optoelectronic devices, and in particular relates to a compound containing a diarylamine substituted spirobifluorene (9,9'-Spirobifluorene) structure and its application in an OLED device.
  • OLED organic electroluminescence
  • the OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers of structures.
  • Industrially applied OLED device structures generally include a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), and light emission.
  • the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in devices with different structures may also be completely different.
  • the rigid in-plane biphenyl unit of the fluorene compound has high thermal stability and chemical stability, and has high fluorescence quantum efficiency in the solid state. Therefore, it can improve the thermal stability and morphological stability of the material when used in OLED devices. Stability, carrier migration stability and good miscibility.
  • Spirobifluorene as a common type of fluorene derivative, can be used as a luminescent material in OLED devices. Taking advantage of its structural advantages, it can improve the performance of OLED devices and prolong its service life.
  • the first object of the present invention is to provide an organic compound containing a diarylamine substituted spirobifluorene structure.
  • the compound has a high glass transition temperature, suitable HOMO and LUMO energy levels, and a high Eg (energy gap), high thermal stability, can be sublimated without decomposition and no residue, in OLED devices The application effect is good, which can effectively improve the device's luminous performance and device life. It is suitable for phosphorescent and fluorescent OLED devices, especially when the compound is used as a hole injection layer material and/or a hole transport layer material.
  • an organic compound containing a spirobifluorene structure substituted with a diarylamine of the present invention has a structure represented by the following chemical formula (1):
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent a substituted or unsubstituted aryl or heteroaryl group, and Ar 1 and Ar 2 may be connected to each other through E 1 to form a ring, Ar 3 and Ar 4 may be Connect to each other through E 2 to form a ring;
  • E 1 and E 2 each independently represent a direct bond, CRR′, NR, O or S, wherein R and R′ each independently represent a C 1 -C 8 linear or branched alkyl group, C 1 -C 8 Alkoxy, C 7 -C 14 aralkyl;
  • S 1 and S 2 each independently represent a direct bond, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene;
  • n and n independently represent integers from 0 to 3;
  • R 1 and R 2 each independently represent hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, Substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted Arylalkenyl, or substituted or unsubstituted heterocyclyl;
  • Ar 1 (Ar 2 )N-(S 1 ) m -and -(S 2 ) n -NAr 3 (Ar 4 ) are different.
  • S 1 and S 2 in the structure shown in formula (1) are direct bonds, that is, the N atoms on both sides are directly connected to the spirobifluorene structure, and the structure is shown in the following chemical formula (2):
  • both R 1 and R 2 represent hydrogen, that is, the structure is represented by the following chemical formula (3):
  • Ar 1 , Ar 2 , Ar 3 , and Ar 4 each independently have 6 to 60 C atoms, and each independently represents Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted Naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzothienyl, Substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted carbazolyl.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently selected from the following structures:
  • the dotted line represents the connection site bonded to nitrogen;
  • R 3 independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, n-octyl , Phenyl, 4-tert-butylphenyl, cycloalkyl.
  • CN coupling reaction can be carried out between dihalogenated fluorenone and brominated biphenyl, followed by ring formation with diarylamines of different structures in turn Arylamino group to obtain the target compound.
  • CN coupling reaction can be carried out between dihalogenated fluorenone and brominated biphenyl, followed by ring formation with diarylamines of different structures in turn Arylamino group to obtain the target compound.
  • the synthesis of dihalogenated fluorenone can refer to the prior art such as CN107075089A, and the full text of which is hereby incorporated by reference.
  • the compound represented by the chemical formula (3) for the -NAr 3 (Ar 4 ) group at the 2 substitution position can also be synthesized through the following process:
  • the object of the present invention is also to provide applications of the above organic compounds in OLED devices, and OLED devices containing the above organic compounds.
  • the OLED device includes: a first electrode; a second electrode disposed facing the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein the organic One or more of the material layers contain the compound represented by chemical formula (1).
  • the organic material layer may be composed of a single-layer structure or a multilayer structure in which two or more organic material layers are stacked.
  • the OLED device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer.
  • the device structure is not limited to this, and may include a smaller number of organic layers.
  • the organic material layer includes a hole injection layer, and the hole injection layer includes a compound of chemical formula (1).
  • the organic material layer includes a hole injection layer
  • the hole injection layer includes a compound of formula (1), and includes a P-type doped material doped at a doping concentration of 1-20 wt%, P-type doped
  • the chemical structural formula of the hybrid material is as follows:
  • the organic material layer includes a hole injection layer, a hole transport layer, and the hole transport layer includes a compound of chemical formula (1).
  • the organic material layer includes a hole injection layer and a hole transport layer.
  • the hole transport layer contains the compound of formula (1)
  • the hole injection layer uses only the compound HAT-CN having the following structural formula:
  • the organic material layer further includes an electron blocking layer that uses the compound HT2 of the following chemical structure:
  • the organic material layer further includes a light-emitting layer, and the light-emitting layer uses the compound EB as the main light emitter and the compound BD as the guest light emitter, wherein the doping ratio of the guest light emitter is 1-10% by weight, both
  • the chemical structural formula is as follows:
  • the organic material layer further includes an electron transport layer that uses the compound ET of the following chemical structure and contains 5 wt% doped lithium quinoline (Lithium8-quinolinolate, abbreviated as LiQ):
  • the organic material layer further includes an electron injection layer, and the compound used for the electron injection layer is lithium fluoride (LiF).
  • the compound used for the electron injection layer is lithium fluoride (LiF).
  • the OLED device of the present invention may be a top emission type, a bottom emission type, or a bidirectional emission type.
  • the beneficial technical effect of the present invention is that when the organic compound of the present invention is used in an OLED device, since the compound has a large conjugated system and good rigidity coplanar, and has a high glass transition temperature and high thermal stability, The non-crystalline thin film of the compound can be prevented from being converted into the crystalline thin film, so that the life of the OLED device is improved.
  • the compounds of the present invention have different HOMO and LOMO energy levels and can be applied to different functional layers of OLED devices.
  • the compound of the present invention has a high triplet energy (characteristic of the spiro ring material), which also makes the device exhibit better stability and lifetime.
  • FIG. 1 is a schematic structural diagram of an OLED device in device application performance characterization
  • reaction conditions not explicitly described in the following preparation examples can be carried out with reference to the conditions suggested in the equipment description or conventional conditions in the art, which can be easily determined by those skilled in the art.
  • intermediates C2-C10 were synthesized by using different raw materials. The details are shown in Table 1 below.
  • the experimental device was fully dried, and to a 500 mL four-necked flask was added 2-bromo-6-chloro-9,9'-spirobifluorene 19.3 g (45 mmol) and 17.9 g (49.5 mmol) N-[1,1 '-Biphenyl-4-yl]-9,9-dimethyl-9H-fluoren-2-amine, add dry and degassed toluene as solvent, and add 6.5g (67.5mmol) of sodium tert-butoxide, 1.2g (2.25mmol) of the catalyst 1,1'-bis (diphenylphosphine) ferrocene, heated to 100-105 °C, the reaction for 16h.
  • intermediate D2-D10 was synthesized by using different raw materials. The details are shown in Table 2 below.
  • the experimental device was fully dried, and D1 (32.0g, 45mmol) and N-phenyl-4-benzidine 12.1g (49.5mmol) were added to a 500mL four-necked flask under nitrogen, and then dried and degassed toluene was added as Solvent, add 6.5g (67.5mmol) of sodium tert-butoxide, 0.88g (0.96mmol) of catalyst Pd 2 (dba) 3 to warm to 80 °C, slowly add 4.5mL of tri-tert-butylphosphine toluene solution with a mass concentration of 10% . After the dropwise addition, the temperature was raised to 100-105°C, and the reaction was carried out for 6 hours.
  • the glass transition temperature Tg is measured by differential scanning calorimetry (DSC, DSC25 differential scanning calorimeter of American TA Company), and the heating rate is 10° C./min; the thermal weightlessness temperature Td is the temperature of 1% weightlessness in a nitrogen atmosphere. Measured on the TGA55 thermogravimetric analyzer of American TA Company, the nitrogen flow rate is 20mL/min; the highest occupied molecular orbital HOMO energy level and the lowest unoccupied molecular orbital LUMO energy level are measured by cyclic voltammetry.
  • the compound of the present invention has a higher glass transition temperature, which can ensure the thermal stability of the compound, thereby avoiding the conversion of the amorphous film of the compound into a crystalline film, so that the produced compound containing the organic compound of the present invention The life of OLED devices has been improved.
