CN110872315A - 一种有机化合物和使用该化合物的有机电致发光器件 - Google Patents

一种有机化合物和使用该化合物的有机电致发光器件 Download PDF

Info

Publication number
CN110872315A
CN110872315A CN201911196557.6A CN201911196557A CN110872315A CN 110872315 A CN110872315 A CN 110872315A CN 201911196557 A CN201911196557 A CN 201911196557A CN 110872315 A CN110872315 A CN 110872315A
Authority
CN
China
Prior art keywords
organic
layer
compound
electroluminescent device
organic electroluminescent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911196557.6A
Other languages
English (en)
Inventor
赵晓宇
汪华月
华万鸣
黄娣
钱烨
杨金萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Hua Hui Photoelectric Technology Co Ltd
Original Assignee
Zhejiang Hua Hui Photoelectric Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Hua Hui Photoelectric Technology Co Ltd filed Critical Zhejiang Hua Hui Photoelectric Technology Co Ltd
Priority to CN201911196557.6A priority Critical patent/CN110872315A/zh
Publication of CN110872315A publication Critical patent/CN110872315A/zh
Priority to PCT/CN2020/112988 priority patent/WO2021103728A1/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/20—Spiro-condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明公开了一种应用于有机电致发光领域的一种有机化合物和使用该化合物的有机电致发光器件，该有机化合物的分子结构式为结构式I所示结构。
Figure DDA0002294776570000011
其特征在于，结构式I中，A1至A4独立地选自取代或未取代的C6‑C60的芳基或杂芳基，其中杂芳基含有选自B、N、O、S、Si及P中至少一个杂原子，且较佳地至少一个N；X独立的选自O、S、Se、C(R)2、Si(R)2、NR、P(＝O)R或羰基；其中R选自H、CN、烷基、芳基。本发明一种有机化合物，具有较好的热稳定性，较高的三线态能级，能够平衡空穴和电子的传递，能量传递更加充分，能有效提高器件的效率和寿命。