  • the compounds of the present invention have different HOMO and LOMO energy levels and can be applied to different functional layers of OLED devices.
  • the organic compound of the present invention is particularly suitable for a hole injection layer (HIL), a hole transport layer (HTL), and/or an electron blocking layer (EBL) in an OLED device. They can be used as a separate layer or as a mixed component in HIL, HTL or EBL.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • an OLED device is manufactured, and the specific steps are as follows: a glass substrate coated with ITO (indium tin oxide) with a thickness of 130 nm (Corning Glass 50mm*50mm*0.7mm) is ultrasonically washed with isopropyl alcohol and pure water respectively 5 minutes, then cleaned with ultraviolet ozone, and then transferred the glass substrate to the vacuum deposition chamber; the hole injection material HAT-CN was thermally deposited on the transparent ITO electrode with a thickness of 5 nm in vacuum (about 10 -7 Torr) Forming a hole injection layer; vacuum depositing a compound 1-192 synthesized in the above preparation example in a thickness of 110 nm on the hole injection layer to form a hole transport layer; vacuum depositing 20 nm in thickness HT2 on the hole transport layer to form electrons Barrier layer; as light-emitting layer, vacuum deposition host EB and 4% guest dopant BD, thickness 25nm; ET compound containing 5% LiQ (8-hydroxyquino
  • the deposition rates of the used organic materials, lithium fluoride, and aluminum are maintained at 0.1 nm/s, 0.05 nm/s, and 0.2 nm/s, respectively.
  • the resulting OLED device emits blue light and has a light emitting area of 9 square millimeters.
  • Example 1 The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, Compound 1-164 was used instead of Compound 1-192 in Example 1.
  • Example 1 The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, Compound 1-202 was used instead of Compound 1-192 in Example 1.
  • Example 1 The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, HT1 was used instead of Compound 1-192 in Example 1.
  • the devices obtained in the above Examples 1-5 and Comparative Example 1 were subjected to performance tests at a current density of 10 mA/cm 2 .
  • the luminous color is judged and defined by the CIE x, y chromaticity coordinates;
  • the driving voltage refers to the voltage with a luminance of 1cd/m 2 ;
  • the current efficiency refers to the luminous luminance at a unit current density;
  • the generated luminous flux; external quantum efficiency (EQE) refers to the ratio of the number of photons that exit the component surface in the observation direction to the number of injected electrons.
  • LT97@1000nits refers to the time when the device is continuously used for more than 1000h, and the device decreases from the initial brightness (100%) to 97%.
  • the compounds used in Examples 1-5 are used as hole transport layers in OLED devices, and have superior hole transport capabilities and exhibit low voltage and high efficiency characteristics compared to benzidine type materials At the same time, based on high triplet energy (the characteristics of the spiral ring material), it shows better stability and life. It can be seen that the OLED device including the present invention has a low driving voltage and a long service life, and exhibits high stability device performance.
  • the device manufacturing process in Examples 6-10 is completely the same.
  • the same substrate and electrode materials are used, and the film thickness of the electrode material is also the same.
  • the difference is that the hole injection materials and The hole transport material was replaced, and the hole injection layer was doped with 2wt% of P-type doped material.
  • the compounds used in Examples 6-10 were used as the hole injection layer host material and hole transport layer in the organic light-emitting device, and the hole injection layer was doped with a P-type doping compound Compared with aniline-based materials, they have excellent hole-transporting capabilities and exhibit low-voltage and high-efficiency characteristics. At the same time, they also exhibit better stability and longevity. It can be seen that the organic light-emitting device including the present invention has a low driving voltage and a long service life, and exhibits high-stability device performance.

Abstract

Disclosed in the present invention are an organic compound containing a diarylamine-substituted 9,9'-spirobifluorene structure, having a structure as represented by chemical formula (1). The compound has a high glass transition temperature, suitable HOMO and LUMO energy levels, and high energy gap Eg and thermal stability, can be sublimated without decomposition and residues, has good application effect in OLED devices, and can effectively improve the light emitting performance and service life of the devices.

Description

二芳基胺取代的螺二芴类化合物及其在OLED器件中的应用Diarylamine substituted spirobifluorene compounds and their application in OLED devices 技术领域Technical field
本发明属于有机化学及光电器件技术领域，具体涉及一种包含二芳基胺取代的螺二芴(9,9'-Spirobifluorene)结构的化合物，及其在OLED器件中的应用。The invention belongs to the technical field of organic chemistry and optoelectronic devices, and in particular relates to a compound containing a diarylamine substituted spirobifluorene (9,9'-Spirobifluorene) structure and its application in an OLED device.
背景技术Background technique
相比于传统液晶显示(LCD)面板，有机电致发光(OLED)器件具备自发光、对比度高、轻薄、色彩饱和度佳、视角宽及反应速度快等优点，被称为“第三代显示器”。随着OLED屏在智能手机、电视、汽车电子市场的广泛应用，OLED面板出货呈快速增长态势，而LCD面板出货则开始走下坡路，导致很多主要从事LCD面板生产的厂家纷纷停产甚至倒闭。根据HIS Markit最新数据显示，由于智能手机市场进入停滞期，液晶显示器销量下降，导致了OLED显示器市场的良好局面。由于很多制造商将推出柔性显示设备以吸引更多买家，OLED的需求还将继续增长。中国OLED产业前景非常广阔，业内企业也正在努力积累发展经验，但国内产业链上游环节薄弱，行业的配套能力欠缺等因素为广大厂商制造了比较大的发展障碍。随着OLED需求的不断增长，必然刺激产业链上游环节的发展。Compared with traditional liquid crystal display (LCD) panels, organic electroluminescence (OLED) devices have the advantages of self-luminescence, high contrast, light and thin, good color saturation, wide viewing angle and fast response speed, and are called "third-generation displays" ". With the widespread use of OLED screens in smartphones, TVs, and automotive electronics markets, OLED panel shipments have shown rapid growth, while LCD panel shipments have begun to decline, leading many manufacturers that are mainly engaged in LCD panel production to stop production or even close down. According to the latest data from HIS Markit, due to the stagnation period in the smartphone market, sales of LCD monitors have declined, resulting in a good situation in the OLED display market. As many manufacturers will introduce flexible display devices to attract more buyers, the demand for OLED will continue to grow. The prospect of China's OLED industry is very broad, and companies in the industry are also working hard to accumulate development experience, but the upstream links of the domestic industrial chain are weak, and the industry's lack of supporting capabilities and other factors have created relatively large development obstacles for the majority of manufacturers. As the demand for OLED continues to grow, it will inevitably stimulate the development of upstream links in the industry chain.
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构通常包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、发光层(EML)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)等多种膜层，也就是说应用于OLED器件的光电功能材料至少包括空穴注入材料、空穴传输材料、发光材料、电子传输材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同的材 料在不同结构器件中的性能表现也可能完全迥异。The OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers of structures. Industrially applied OLED device structures generally include a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), and light emission. Layer (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL) and other film layers, that is to say, the photoelectric functional materials used in OLED devices include at least hole injection materials, For hole transport materials, luminescent materials, electron transport materials, etc., the types and matching forms of materials are characterized by richness and diversity. In addition, for the matching of OLED devices with different structures, the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in devices with different structures may also be completely different.
芴类化合物刚性的平面内联苯单元使其热稳定性和化学稳定性都较高，在固态时具有较高的荧光量子效率，因此用于OLED器件中可以提高材料的热稳定性、形态稳定性、载流子迁移的稳定性及良好的互溶性等。螺二芴作为常见的一类芴衍生物，可以作为OLED器件中的发光材料，利用其结构优势，可改善OLED器件的性能，延长使用寿命。The rigid in-plane biphenyl unit of the fluorene compound has high thermal stability and chemical stability, and has high fluorescence quantum efficiency in the solid state. Therefore, it can improve the thermal stability and morphological stability of the material when used in OLED devices. Stability, carrier migration stability and good miscibility. Spirobifluorene, as a common type of fluorene derivative, can be used as a luminescent material in OLED devices. Taking advantage of its structural advantages, it can improve the performance of OLED devices and prolong its service life.
发明内容Summary of the invention
本发明的目的首先在于提供一种含二芳基胺取代的螺二芴结构的有机化合物。该化合物具有较高的玻璃化温度、合适的HOMO和LUMO能级、及较高的Eg(能隙)，热稳定性高，能够在不发生分解和没有残留物的情况下升华，在OLED器件中应用效果良好，可有效提升器件发光性能和器件寿命，适用于磷光和荧光的OLED器件，尤其是在化合物作为空穴注入层材料和/或空穴传输层材料时情况如此。The first object of the present invention is to provide an organic compound containing a diarylamine substituted spirobifluorene structure. The compound has a high glass transition temperature, suitable HOMO and LUMO energy levels, and a high Eg (energy gap), high thermal stability, can be sublimated without decomposition and no residue, in OLED devices The application effect is good, which can effectively improve the device's luminous performance and device life. It is suitable for phosphorescent and fluorescent OLED devices, especially when the compound is used as a hole injection layer material and/or a hole transport layer material.