Description

一种有机化合物和使用该化合物的有机电致发光器件
技术领域
本发明涉及有机电致发光领域的一种有机化合物和使用该化合物的有机电致发光器件，具体为三苯胺衍生物和使用该化合物的有机电致发光器件。
背景技术
有机电致发光器件(OLED:Organic Light EmissionDiodes)有视角广阔、响应速度快、色彩质量高、可实现柔性发光等优点，具有广阔的应用前景。OLED器件通常是类三明治结构，包括正负电极膜层及夹在电极膜层之间的有机功能材料层。对OLED器件的电极施加电压，正电荷从正极注入，负电荷从负极注入，在电场作用下正负电荷在有机层中迁移相遇复合发光。已被广泛应用于新型照明灯具、智能手机及平板电脑等产品的显示面板，进一步还将向电视等大尺寸显示产品应用领域扩展，是一种发展快、技术要求高的新型显示技术。
一个效率好寿命长的有机电致发光器件通常是器件结构与各种有机材料的优化搭配的结果。常见的OLED器件通常包括以下种类的有机材料：空穴注入材料、空穴传输材料、电子传输材料，以及各色的发光材料(染料或者掺杂客体材料)和相应的主体材料等。
现在的磷光电致发光器件中大多采用主客体结构，即将磷光发射物质以一定的浓度掺杂在主体物质中，以避免三重态-三重态湮灭，提高磷光发射效率。作为现有的蓝光主体材料是基于蒽的稠环类衍生物，如专利CN1914293B、CN102448945B、US2015287928A1等所述，然而这些化合物存在发光效率和亮度不充分及器件寿命较差的问题。作为现有技术的发蓝光客体化合物，可采用的是芳基乙烯基胺类化合物(WO 04/013073,WO 04/016575,WO04/018587)。然而，这些化合物的热稳定性差，易分解，导致器件的寿命差，是目前产业上OLED材料最主要的缺点。此外，这些化合物的色纯度差，难以实现深蓝色的发光。另外，US7233019、KR 2006-0006760等专利公开了利用芳基胺取代基的芘系化合物的有机电致发光元件，但是因为蓝光的色纯度低，很难实现深蓝发光。
在磷光主体材料中，最常使用的是空穴传输型主体材料。这类材料的分子中含有电子给体，如咔唑和三苯胺结构，具有空穴传输的特点。三苯胺具有很高的三线态能级，ET为3.04eV，经常使用空的穴传输材料TAPC、TcTa、TPD等都是三苯胺的衍生物。大多数三苯胺的衍生物的HOMO能级要比咔唑衍生物高，大概为-5.3eV，而且它与ITO的功函数接近，HOMO也与空穴传输材料NPB接近，有利于空穴的注入，因此它们适合于做电致磷光主体材料。但是由于三苯胺分子结构是扭曲的，缺少刚性，使得三苯胺衍生物的热稳定性和形貌稳定性不够好，这影响了它们的实际应用。所以关于三苯胺衍生物作为磷光主体材料的报道不是很多。为了提高三苯胺的刚性结构，Yang课题组合成了桥联结构的三苯胺衍生物FATPA，[“Afully diarylmethylene-bridged triphenylamine derivative as novel host forhighly efficient green phosphorescent OLEDs”,Org.Lett.2009,11,1503.]它是通过苯胺的邻位与二苯甲烷的亚甲基连接，三苯胺形成了接近平面的环状结构，这样的结构使得分子具有较高的玻璃转化温度，Tg为178℃。该分子同时保持了较高的三线态能级(ET＝2.78eV)和HOMO(-5.22eV)能级。
相对于红色磷光材料和绿色磷光材料，蓝色磷光材料是开发得最晚的，也是最不成熟的。这主要是由蓝色磷光波长短能级高，为了获得短波长发光，就必须拉大配体的能隙，即通过修配体的化学结构来拉大配体的HOMO和LUMO的能级，但是，这样又会导致配体和金属之间的配位键的减弱，一方面使得配合物的稳定性降低，配合物容易发生键断裂，而且会加速配合物以非辐射方式衰减会到基态，使磷光效率降低。因此，在蓝色磷光材料中，波长的蓝移和高效发光是一对矛盾，同时兼有两者是两难的选择。同时这也是器件的结构中起发光作用的磷光掺杂材料往往要搭配的主体材料使用的原因，但蓝色磷光材料的三线态能级比较高，所以常常需要比其三线态能级高的主体材料与之相匹配，这样才能保证将能量传递给客体蓝色磷光材料，释放出磷光。如果主体材料的三线态能级低于蓝色磷光材料的三线态能级，则能量会传递到主体材料上释放，而主体材料是纯的有机化合物，在室温下是看不到磷光的，所以器件的发光效率会降低。同时现有的蓝光材料存在热稳定性差，易分解，导致器件的寿命差；色纯度差，难以实现深蓝色的发光，因此在体现天然颜色的全彩色显示器方面有问题。因此，仍需进一步改进材料。高性能的蓝光材料一直是人们的开发重点。