为了实现上述目的，本发明的一种含二芳基胺取代的螺二芴结构的有机化合物，具有下述化学式(1)所示的结构：In order to achieve the above object, an organic compound containing a spirobifluorene structure substituted with a diarylamine of the present invention has a structure represented by the following chemical formula (1):
Figure PCTCN2019120526-appb-000001
Figure PCTCN2019120526-appb-000001
其中，among them,
Ar 1、Ar 2、Ar 3、Ar 4各自独立地表示经取代或未经取代的芳基或杂芳基，并且Ar 1和Ar 2可通过E 1彼此连接成环，Ar 3和Ar 4可通过E 2彼此连接成环； Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent a substituted or unsubstituted aryl or heteroaryl group, and Ar 1 and Ar 2 may be connected to each other through E 1 to form a ring, Ar 3 and Ar 4 may be Connect to each other through E 2 to form a ring;
E 1和E 2各自独立地表示直接键、CRR’、NR、O或S，其中R和R’各自独立地表示C 1-C 8的直链或支链烷基、C 1-C 8的烷氧基、C 7-C 14的芳烷基； E 1 and E 2 each independently represent a direct bond, CRR′, NR, O or S, wherein R and R′ each independently represent a C 1 -C 8 linear or branched alkyl group, C 1 -C 8 Alkoxy, C 7 -C 14 aralkyl;
S 1和S 2各自独立地表示直接键、经取代或未经取代的亚芳基、经取代或未经取代的亚杂芳基； S 1 and S 2 each independently represent a direct bond, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene;
m和n各自独立地表示0至3的整数；m and n independently represent integers from 0 to 3;
R 1和R 2各自独立地表示氢、氘、卤素、腈基、经取代或未经取代的烷基、经取代或未经取代的环烷基、经取代或未经取代的烷氧基、经取代或未经取代的芳基、经取代或未经取代的芳氧基、经取代或未经取代的芳烷基、经取代或未经取代的烷基芳基、经取代或未经取代的芳烯基、或者经取代或未经取代的杂环基； R 1 and R 2 each independently represent hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, Substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted Arylalkenyl, or substituted or unsubstituted heterocyclyl;
前提是，Ar 1(Ar 2)N-(S 1) m-和-(S 2) n-NAr 3(Ar 4)不同。 The premise is that Ar 1 (Ar 2 )N-(S 1 ) m -and -(S 2 ) n -NAr 3 (Ar 4 ) are different.
作为本发明的优选实施方式，式(1)所示结构中的S 1、S 2为直接键，即两侧的N原子直接与螺二芴结构相连，结构如下述化学式(2)所示： As a preferred embodiment of the present invention, S 1 and S 2 in the structure shown in formula (1) are direct bonds, that is, the N atoms on both sides are directly connected to the spirobifluorene structure, and the structure is shown in the following chemical formula (2):
Figure PCTCN2019120526-appb-000002
Figure PCTCN2019120526-appb-000002
进一步优选地，R 1和R 2均表示氢，即结构如下述化学式(3)所示： Further preferably, both R 1 and R 2 represent hydrogen, that is, the structure is represented by the following chemical formula (3):
Figure PCTCN2019120526-appb-000003
Figure PCTCN2019120526-appb-000003
更为优选地，上述化学式(1)、(2)和(3)所示结构中，Ar 1、Ar 2、Ar 3、Ar 4各自独立地具有6-60个C原子，且各自独立地表示经取代或未经取代的苯基、经取代或未经取代的联苯基、经取代或未经取代的三联苯基、经取代或未经取代的四联苯基、经取代或未经取代的萘基、经取代或未经 取代的菲基、经取代或未经取代的芴基、经取代或未经取代的螺二芴基、经取代或未经取代的二苯并噻吩基、经取代或未经取代的二苯并呋喃基、或者经取代或未经取代的咔唑基。 More preferably, in the structures represented by the above chemical formulas (1), (2), and (3), Ar 1 , Ar 2 , Ar 3 , and Ar 4 each independently have 6 to 60 C atoms, and each independently represents Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted Naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzothienyl, Substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted carbazolyl.
特别优选地，Ar 1、Ar 2、Ar 3、Ar 4各自独立地选自下列结构： Particularly preferably, Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently selected from the following structures:
Figure PCTCN2019120526-appb-000004
Figure PCTCN2019120526-appb-000004
其中，虚线表示与氮键合的连接位；R 3各自独立地表示甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、环庚基、正辛基、苯基、4-叔丁基苯基、环烷基。 Among them, the dotted line represents the connection site bonded to nitrogen; R 3 independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, n-octyl , Phenyl, 4-tert-butylphenyl, cycloalkyl.
非限制性地，下文列出了本发明所述有机化合物的部分优选实例，包括：Without limitation, the following lists some preferred examples of organic compounds of the present invention, including:
Figure PCTCN2019120526-appb-000005
Figure PCTCN2019120526-appb-000005
Figure PCTCN2019120526-appb-000006
Figure PCTCN2019120526-appb-000006
Figure PCTCN2019120526-appb-000007
Figure PCTCN2019120526-appb-000007
Figure PCTCN2019120526-appb-000008
Figure PCTCN2019120526-appb-000008
Figure PCTCN2019120526-appb-000009
Figure PCTCN2019120526-appb-000009
Figure PCTCN2019120526-appb-000010
Figure PCTCN2019120526-appb-000010
Figure PCTCN2019120526-appb-000011
Figure PCTCN2019120526-appb-000011
在确定了本发明上述有机化合物及其结构特征后，如何制备该化合物对有机化学领域的技术人员来说是容易确定的。典型地，可通过二卤代芴酮与溴代联苯加成，成环后依次与不同结构的二芳基胺之间进行Buchwald–Hartwig偶联反应(C-N偶联反应)，分步引入二芳基胺基基团，得到目标化合物。其中，二卤代芴酮的合成可参考现有技术如CN107075089A，在此将其全文引入以作为参考。After determining the above-mentioned organic compound and its structural features of the present invention, how to prepare the compound is easily determined by those skilled in the art of organic chemistry. Typically, the Buchwald–Hartwig coupling reaction (CN coupling reaction) can be carried out between dihalogenated fluorenone and brominated biphenyl, followed by ring formation with diarylamines of different structures in turn Arylamino group to obtain the target compound. Among them, the synthesis of dihalogenated fluorenone can refer to the prior art such as CN107075089A, and the full text of which is hereby incorporated by reference.
示例性地，以合成化学式(3)所示化合物为代表，合成工艺如下：Exemplarily, represented by the compound represented by the synthetic chemical formula (3), the synthesis process is as follows:
Figure PCTCN2019120526-appb-000012
Figure PCTCN2019120526-appb-000012
由溴代联苯在正丁基锂试剂作用下与二卤代芴酮A加成，得到中间体醇B，水解后环合生成二卤代螺二芴C，再与不同的二芳基胺进行C-N偶联，先得到单二芳基胺取代的化合物D，再得到目标化合物。Addition of brominated biphenyls with dihalofluorenone A under the action of n-butyllithium reagent yields intermediate alcohol B, which is cyclized after hydrolysis to form dihalospirobifluorene C, which is then reacted with different diarylamines By performing CN coupling, the compound D substituted with monodiarylamine is obtained first, and then the target compound is obtained.
除此之外，也可采用基于相同反应原理的其它类似过程合成目标化合物。例如，针对-NAr 3(Ar 4)基团在2取代位的化学式(3)所示化合物，还可经由以下工艺合成： In addition, other similar processes based on the same reaction principle can also be used to synthesize the target compound. For example, the compound represented by the chemical formula (3) for the -NAr 3 (Ar 4 ) group at the 2 substitution position can also be synthesized through the following process:
Figure PCTCN2019120526-appb-000013
Figure PCTCN2019120526-appb-000013
由溴代芴酮与二芳基胺进行C-N偶联，得到单二芳基胺取代的芴酮，然后与NBS反应，得到溴代单二芳基胺取代的芴酮，……随后在正丁基锂试剂作用下与溴代联苯反应，得到中间体醇，经水解后环合生成单二芳基 胺取代的溴代螺二芴，最后再与二芳基胺进行C-N偶联，得到目标化合物。CN coupling of brominated fluorenone and diarylamine to obtain monodiarylamine-substituted fluorenone, and then reacted with NBS to obtain brominated monodiarylamine-substituted fluorenone, followed by n-butyl Lithium reagent reacts with brominated biphenyl to obtain an intermediate alcohol. After hydrolysis, it cyclizes to form monodiarylamine-substituted bromospirobifluorene. Finally, CN is coupled with the diarylamine to obtain the target. Compound.