本发明化合物不对称的结构特性提高器件效率，热稳定性、成膜等性能，本专利比较相对合成路线简单。本发明的有机化合物应用于OLED器件中的发光层，并当作蓝光材料使用，本发明化合物三苯胺与芴连接起来三苯胺衍生物，由于螺环上的C原子阻断了三苯胺与其它苯环的共轭，使得分子的三线态得到了维持，具有较高的三线态能级，能量传递更加充分；电子和空穴的传递更加平衡，器件的效率和寿命更高。
发明内容
本发明为解决常用蓝色磷光材料的玻璃化温度较低，材料本身稳定性不高，且在高亮度下具有高效率滚降，阻碍其广泛使用的问题，而提供一种有机化合物、其合成方法及其在有机电致发光领域的应用。该有机化合物的分子结构如结构式I所示：
Figure BDA0002294776550000031
其中，结构式I中，A1至A4独立地选自取代或未取代的C6-C60的芳基或杂芳基，其中杂芳基含有选自B、N、O、S、Si及P中至少一个杂原子，且较佳地至少一个N；X独立的选自O、S、Se、C(R)2、Si(R)2、NR、P(＝O)R或羰基，其中R选自H、CN、烷基、芳基。
优选的，本发明一种有机化合物独立地选自下列化合物：
Figure BDA0002294776550000041
Figure BDA0002294776550000051
Figure BDA0002294776550000061
Figure BDA0002294776550000071
Figure BDA0002294776550000081
本发明还提供了一种有机电致发光器件，该器件包括阴极层、阳极层和有机层，该有机层包括空穴注入层、空穴传输层、发光层、空穴阻挡层、电子注入层或电子传输层中至少一层，其中有机层中至少有一层含有如结构式I所表示的化合物。
其中，结构式I所表示的磷光一种有机化合物如前所述。
进一步的，结构式I所表示的一种有机化合物作为有机电致发光器件发光层的一种有机材料。
进一步的，结构式I所表示的一种有机化合物作为有机电致发光器件发光层的客体掺杂剂。
进一步的，如结构式I所表示的化合物可以单独使用在有机电致发光器件中，或和其他化合物混合使用；如结构式I所表示的化合物可以使用其中一种化合物，也可以同时使用结构式I中的两种或两种以上化合物；单独使用一种选自结构式I所述的化合物，或同时使用两种以上选自结构式I所述的化合物。
在本发明中，所述发光层可以为红色、黄色或蓝色发光层。在本发明中，所述发光层为蓝色发光层时，采用上述所述的有机电致器件用化合物作为蓝色主体或蓝色掺杂，可得到高效率、高分辨率、高亮度及长寿命的有机电致器件。
在本发明中，所述有机物层优选包括电子传输层，所述电子传输层包括上述技术方案所述的有机电致器件用化合物。在本发明中，所述电子传输层优选还包括金属化合物。
在本发明中，所述有机物层优选包括发光层和电子传输层，所述发光层和电子传输层均含有上述技术方案所述的有机电致器件用化合物，所述发光层和电子传输层中的有机化合物可以相同也可以不同。
本发明对所述有机电致器件的制备方法没有特殊的限制，除了使用式(I)的有机电致器件用化合物之外，采用本领域技术人员熟知的发光器件的制备方法和材料制备得到即可。
本发明所述的有机电致器件是有机光伏器件、有机发光器件(OLED)、有机太阳电池(OSC)、电子纸(e-paper)、有机感光体(OPC)、有机薄膜晶体管(OTFT)及有机内存器件(Organic Memory Element)中任意一种。
在本发明中，有机电致器件是可以利用喷溅涂覆法、电子束蒸发、真空蒸镀等方法在基板上蒸镀金属或具有导电性的氧化物以及它们的合金形成阳极；在制备得到的阳极表面按顺序蒸镀空穴注入层、空穴传输层、发光层、空气阻挡层和电子传输层，以后再蒸镀阴极的方法制备。以上方法以外基板上按阴极、有机物层、阳极顺序蒸镀制作有机电致器件。所述有机物层是也可以包括空穴注入层、空穴传输层、发光层、空穴阻挡层及电子传输层等多层结构。在本发明中有机物层是采用高分子材料按溶剂工程(旋转涂膜(spin-coating)、薄带成型(tape-casting)、刮片法(doctor-blading)、丝网印刷(Screen-Printing)、喷墨印刷或热成像(Thermal-Imaging)等)替代蒸镀方法制备，可以减少器件层数。
根据本发明的有机电致器件所使用的材料可以分为顶发射、低发射或双面发射。根据本发明实施方案的有机电致器件的化合物可以有机发光器件类似的原理适用于有机太阳能电池、照明的OLED、柔性OLED、有机感光体，有机薄膜晶体管等电致器件方面。
与现有技术相比，本发明的有益效果是：
本发明新型磷光一种有机化合物分子量比较大，通过单键连接的多个共轭平面基团，空间对称性差，不易结晶分解，提高了材料的玻璃化温度，保证了材料长时间蒸镀不被分解；.本发明的有机化合物应用于电致发光器件，具有较大的三线态能级T1能够阻挡激子扩散，提高器件的效率和寿命；本发明的有机磷光一种有机化合物能够平衡空穴和电子的传递，提高器件的寿命。
附图说明
图1为本发明的一种有机电致发光二极管器件结构层图；
其中，110代表基板，120表示阳极，130表示空穴注入层，140表示空穴传输层，150表示发光层，160表示空穴阻挡层，170表示电子传输层，180表示电子注入层，190表示阴极。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合具体实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
中间体的合成流程：
Figure BDA0002294776550000101
Figure BDA0002294776550000111
1.中间体1-a的合成
向500ml圆底烧瓶反应器中投入3-溴-2-碘苯甲酸甲酯(25.0g,73mmol)、2-溴苯硼酸(17.7g,88mmol)、四(三苯基膦)钯(1.7g,0.15mmol)、碳酸钾(20.2g,146.7mmol)，并投入甲苯125mL、四氢呋喃125mL、水50mL。在氮气条件下，使反应器的温度上升到80℃，并搅拌10小时，待反应完毕，将反应器的温度降低至室温，并用乙酸乙酯提取并分离有几层。将有机层减压浓缩后通过柱层析法进行分离，从而获得中间体1-a(15.1g,收率，61％)。
2.中间体1-b的合成
向500ml圆底烧瓶反应器中投入中间体1-a(15.1g,44.5mmol)、氢氧化钠(2.14g,54mmol)加热回流搅拌使其反应48小时，待反应完毕，将反应器的温度降低至室温，在冷却的溶液中滴加盐酸酸化，将生成的固体搅拌30分钟之后过滤。利用二氯甲烷和正己烷进行重结晶，从而获得中间体1-b(14.1g,收率，89％)。
3.中间体1-c的合成
向250ml圆底烧瓶中投入中间体1-b(14.1g,39.6mmol)、甲磺酸145mL，并加热至80℃反应3小时。利用薄层色谱法确认反应借宿之后冷却至室温。将反应溶液缓慢滴加到冰水150mL之后搅拌30分钟。并将生成的固体过滤之后用水和甲醇进行清洗而获得了中间体1-c(11.1g,收率，83％)。
4.中间体2-a的合成
在氮气氛围下，将中间体1-c(11.1g,32.9mmol)、2,2'-联苯二硼酸：8.0g,33.1mmol)、四(三苯基膦)钯(0)：1.1g、碳酸氢钠：10.0g、甲苯：100mL、乙醇：50mL、水：50mL投入烧瓶中，进行12小时的加热回流搅拌。冷却至室温(25℃)后，将反应溶液转移至分液漏斗中，用甲苯进行萃取。之后，将有机层用硫酸钠进行干燥，进行过滤、浓缩。将残渣用硅胶柱色谱进行纯化，得到了白色固体2-a(6.3g产率58％)。
5.中间体2-b的合成
在1L圆底烧瓶中加入2-a(6.3g,19.1mmol)、二氯甲烷180mL并常温搅拌。将溴(3.4mL,66mmol)稀释滴加到二氯甲烷50mL，常温下搅拌8小时，反应完毕后在反应容器中国投入丙酮100mL并搅拌。将生成的固体过滤之后利用丙酮进行清洗。用一氯苯重结晶固体而获得中间体2-b(7.2g,收率，77％)。
6.中间体4-c的合成
Figure BDA0002294776550000121
在250mL圆底烧瓶中加入4-a(6.2g,25.0mmol)和四氢呋喃100mL，并在氮气氛围下冷却至-78℃。在冷却的反应溶液中将正丁基锂(0.026mol)在相同温度下滴加。将反应溶液反应2小时后，分多次每次加入小量的中间体2-b(7.2g,14.7mmol)，并在常温下搅拌。当反应溶液颜色改变时，利用TLC确认反应结束。投入H2O 50mL使反应结束，并利用乙酸乙酯和水进行萃取。将有机层进行非减压浓缩，然后利用乙腈进行重结晶而获得中间体4-b(7.8g,收率，81％)。
在250mL圆底烧瓶中加入4-b(7.8g,11.8mmol)和醋酸120mL、硫酸2mL，并搅拌回流5小时。当固体生成时，利用薄层色谱法确认反应结束，冷却至室温。生成的固体过滤后用水、甲醇清洗，肉厚溶解在一氯苯并进行硅胶过滤、浓缩之后常温冷却，从而获得中间体4-c(6.8g,收率，90％)。生成的化合物通过用LC-MS确定。LC-MS：M/Z 641.0(M+H)+。
7.中间体5-c的合成
Figure BDA0002294776550000131
中间体5-c的合同方法同中间体4-c，合成获得中间体5-c(6.9g)。生成的化合物通过用LC-MS确定。LC-MS：M/Z 656.9(M+H)+。
实施例1
化合物C-6的合成
Figure BDA0002294776550000132