本发明的目的还在于提供上述有机化合物在OLED器件中的应用，以及包含上述有机化合物的OLED器件。The object of the present invention is also to provide applications of the above organic compounds in OLED devices, and OLED devices containing the above organic compounds.
作为示例性实施方案，所述OLED器件包括：第一电极；设置成面向第一电极的第二电极；以及设置在第一电极与第二电极之间的一个或多个有机材料层，其中有机材料层中的一个或多个层包含化学式(1)所示的化合物。As an exemplary embodiment, the OLED device includes: a first electrode; a second electrode disposed facing the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein the organic One or more of the material layers contain the compound represented by chemical formula (1).
有机材料层可以由单层结构构成，也可以由其中堆叠有两个或更多个有机材料层的多层结构构成。例如，本发明的OLED器件可以具有包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层等作为有机材料层的结构。器件结构不限于此，也可以包括较少数量的有机层。The organic material layer may be composed of a single-layer structure or a multilayer structure in which two or more organic material layers are stacked. For example, the OLED device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. The device structure is not limited to this, and may include a smaller number of organic layers.
作为示例性实施方案，有机材料层包括空穴注入层，且空穴注入层包含化学式(1)的化合物。As an exemplary embodiment, the organic material layer includes a hole injection layer, and the hole injection layer includes a compound of chemical formula (1).
作为示例性实施方案，有机材料层包括空穴注入层，空穴注入层包含化学式(1)的化合物，并且包含以1-20wt％的掺杂浓度掺杂的P型掺杂材料，P型掺杂材料的化学结构式如下：As an exemplary embodiment, the organic material layer includes a hole injection layer, the hole injection layer includes a compound of formula (1), and includes a P-type doped material doped at a doping concentration of 1-20 wt%, P-type doped The chemical structural formula of the hybrid material is as follows:
Figure PCTCN2019120526-appb-000014
Figure PCTCN2019120526-appb-000014
作为示例性实施方案，有机材料层包括空穴注入层、空穴传输层，且空穴传输层包含化学式(1)的化合物。As an exemplary embodiment, the organic material layer includes a hole injection layer, a hole transport layer, and the hole transport layer includes a compound of chemical formula (1).
作为示例性实施方案，有机材料层包括空穴注入层、空穴传输层，空穴传输层包含化学式(1)的化合物时，空穴注入层仅使用具有下列结构式的化合物HAT-CN：As an exemplary embodiment, the organic material layer includes a hole injection layer and a hole transport layer. When the hole transport layer contains the compound of formula (1), the hole injection layer uses only the compound HAT-CN having the following structural formula:
Figure PCTCN2019120526-appb-000015
Figure PCTCN2019120526-appb-000015
作为示例性实施方案，有机材料层还包括电子阻挡层，电子阻挡层使用以下化学结构的化合物HT2：As an exemplary embodiment, the organic material layer further includes an electron blocking layer that uses the compound HT2 of the following chemical structure:
Figure PCTCN2019120526-appb-000016
Figure PCTCN2019120526-appb-000016
作为示例性实施方案，有机材料层还包括发光层，并且发光层使用化合物EB作为主发光体，化合物BD作为客发光体，其中客发光体的掺杂比例在1-10重量％，两者的化学结构式如下：As an exemplary embodiment, the organic material layer further includes a light-emitting layer, and the light-emitting layer uses the compound EB as the main light emitter and the compound BD as the guest light emitter, wherein the doping ratio of the guest light emitter is 1-10% by weight, both The chemical structural formula is as follows:
Figure PCTCN2019120526-appb-000017
Figure PCTCN2019120526-appb-000017
作为示例性实施方案，有机材料层还包括电子传输层，电子传输层使用以下化学结构的化合物ET，并且包含掺杂5重量％的喹啉锂(Lithium8-quinolinolate，简写成LiQ)：As an exemplary embodiment, the organic material layer further includes an electron transport layer that uses the compound ET of the following chemical structure and contains 5 wt% doped lithium quinoline (Lithium8-quinolinolate, abbreviated as LiQ):
Figure PCTCN2019120526-appb-000018
Figure PCTCN2019120526-appb-000018
作为示例性实施方案，有机材料层还包括电子注入层，电子注入层使用的化合物为氟化锂(LiF)。As an exemplary embodiment, the organic material layer further includes an electron injection layer, and the compound used for the electron injection layer is lithium fluoride (LiF).
根据所使用的材料，本发明的OLED器件可以为顶部发光型、底部发光型或双向发光型。According to the materials used, the OLED device of the present invention may be a top emission type, a bottom emission type, or a bidirectional emission type.
本发明有益的技术效果在于：本发明的有机化合物用于OLED器件时，由于化合物具有大的共轭体系和较好的刚性共面，而且玻璃化转变温度高，有较高的热稳定性，可以避免化合物的非结晶性薄膜转变成结晶性薄膜，使得OLED器件的寿命得到提升。另外，本发明的化合物具有不同的HOMO和LOMO能级，可应用于OLED器件不同的功能层。同时，本发明的化合物具有高三重态能量(螺环材料的特性)，也使得器件表现出更好的稳定性及寿命。The beneficial technical effect of the present invention is that when the organic compound of the present invention is used in an OLED device, since the compound has a large conjugated system and good rigidity coplanar, and has a high glass transition temperature and high thermal stability, The non-crystalline thin film of the compound can be prevented from being converted into the crystalline thin film, so that the life of the OLED device is improved. In addition, the compounds of the present invention have different HOMO and LOMO energy levels and can be applied to different functional layers of OLED devices. At the same time, the compound of the present invention has a high triplet energy (characteristic of the spiro ring material), which also makes the device exhibit better stability and lifetime.
附图说明BRIEF DESCRIPTION
图1为器件应用性能表征中OLED器件的结构示意图；其中，FIG. 1 is a schematic structural diagram of an OLED device in device application performance characterization; wherein,
1、透明基板，2、ITO阳极层，3、空穴注入层，4、空穴传输层，5、电子阻挡层，6、发光层，7、电子传输层，8、电子注入层，9、阴极层。1. Transparent substrate, 2. ITO anode layer, 3. Hole injection layer, 4. Hole transport layer, 5. Electron blocking layer, 6. Light emitting layer, 7, Electron transport layer, 8, Electron injection layer, 9. Cathode layer.
具体实施方式detailed description
通过以下实施例更详细地说明本发明，但不希望因此限制本发明。在这些内容的基础上，本领域技术人员将能够在不付出创造性劳动的情况下在所公开的整个范围内实施本发明和制备根据本发明的其它化合物，和将这些化合物用于电子器件中或使用根据本发明所述的方法。The invention is illustrated in more detail by the following examples, but it is not intended to limit the invention accordingly. On the basis of these contents, those skilled in the art will be able to implement the present invention and prepare other compounds according to the present invention within the entire range disclosed without creative efforts, and use these compounds in electronic devices or The method according to the invention is used.
制备实施例Preparation Example
如无特殊说明，下列制备实施例中未明确记载的反应条件可参照设备说明书中建议的条件或本领域常规条件进行，这对本领域技术人员而言是容易确定的。Unless otherwise specified, the reaction conditions not explicitly described in the following preparation examples can be carried out with reference to the conditions suggested in the equipment description or conventional conditions in the art, which can be easily determined by those skilled in the art.