在250mL圆底烧瓶中加入(6.8g,10.6mmol)、二(4-甲基苯基)胺(5.0g,25.4mol)、Pd2(dba)3(0.08g,0.4mmol)、叔丁醇钠(3.4g,0.035mol)、三叔丁基膦(0.07g,0.4mmol)、甲苯60mL,并回流搅拌2小时。在反应完毕之后常温冷却。利用二氯甲烷和水对反应溶液进行萃取。分离有机层，并用硫酸镁进行干燥，然后减压浓缩。利用柱层析法对物质进行分离提纯，后利用二氯甲烷和丙酮进行重结晶而获得化合物C-6(3.7g,40％)。生成的化合物通过用LC-MS确定。LC-MS:M/Z 873.3(M+H)+。理论元素含量(％)C65H48N2O：C,89.42；H,5.54；N,3.21；O,1.83。上述结果证实获得产物为目标产品。
实施例2
化合物C-9的合成
Figure BDA0002294776550000133
化合物C-9的合成步骤如上述反应式，制备及确认方法同化合物C-6，可获得化合物C-9(4.4g,38％)。LC-MS：M/Z 1081.4(M+H)+。
实施例3
化合物C-11的合成
Figure BDA0002294776550000141
化合物C-11的合成步骤如上述反应式，制备及确认方法同化合物C-6，可获得化合物C-9(4.7g,40％)。LC-MS：M/Z 1121.4(M+H)+。
实施例4
化合物C-20的合成
Figure BDA0002294776550000142
化合物C-20的合成步骤如上述反应式，制备及确认方法同化合物C-6，可获得化合物C-9(4.1g,44％)。LC-MS：M/Z 881.3(M+H)+。
实施例5
化合物C-28的合成
Figure BDA0002294776550000151
化合物C-28的合成步骤如上述反应式，制备及确认方法同化合物C-6，可获得化合物C-28(4.3g,39％)。LC-MS：M/Z 1050.3(M+H)+。
实施例6
化合物C-38的合成
Figure BDA0002294776550000152
化合物C-38的合成步骤如上述反应式，制备及确认方法同化合物C-6，可获得化合物C-38(4.4g,45％)。LC-MS：M/Z 917.3(M+H)+。
实施例7
化合物C-43的合成
Figure BDA0002294776550000153
化合物C-43的合成步骤如上述反应式，制备及确认方法同化合物C-6，可获得化合物C-43(3.7g,40％)。LC-MS：M/Z 861.3(M+H)+。
本发明还通过热蒸镀的方式制备了8个底发光器件(各个具体的器件结构如下：
器件实施例：
将费希尔公司涂层厚度为
Figure BDA00022947765500001612
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，再用蒸馏水反复清洗2次，超声波洗涤10分钟，蒸馏水清洗结束后，采用异丙醇、丙酮、甲醇溶剂按顺序进行超声波洗涤后干燥，将干燥后的基板转移到等离子体清洗机里，将上述基板洗涤5分钟后送到蒸镀机里。
在已经清洗好的ITO透明电极上依次蒸镀空穴注入层2-TNATA蒸镀厚度为
Figure BDA0002294776550000161
空穴传输层a-NPD蒸镀厚度为
Figure BDA0002294776550000162
ADN(9,10-二(2-萘基)蒽)和5％的BD1～BD3或本发明一种有机化合物蒸镀厚度为
Figure BDA0002294776550000163
空穴阻挡层及电子传输层TPBi蒸镀厚度为
Figure BDA0002294776550000164
LiF蒸镀厚度为
Figure BDA0002294776550000165
和Al蒸镀厚度为
Figure BDA0002294776550000166
形成阴极；上述过程有机物蒸镀速度保持
Figure BDA0002294776550000167
/sec，LiF的蒸镀速度为
Figure BDA0002294776550000168
Al的蒸镀速度为
Figure BDA0002294776550000169
Figure BDA00022947765500001610
表1为本发明实施例和比较例制备得到的有机发光器件的性能检测结果。
[表1]
Figure BDA00022947765500001611
Figure BDA0002294776550000171
从上述表1结果中，采用本发明提供的有机电致器件用化合物制备有机电致器件，有机电致器件的发光效率和寿命特性显著提高。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (7)