1.中间体的合成1. Synthesis of intermediates
1.1中间体C(同侧位取代二卤代螺二芴)的合成1.1 Synthesis of Intermediate C (Iso-substituted dihalospirobifluorene)
Figure PCTCN2019120526-appb-000019
Figure PCTCN2019120526-appb-000019
(1)实施例C1：合成2-溴-6-氯-9,9’-螺二芴(1) Example C1: Synthesis of 2-bromo-6-chloro-9,9’-spirobifluorene
Figure PCTCN2019120526-appb-000020
Figure PCTCN2019120526-appb-000020
将实验装置充分干燥，在氮气下向1L四口烧瓶中加入35g 2-溴-1,1'-联苯(152mmo1)和400mL干燥过的四氢呋喃，搅拌溶解后用液氮降温至-78℃以下，缓慢滴加61mL 2.5M(152mmol)的n-BuLi正己烷溶 液；滴加结束后在-78℃下搅拌1h，然后在该温度下分批加入45g(152mmo1)2-溴-6-氯-9-芴酮固体，加结束后在-78℃下保温1h，然后在室温下搅拌12h。待反应结束，滴加4M盐酸溶液淬灭反应，用乙酸乙酯萃取，有机相用饱和食盐水洗涤，旋干除去溶剂，得到中间体醇B1。Fully dry the experimental device, add 35g of 2-bromo-1,1'-biphenyl (152mmo1) and 400mL of dried tetrahydrofuran to a 1L four-necked flask under nitrogen, stir and dissolve, and cool to -78℃ below with liquid nitrogen , Slowly add 61mL of 2.5M (152mmol) n-BuLi n-hexane solution; after the dropwise addition, stir at -78℃ for 1h, then add 45g (152mmo1) 2-bromo-6-chloro- in batches at this temperature 9-Fluorone solid, after the addition was kept at -78 ℃ for 1h, and then stirred at room temperature for 12h. After the reaction was completed, 4M hydrochloric acid solution was added dropwise to quench the reaction, extracted with ethyl acetate, the organic phase was washed with saturated brine, and the solvent was removed by rotary drying to obtain the intermediate alcohol B1.
在不进行任何提纯的情况下，再投料到1L的干燥三口烧瓶中，加入160mL乙酸和5g 36％盐酸，升温回流3h，结束反应。冷却至室温后，过滤，用水洗涤两次，干燥，柱层析提纯，得到36.6g类白色固体产物C1，产率为56％。Without any purification, it was added to a 1L dry three-necked flask, 160mL of acetic acid and 5g of 36% hydrochloric acid were added, and the temperature was raised to reflux for 3h to complete the reaction. After cooling to room temperature, it was filtered, washed twice with water, dried, and purified by column chromatography to obtain 36.6 g of off-white solid product C1 with a yield of 56%.
对中间体C1的结构进行表征，结果如下所示。The structure of intermediate C1 was characterized and the results are shown below.
1H NMR(CDCl 3,400MHz)δ:7.89(d,J＝7.5Hz,2H),7.83(s,1H),7.77(d,J＝8.1Hz,1H),7.61(s,1H),7.54(d,J＝7.5Hz,2H),7.44(d,J＝8.1Hz,1H),7.39-7.27(m,6H)； 1 H NMR (CDCl 3 , 400 MHz) δ: 7.89 (d, J = 7.5 Hz, 2H), 7.83 (s, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.61 (s, 1H), 7.54 (d, J = 7.5 Hz, 2H), 7.44 (d, J = 8.1 Hz, 1H), 7.39-7.27 (m, 6H);
IR(KBr)ν:3057,3028,1593,1516,1483,1450,1279,758,694cm -1； IR(KBr)ν: 3057,3028,1593,1516,1483,1450,1279,758,694cm -1 ;
MS[M+H] +＝428.99. MS[M+H] + = 428.99.
(2)中间体C2-C10(2) Intermediate C2-C10
参照中间体C1的制备方法，通过采用不同原料合成中间体C2-C10。具体如下表1中所示。Referring to the preparation method of intermediate C1, intermediates C2-C10 were synthesized by using different raw materials. The details are shown in Table 1 below.
表1Table 1
Figure PCTCN2019120526-appb-000021
Figure PCTCN2019120526-appb-000021
Figure PCTCN2019120526-appb-000022
Figure PCTCN2019120526-appb-000022
1.2中间体D(氯代螺二芴单取代二芳基衍生物)的合成1.2 Synthesis of Intermediate D (monosubstituted diaryl derivative of chlorospirobifluorene)
Figure PCTCN2019120526-appb-000023
Figure PCTCN2019120526-appb-000023
(1)实施例D1：合成N-([1,1'-联苯基-4-基)-6-氯-N-(9-9-二甲基-9-芴-2-基)-9,9'-螺二芴基-2-胺](1) Example D1: Synthesis of N-([1,1'-biphenyl-4-yl)-6-chloro-N-(9-9-dimethyl-9-fluoren-2-yl)- 9,9'-spirobifluorenyl-2-amine]
Figure PCTCN2019120526-appb-000024
Figure PCTCN2019120526-appb-000024
将实验装置充分干燥，在氮气下向500mL四口烧瓶中加入2-溴-6-氯-9,9’-螺二芴19.3g(45mmol)和17.9g(49.5mmol)N-[1,1'-联苯-4-基]-9,9-二甲基-9H-芴-2-胺，再加入干燥并脱气过的甲苯作溶剂，加入6.5g(67.5mmol)叔丁醇钠，1.2g(2.25mmol)催化剂1,1'-双(二苯基膦)二茂铁，升温至100-105℃，反应16h。待反应结束，冷却至室温，用甲苯稀释，垫硅胶过滤，滤液真空蒸去溶剂，得到粗品，粗品用柱层析提纯，得到18.6g产物D1，产率为58％。The experimental device was fully dried, and to a 500 mL four-necked flask was added 2-bromo-6-chloro-9,9'-spirobifluorene 19.3 g (45 mmol) and 17.9 g (49.5 mmol) N-[1,1 '-Biphenyl-4-yl]-9,9-dimethyl-9H-fluoren-2-amine, add dry and degassed toluene as solvent, and add 6.5g (67.5mmol) of sodium tert-butoxide, 1.2g (2.25mmol) of the catalyst 1,1'-bis (diphenylphosphine) ferrocene, heated to 100-105 ℃, the reaction for 16h. After the reaction was completed, it was cooled to room temperature, diluted with toluene, filtered through a silica gel pad, and the solvent was distilled off in vacuo to obtain the crude product. The crude product was purified by column chromatography to obtain 18.6 g of product D1 with a yield of 58%.
MS[M+H] +＝710.23。 MS[M+H] + = 710.23.
(2)D2-D10(2) D2-D10
参照中间体D1的制备方法，通过采用不同原料合成中间体D2-D10。具体如下表2所示。Referring to the preparation method of intermediate D1, intermediate D2-D10 was synthesized by using different raw materials. The details are shown in Table 2 below.
表2Table 2
Figure PCTCN2019120526-appb-000025
Figure PCTCN2019120526-appb-000025
Figure PCTCN2019120526-appb-000026
Figure PCTCN2019120526-appb-000026
Figure PCTCN2019120526-appb-000027
Figure PCTCN2019120526-appb-000027
2.目标化合物的合成2. Synthesis of target compound
Figure PCTCN2019120526-appb-000028
Figure PCTCN2019120526-appb-000028
以下实施例优选部分中间体D，合成相应的目标化合物。In the following examples, some intermediates D are preferred to synthesize the corresponding target compounds.
(1)合成化合物1-192：(1) Synthesis of compound 1-192:
Figure PCTCN2019120526-appb-000029
Figure PCTCN2019120526-appb-000029
将实验装置充分干燥，在氮气下向500mL四口烧瓶中加入D1(32.0g，45mmol)和N-苯基-4-联苯胺12.1g(49.5mmol)，再加入干燥并脱气过的甲苯作溶剂，加入6.5g(67.5mmol)叔丁醇钠，0.88g(0.96mmol)催化剂Pd 2(dba) 3升温至80℃，缓慢滴加4.5mL质量浓度为10％的三叔丁基膦甲苯溶液。滴加完毕后升温至100-105℃，反应6h。待反应结束， 冷却至室温，用甲苯稀释，垫硅胶过滤，滤液真空蒸去溶剂，得到粗品，粗品用柱层析提纯，得到23.6g产物1-192，产率为57％。 The experimental device was fully dried, and D1 (32.0g, 45mmol) and N-phenyl-4-benzidine 12.1g (49.5mmol) were added to a 500mL four-necked flask under nitrogen, and then dried and degassed toluene was added as Solvent, add 6.5g (67.5mmol) of sodium tert-butoxide, 0.88g (0.96mmol) of catalyst Pd 2 (dba) 3 to warm to 80 ℃, slowly add 4.5mL of tri-tert-butylphosphine toluene solution with a mass concentration of 10% . After the dropwise addition, the temperature was raised to 100-105°C, and the reaction was carried out for 6 hours. After the reaction was completed, it was cooled to room temperature, diluted with toluene, filtered with silica gel, and the solvent was evaporated in vacuo to obtain the crude product. The crude product was purified by column chromatography to obtain 23.6g of product 1-192 with a yield of 57%.
产物化合物1-192的结构表征数据如下所示。Structural characterization data of product compound 1-192 are shown below.
1H NMR(CDCl 3,400MHz)δ:7.90-7.84(m,5H),7.74(d,J＝7.5Hz,4H),7.61-7.54(m,8H),7.47(t,J＝7.5Hz,4H),7.41-7.35(m,10H),7.33-7.27(m,4H),7.25-7.20(m,3H),7.14(d,J＝7.5Hz,1H),7.09-7.04(m,4H),6.99(t,J＝7.5Hz,1H),1.68(s,6H)； 1 H NMR (CDCl 3 , 400 MHz) δ: 7.90-7.84 (m, 5H), 7.74 (d, J=7.5 Hz, 4H), 7.61-7.54 (m, 8H), 7.47 (t, J=7.5 Hz, 4H), 7.41-7.35(m, 10H), 7.33-7.27(m, 4H), 7.25-7.20(m, 3H), 7.14(d, J=7.5Hz, 1H), 7.09-7.04(m, 4H) , 6.99 (t, J = 7.5 Hz, 1H), 1.68 (s, 6H);
IR(KBr)ν:3067,3034,1595,1494,1468,1332,1273,807,761,696cm -1； IR(KBr)ν: 3067,3034,1595,1494,1468,1332,1273,807,761,696cm -1 ;
MS[M+H] +＝919.42. MS[M+H] + =919.42.
(2)参照化合物1-192的制备方法，以D2-D10和不同的二芳基胺为原料，合成相应的目标化合物。具体如下表3所示。(2) Referring to the preparation method of compound 1-192, using D2-D10 and different diarylamines as raw materials, the corresponding target compounds are synthesized. The details are shown in Table 3 below.
表3table 3
Figure PCTCN2019120526-appb-000030
Figure PCTCN2019120526-appb-000030
Figure PCTCN2019120526-appb-000031
Figure PCTCN2019120526-appb-000031
Figure PCTCN2019120526-appb-000032
Figure PCTCN2019120526-appb-000032
性能表征Performance characterization
3.化合物物理性能3. Compound physical properties
以部分化合物为例，对本发明的有机化合物的热性能、HOMO能级和LUMO能级进行测试。检测对象及其结果如表4所示。Taking some compounds as examples, the thermal performance, HOMO energy level and LUMO energy level of the organic compound of the present invention are tested. The detection objects and their results are shown in Table 4.
表4Table 4
化合物Chemical compound Tg(℃)Tg(℃) Td(℃)Td(℃) HOMO(eV)HOMO(eV) LUMO(eV)LUMO(eV) 适用的功能层Applicable functional layer
1-1921-192 185185 497497 5.565.56 2.302.30 HIL，HTLHIL, HTL
1-921-92 178178 489489 5.475.47 2.262.26 HIL，HTLHIL, HTL
1-1641-164 175175 483483 5.235.23 2.152.15 HIL，HTL，EBLHIL, HTL, EBL
1-1971-197 197197 519519 5.345.34 2.282.28 HIL，HTLHIL, HTL
1-2021-202 191191 505505 5.555.55 2.322.32 HIL，HTLHIL, HTL
其中，玻璃化温度Tg由示差扫描量热法(DSC，美国TA公司DSC25示差扫描量热仪)测定，升温速率10℃/min；热失重温度Td是在氮气气氛中失重1％的温度，在美国TA公司的TGA55热重分析仪上进行测定，氮气流 量为20mL/min；最高占据分子轨道HOMO能级和最低未占分子轨道LUMO能级，是由循环伏安法测得。Among them, the glass transition temperature Tg is measured by differential scanning calorimetry (DSC, DSC25 differential scanning calorimeter of American TA Company), and the heating rate is 10° C./min; the thermal weightlessness temperature Td is the temperature of 1% weightlessness in a nitrogen atmosphere. Measured on the TGA55 thermogravimetric analyzer of American TA Company, the nitrogen flow rate is 20mL/min; the highest occupied molecular orbital HOMO energy level and the lowest unoccupied molecular orbital LUMO energy level are measured by cyclic voltammetry.
由表4数据可知，本发明化合物有较高的玻璃化转变温度，可以保证化合物的热稳定性，从而避免化合物的非结晶性薄膜转变成结晶性薄膜，使得所制作的含有本发明有机化合物的OLED器件的寿命得到提升。同时，本发明化合物具有不同的HOMO和LOMO能级，可应用于OLED器件不同的功能层。It can be seen from the data in Table 4 that the compound of the present invention has a higher glass transition temperature, which can ensure the thermal stability of the compound, thereby avoiding the conversion of the amorphous film of the compound into a crystalline film, so that the produced compound containing the organic compound of the present invention The life of OLED devices has been improved. At the same time, the compounds of the present invention have different HOMO and LOMO energy levels and can be applied to different functional layers of OLED devices.
4.OLED器件应用4. OLED device application
本发明的有机化合物特别适用于OLED器件中的空穴注入层(HIL)、空穴传输层(HTL)和/或电子阻挡层(EBL)。它们可作为单独的层，也可作为HIL、HTL或EBL中的混合组分。The organic compound of the present invention is particularly suitable for a hole injection layer (HIL), a hole transport layer (HTL), and/or an electron blocking layer (EBL) in an OLED device. They can be used as a separate layer or as a mixed component in HIL, HTL or EBL.
以下结合附图1，通过实施例1-10和比较实施例1-2详细说明本发明的有机化合物在OLED器件中作为不同功能层材料的应用效果。The application effect of the organic compound of the present invention as a material for different functional layers in an OLED device will be described in detail below with reference to FIG. 1 through Examples 1-10 and Comparative Examples 1-2.
其中使用到的有机材料的结构式如下，它们都是现有的已知在售化合物，由市场采购获得：The structural formulas of the organic materials used are as follows. They are all existing known compounds for sale, which are purchased from the market:
Figure PCTCN2019120526-appb-000033
Figure PCTCN2019120526-appb-000033
实施例1Example 1
参照图1所示结构，制造OLED器件，具体步骤为：将镀有厚度为130nm的ITO(氧化铟锡)的玻璃基板(康宁玻璃50mm*50mm*0.7mm)分别用异 丙醇和纯水超声洗涤5分钟，再用紫外线臭氧清洗，之后将玻璃基板传送至真空沉积室中；将空穴注入材料HAT-CN以5nm的厚度真空(约10 -7Torr)热沉积在透明ITO电极上，由此形成空穴注入层；在空穴注入层上真空沉积110nm厚度的上述制备实施例中合成的化合物1-192，形成空穴传输层；在空穴传输层上真空沉积20nm厚度的HT2，形成电子阻挡层；作为发光层，真空沉积主体EB和4％的客体掺杂剂BD，厚度为25nm；使用包含掺杂5％LiQ(8-羟基喹啉锂)的ET化合物形成电子传输层，厚度为25nm；最后按顺序沉积1nm厚的氟化锂(电子注入层)和150nm厚度的铝形成阴极；将该器件从沉积室传送至手套箱中，随即用UV可固化环氧树脂及含有吸湿剂的玻璃盖板进行封装，从而制造出OLED器件。 Referring to the structure shown in FIG. 1, an OLED device is manufactured, and the specific steps are as follows: a glass substrate coated with ITO (indium tin oxide) with a thickness of 130 nm (Corning Glass 50mm*50mm*0.7mm) is ultrasonically washed with isopropyl alcohol and pure water respectively 5 minutes, then cleaned with ultraviolet ozone, and then transferred the glass substrate to the vacuum deposition chamber; the hole injection material HAT-CN was thermally deposited on the transparent ITO electrode with a thickness of 5 nm in vacuum (about 10 -7 Torr) Forming a hole injection layer; vacuum depositing a compound 1-192 synthesized in the above preparation example in a thickness of 110 nm on the hole injection layer to form a hole transport layer; vacuum depositing 20 nm in thickness HT2 on the hole transport layer to form electrons Barrier layer; as light-emitting layer, vacuum deposition host EB and 4% guest dopant BD, thickness 25nm; ET compound containing 5% LiQ (8-hydroxyquinoline lithium) doped to form an electron transport layer, thickness is 25nm; finally deposit 1nm thick lithium fluoride (electron injection layer) and 150nm thick aluminum to form the cathode; transfer the device from the deposition chamber to the glove box, and then use UV curable epoxy resin and moisture-containing The glass cover is encapsulated to produce an OLED device.