1.一种应用于有机电致发光领域的有机化合物，该有机化合物的分子结构式为结构式I所示结构；
Figure FDA0002294776540000011
其特征在于，结构式I中，A1至A4独立地选自取代或未取代的C6-C60的芳基或杂芳基，其中杂芳基含有选自B、N、O、S、Si及P中至少一个杂原子，且较佳地至少一个N；X独立的选自O、S、Se、C(R)2、Si(R)2、NR、P(＝O)R或羰基，其中R选自H、CN、烷基、芳基。
2.根据权利要求1所述的一种应用于有机电致发光领域的有机化合物，其特征在于：所述有机化合物独立地选自下列化合物：
Figure FDA0002294776540000012
Figure FDA0002294776540000021
Figure FDA0002294776540000031
Figure FDA0002294776540000041
Figure FDA0002294776540000051
Figure FDA0002294776540000061
3.一种有机电致发光器件，包括阴极层、阳极层和有机层，该有机层包括空穴注入层、空穴传输层、发光层、空穴阻挡层、电子注入层、电子传输层中的至少一层，其特征在于：该器件的有机层中至少有一层含有如权利要求1所述的有机化合物。
4.根据权利要求3所述的有机电致发光器件，其特征在于，有机电致发光器件发光层中含有权利要求1所述的化合物。
5.根据权利要求3或权利要求4所述的有机电致发光器件，其特征在于，权利要求1所述的化合物在有机电致发光器件发光层中作为客体掺杂剂使用。
6.根据权利要求3所述的有机电致发光器件，其特征在于，权利要求1所述的化合物可以单独使用，或和其他化合物混合使用。
7.根据权利要求3所述的有机电致发光器件，其特征在于，单独使用一种选自如权利要求2所述的有机化合物，或同时使用两种或两种以上选自如权利要求2所述的有机化合物。
CN201911196557.6A 2019-11-29 2019-11-29 一种有机化合物和使用该化合物的有机电致发光器件 Pending CN110872315A (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201911196557.6A CN110872315A (zh) 2019-11-29 2019-11-29 一种有机化合物和使用该化合物的有机电致发光器件
PCT/CN2020/112988 WO2021103728A1 (zh) 2019-11-29 2020-09-02 一种有机化合物和使用该化合物的有机电致发光器件