在上述制造步骤中，使用的有机材料、氟化锂和铝的沉积速率分别保持在0.1nm/s、0.05nm/s、0.2nm/s。In the above manufacturing steps, the deposition rates of the used organic materials, lithium fluoride, and aluminum are maintained at 0.1 nm/s, 0.05 nm/s, and 0.2 nm/s, respectively.
所得OLED器件发射蓝光且具有9平方毫米的发光区域。The resulting OLED device emits blue light and has a light emitting area of 9 square millimeters.
实施例2Example 2
以与实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-92代替实施例1中的化合物1-192。The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, Compound 1-92 was used instead of Compound 1-192 in Example 1.
实施例3Example 3
以与实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-164代替实施例1中的化合物1-192。The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, Compound 1-164 was used instead of Compound 1-192 in Example 1.
实施例4Example 4
以与实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-197代替实施例1中的化合物1-192。The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, Compound 1-197 was used instead of Compound 1-192 in Example 1.
实施例5Example 5
以与实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-202代替实施例1中的化合物1-192。The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, Compound 1-202 was used instead of Compound 1-192 in Example 1.
比较实施例1Comparative Example 1
以与实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用HT1代替实施例1中的化合物1-192。The experiment was conducted in the same manner as in Example 1, except that as the hole transport layer, HT1 was used instead of Compound 1-192 in Example 1.
实施例1-5和比较实施例1所制作的OLED器件结构如表5所示，测试结果如表6所示。The structures of the OLED devices fabricated in Examples 1-5 and Comparative Example 1 are shown in Table 5, and the test results are shown in Table 6.
表5table 5
Figure PCTCN2019120526-appb-000034
Figure PCTCN2019120526-appb-000034
将上述实施例1-5和比较实施例1所得器件在10mA/cm 2电流密度下进行性能测试。其中，发光颜色用CIE x,y色度坐标来判别与定义；驱动电 压是指亮度为1cd/m 2的电压；电流效率是指单位电流密度下的发光亮度；发光效率是指消耗单位电功率所产生的光通量；外部量子效率(external quantum efficiency,EQE)是指在观测方向上射出组件表面的光子数目与注入电子数目的比率。LT97@1000nits是指连续使用1000h以上，器件从初始亮度(100％)降低到97％的时间。 The devices obtained in the above Examples 1-5 and Comparative Example 1 were subjected to performance tests at a current density of 10 mA/cm 2 . Among them, the luminous color is judged and defined by the CIE x, y chromaticity coordinates; the driving voltage refers to the voltage with a luminance of 1cd/m 2 ; the current efficiency refers to the luminous luminance at a unit current density; The generated luminous flux; external quantum efficiency (EQE) refers to the ratio of the number of photons that exit the component surface in the observation direction to the number of injected electrons. LT97@1000nits refers to the time when the device is continuously used for more than 1000h, and the device decreases from the initial brightness (100%) to 97%.
结果如表6所示。The results are shown in Table 6.
表6Table 6
Figure PCTCN2019120526-appb-000035
Figure PCTCN2019120526-appb-000035
如上表所示，实施例1-5中使用的化合物用作OLED器件中的空穴传输层，与联苯胺型材料相比，具有优异的空穴传输的能力而表现出低电压和高效率特性，同时，基于高三重态能量(螺环材料的特性)而表现出更好的稳定性及寿命。可见包含本发明的OLED器件具有低驱动电压及长使用寿命，展现高稳定性的器件性能。As shown in the above table, the compounds used in Examples 1-5 are used as hole transport layers in OLED devices, and have superior hole transport capabilities and exhibit low voltage and high efficiency characteristics compared to benzidine type materials At the same time, based on high triplet energy (the characteristics of the spiral ring material), it shows better stability and life. It can be seen that the OLED device including the present invention has a low driving voltage and a long service life, and exhibits high stability device performance.
为进一步验证本发明的应用性能优势，参照上述实施例1的方式，制造具有如表7中所示结构的OLED器件。 表7In order to further verify the application performance advantages of the present invention, referring to the manner of Example 1 above, an OLED device having the structure shown in Table 7 is manufactured. Table 7
Figure PCTCN2019120526-appb-000036
Figure PCTCN2019120526-appb-000036
与比较例2相比，实施例6-10中器件制作工艺完全相同，采用了相同的基板和电极材料，电极材料的膜厚也保持一致，所不同的是对器件中的空穴注入材料和空穴传输材料做了更换，并在空穴注入层掺杂了2wt％的P型掺杂材料。Compared with Comparative Example 2, the device manufacturing process in Examples 6-10 is completely the same. The same substrate and electrode materials are used, and the film thickness of the electrode material is also the same. The difference is that the hole injection materials and The hole transport material was replaced, and the hole injection layer was doped with 2wt% of P-type doped material.
将上述实施例6-10和比较实施例2所得器件在10mA/cm 2电流密度下进行性能测试。结果如表8所示。 The devices obtained in the above Examples 6-10 and Comparative Example 2 were subjected to performance tests at a current density of 10 mA/cm 2 . The results are shown in Table 8.
表8Table 8
Figure PCTCN2019120526-appb-000037
Figure PCTCN2019120526-appb-000037
如上表所示，实施例6-10中使用的化合物用作有机发光器件中的空穴注入层主体材料、空穴传输层，同时在空穴注入层掺杂了P型掺杂化合 物，与联苯胺型材料相比，具有优异的空穴传输的能力而表现出低电压和高效率特性，同时，也表现出更好的稳定性及寿命。可见包含本发明的有机发光器件具有低驱动电压及长使用寿命，展现高稳定性的器件性能。As shown in the above table, the compounds used in Examples 6-10 were used as the hole injection layer host material and hole transport layer in the organic light-emitting device, and the hole injection layer was doped with a P-type doping compound Compared with aniline-based materials, they have excellent hole-transporting capabilities and exhibit low-voltage and high-efficiency characteristics. At the same time, they also exhibit better stability and longevity. It can be seen that the organic light-emitting device including the present invention has a low driving voltage and a long service life, and exhibits high-stability device performance.
以上所述仅为本发明的优选实施例，并不用于限制本发明，对于本领域技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (19)

  1. 一种含二芳基胺取代的螺二芴结构的有机化合物，具有下述化学式(1)所示的结构：An organic compound containing a diarylamine-substituted spirobifluorene structure, having a structure represented by the following chemical formula (1):
    Figure PCTCN2019120526-appb-100001
    Figure PCTCN2019120526-appb-100001
    其中，among them,
    Ar 1、Ar 2、Ar 3、Ar 4各自独立地表示经取代或未经取代的芳基或杂芳基，并且Ar 1和Ar 2可通过E 1彼此连接成环，Ar 3和Ar 4可通过E 2彼此连接成环； Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent a substituted or unsubstituted aryl or heteroaryl group, and Ar 1 and Ar 2 may be connected to each other through E 1 to form a ring, Ar 3 and Ar 4 may be Connect to each other through E 2 to form a ring;
    E 1和E 2各自独立地表示直接键、CRR’、NR、O或S，其中R和R’各自独立地表示C 1-C 8的直链或支链烷基、C 1-C 8的烷氧基、C 7-C 14的芳烷基； E 1 and E 2 each independently represent a direct bond, CRR′, NR, O or S, wherein R and R′ each independently represent a C 1 -C 8 linear or branched alkyl group, C 1 -C 8 Alkoxy, C 7 -C 14 aralkyl;
    S 1和S 2各自独立地表示直接键、经取代或未经取代的亚芳基、经取代或未经取代的亚杂芳基； S 1 and S 2 each independently represent a direct bond, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene;
    m和n各自独立地表示0至3的整数；m and n independently represent integers from 0 to 3;
    R 1和R 2各自独立地表示氢、氘、卤素、腈基、经取代或未经取代的烷基、经取代或未经取代的环烷基、经取代或未经取代的烷氧基、经取代或未经取代的芳基、经取代或未经取代的芳氧基、经取代或未经取代的芳烷基、经取代或未经取代的烷基芳基、经取代或未经取代的芳烯基、或者经取代或未经取代的杂环基； R 1 and R 2 each independently represent hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, Substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted Arylalkenyl, or substituted or unsubstituted heterocyclyl;
    前提是，Ar 1(Ar 2)N-(S 1) m-和-(S 2) n-NAr 3(Ar 4)不同。 The premise is that Ar 1 (Ar 2 )N-(S 1 ) m -and -(S 2 ) n -NAr 3 (Ar 4 ) are different.
  2. 根据权利要求1所述的有机化合物，其特征在于，结构如下述化学式(2)所示：The organic compound according to claim 1, wherein the structure is represented by the following chemical formula (2):
    Figure PCTCN2019120526-appb-100002
    Figure PCTCN2019120526-appb-100002
  3. 根据权利要求1或2所述的有机化合物，其特征在于，结构如下述化学式(3)所示：The organic compound according to claim 1 or 2, wherein the structure is represented by the following chemical formula (3):
    Figure PCTCN2019120526-appb-100003
    Figure PCTCN2019120526-appb-100003
  4. 根据权利要求1-3中任一项所述的有机化合物，其特征在于：Ar 1、Ar 2、Ar 3、Ar 4各自独立地具有6-60个C原子，且各自独立地表示经取代或未经取代的苯基、经取代或未经取代的联苯基、经取代或未经取代的三联苯基、经取代或未经取代的四联苯基、经取代或未经取代的萘基、经取代或未经取代的菲基、经取代或未经取代的芴基、经取代或未经取代的螺二芴基、经取代或未经取代的二苯并噻吩基、经取代或未经取代的二苯并呋喃基、或者经取代或未经取代的咔唑基。 The organic compound according to any one of claims 1 to 3, characterized in that Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently have 6 to 60 C atoms, and each independently represents a substituted or Unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted naphthyl , Substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted Substituted dibenzofuranyl, or substituted or unsubstituted carbazolyl.
  5. 根据权利要求4所述的有机化合物，其特征在于，Ar 1、Ar 2、Ar 3、Ar 4各自独立地选自下列结构： The organic compound according to claim 4, wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently selected from the following structures:
    Figure PCTCN2019120526-appb-100004
    Figure PCTCN2019120526-appb-100004
    其中，虚线表示与氮键合的连接位；R 3各自独立地表示甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、环庚基、正辛基、苯基、4-叔丁基苯基、环烷基。 Among them, the dotted line represents the connection site bonded to nitrogen; R 3 independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, n-octyl , Phenyl, 4-tert-butylphenyl, cycloalkyl.
  6. 权利要求1-3中任一项所述的有机化合物的制备方法，包括：二卤代芴酮与溴代联苯加成，成环后依次与不同结构的二芳基胺之间进行C-N偶联反应，分步引入二芳基胺基基团，得到目标化合物。The method for preparing an organic compound according to any one of claims 1 to 3, comprising: addition of a dihalogenated fluorenone and a brominated biphenyl, followed by CN coupling between diarylamines of different structures in turn In the joint reaction, the diarylamine group is introduced step by step to obtain the target compound.
  7. 权利要求3所述的有机化合物的制备方法，包括：The method for preparing an organic compound according to claim 3, comprising:
    由溴代联苯在正丁基锂试剂作用下与二卤代芴酮A加成，得到中间体醇B，水解后环合生成二卤代螺二芴C，再与不同的二芳基胺进行C-N偶联，先得到单二芳基胺取代的化合物D，再得到目标化合物；Addition of brominated biphenyls with dihalofluorenone A under the action of n-butyllithium reagent yields intermediate alcohol B, which is cyclized after hydrolysis to form dihalospirobifluorene C, which is then reacted with different diarylamines Perform CN coupling to obtain compound D substituted by monodiarylamine first, and then obtain the target compound;
    合成工艺如下：The synthesis process is as follows:
    Figure PCTCN2019120526-appb-100005
    Figure PCTCN2019120526-appb-100005
  8. 权利要求3所述的有机化合物的制备方法，包括：The method for preparing an organic compound according to claim 3, comprising:
    由溴代芴酮与二芳基胺进行C-N偶联，得到单二芳基胺取代的芴酮，然后与NBS反应，得到溴代单二芳基胺取代的芴酮，随后在正丁基锂试剂作用下与溴代联苯反应，得到中间体醇，经水解后环合生成单二芳基胺取代的溴代螺二芴，最后再与二芳基胺进行C-N偶联，得到目标化合物；CN coupling of brominated fluorenone and diarylamine to obtain monodiarylamine substituted fluorenone, and then reacted with NBS to obtain brominated monodiarylamine substituted fluorenone, followed by n-butyl lithium Under the action of the reagent, it reacts with the brominated biphenyl to obtain an intermediate alcohol, which is cyclized after hydrolysis to form a monodiarylamine-substituted bromospirobifluorene, and finally CN is coupled with the diarylamine to obtain the target compound;
    合成工艺如下：The synthesis process is as follows:
    Figure PCTCN2019120526-appb-100006
    Figure PCTCN2019120526-appb-100006
  9. 权利要求1-5中任一项所述的有机化合物在OLED器件中的应用。Use of the organic compound according to any one of claims 1 to 5 in OLED devices.
  10. 一种OLED器件，包括：第一电极；设置成面向第一电极的第二电极；以及设置在第一电极与第二电极之间的一个或多个有机材料层，其中有机材料层中的一个或多个层包含权利要求1-5中任一项所述的有机化合物。An OLED device includes: a first electrode; a second electrode disposed facing the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one of the organic material layers Or the multiple layers contain the organic compound according to any one of claims 1-5.
  11. 根据权利要求10所述的OLED器件，其特征在于：有机材料层包括空穴注入层，且空穴注入层包含权利要求1-5中任一项所述的有机化合物。The OLED device according to claim 10, wherein the organic material layer includes a hole injection layer, and the hole injection layer includes the organic compound according to any one of claims 1-5.
  12. 根据权利要求10所述的OLED器件，其特征在于：有机材料层包括空穴注入层，空穴注入层包含权利要求1-5中任一项所述的有机化合物，并且包含以1-20wt％的掺杂浓度掺杂的P型掺杂材料。The OLED device according to claim 10, wherein the organic material layer includes a hole injection layer, the hole injection layer includes the organic compound according to any one of claims 1-5, and contains 1-20wt% P-type doping material doped with a doping concentration.
  13. 根据权利要求10所述的OLED器件，其特征在于：有机材料层包括空穴注入层、空穴传输层，且空穴传输层包含权利要求1-5中任一项所述的有机化合物。The OLED device according to claim 10, wherein the organic material layer includes a hole injection layer and a hole transport layer, and the hole transport layer includes the organic compound according to any one of claims 1-5.
  14. 根据权利要求13所述的OLED器件，其特征在于，空穴注入层仅使用具有下列结构式的化合物HAT-CN：The OLED device according to claim 13, wherein the hole injection layer uses only the compound HAT-CN having the following structural formula:
    Figure PCTCN2019120526-appb-100007
    Figure PCTCN2019120526-appb-100007
  15. 根据权利要求10-14中任一项所述的OLED器件，其特征在于，有机材料层还包括电子阻挡层，电子阻挡层使用以下化学结构的化合物HT2：The OLED device according to any one of claims 10-14, wherein the organic material layer further includes an electron blocking layer, and the electron blocking layer uses the compound HT2 of the following chemical structure:
    Figure PCTCN2019120526-appb-100008
    Figure PCTCN2019120526-appb-100008
  16. 根据权利要求10-14中任一项所述的OLED器件，其特征在于，有机材料层还包括发光层，并且发光层使用化合物EB作为主发光体，化合物BD作为客发光体，其中客发光体的掺杂比例在1-10重量％，两者的化学结构式如下：The OLED device according to any one of claims 10 to 14, wherein the organic material layer further includes a light-emitting layer, and the light-emitting layer uses a compound EB as a main light emitter and a compound BD as a guest light emitter, wherein the guest light emitter The doping ratio is between 1-10% by weight, the chemical structure of the two is as follows:
    Figure PCTCN2019120526-appb-100009
    Figure PCTCN2019120526-appb-100009
  17. 根据权利要求10-14中任一项所述的OLED器件，其特征在于，有机材料层还包括电子传输层，电子传输层使用以下化学结构的化合物ET，并且包含掺杂5重量％的喹啉锂：The OLED device according to any one of claims 10 to 14, wherein the organic material layer further includes an electron transport layer, the electron transport layer uses a compound ET of the following chemical structure, and contains quinoline doped with 5 wt% lithium:
    Figure PCTCN2019120526-appb-100010
    Figure PCTCN2019120526-appb-100010
  18. 根据权利要求10-14中任一项所述的OLED器件，其特征在于，有机材料层还包括电子注入层，电子注入层使用的化合物为氟化锂。The OLED device according to any one of claims 10 to 14, wherein the organic material layer further includes an electron injection layer, and the compound used for the electron injection layer is lithium fluoride.
  19. 根据权利要求10-18中任一项所述的OLED器件，其特征在于：OLED器件为顶部发光型、底部发光型或双向发光型。The OLED device according to any one of claims 10 to 18, characterized in that the OLED device is a top-emission type, a bottom-emission type or a bidirectional-emission type.
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