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911196557.6A CN110872315A (zh) 2019-11-29 2019-11-29 一种有机化合物和使用该化合物的有机电致发光器件

Publications (1)

Publication Number Publication Date
CN110872315A true CN110872315A (zh) 2020-03-10

Family

ID=69717436

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911196557.6A Pending CN110872315A (zh) 2019-11-29 2019-11-29 一种有机化合物和使用该化合物的有机电致发光器件

Country Status (2)

Country Link
CN (1) CN110872315A (zh)
WO (1) WO2021103728A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170974A (zh) * 2019-12-31 2020-05-19 浙江华显光电科技有限公司 一种主体化合物和使用该化合物的电致发光器件
WO2021103728A1 (zh) * 2019-11-29 2021-06-03 浙江华显光电科技有限公司 一种有机化合物和使用该化合物的有机电致发光器件

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101035878A (zh) * 2004-09-24 2007-09-12 Lg化学株式会社 新型化合物以及使用该化合物的有机发光器件（10）
CN109400485A (zh) * 2018-11-27 2019-03-01 长春海谱润斯科技有限公司 一种芳香胺化合物及其有机电致发光器件
WO2019103397A1 (ko) * 2017-11-24 2019-05-31 주식회사 두산 유기 화합물 및 이를 포함하는 유기 전계 발광 소자
KR20190085880A (ko) * 2018-01-11 2019-07-19 주식회사 엘지화학 다환 화합물 및 이를 포함하는 유기 발광 소자

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10608185B2 (en) * 2016-10-17 2020-03-31 Univeral Display Corporation Organic electroluminescent materials and devices
US11917843B2 (en) * 2017-07-26 2024-02-27 Universal Display Corporation Organic electroluminescent materials and devices
KR102141293B1 (ko) * 2018-01-11 2020-08-05 주식회사 엘지화학 다환 화합물 및 이를 포함하는 유기 발광 소자
CN110872315A (zh) * 2019-11-29 2020-03-10 浙江华显光电科技有限公司 一种有机化合物和使用该化合物的有机电致发光器件

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101035878A (zh) * 2004-09-24 2007-09-12 Lg化学株式会社 新型化合物以及使用该化合物的有机发光器件（10）
WO2019103397A1 (ko) * 2017-11-24 2019-05-31 주식회사 두산 유기 화합물 및 이를 포함하는 유기 전계 발광 소자
KR20190085880A (ko) * 2018-01-11 2019-07-19 주식회사 엘지화학 다환 화합물 및 이를 포함하는 유기 발광 소자
CN109400485A (zh) * 2018-11-27 2019-03-01 长春海谱润斯科技有限公司 一种芳香胺化合物及其有机电致发光器件

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021103728A1 (zh) * 2019-11-29 2021-06-03 浙江华显光电科技有限公司 一种有机化合物和使用该化合物的有机电致发光器件
CN111170974A (zh) * 2019-12-31 2020-05-19 浙江华显光电科技有限公司 一种主体化合物和使用该化合物的电致发光器件
CN111170974B (zh) * 2019-12-31 2023-07-04 浙江华显光电科技有限公司 一种主体化合物和使用该化合物的电致发光器件

Also Published As

Publication number Publication date
WO2021103728A1 (zh) 2021-06-03

Similar Documents

Publication Publication Date Title
CN105431407B (zh) 有机电致发光元件和电子仪器
KR101823704B1 (ko) 아미노안트라센 유도체 및 그것을 이용한 유기 전기 발광 소자
KR101826730B1 (ko) 오원자 헤테로 고리를 포함하는 유기전기소자용 화합물, 이를 포함하는 유기전기소자 및 그 전자 장치
CN109748898B (zh) 有机电致发光化合物及其制备方法和有机电致发光器件
KR20110018688A (ko) 티안트렌 구조를 가지는 화합물 및 이를 이용한 유기전기소자, 그 단말
CN113248532B (zh) 一种有机化合物及含有该化合物的有机光电元件与应用
CN111116628A (zh) 一种有机化合物和使用该化合物的有机电致发光器件
CN110078755B (zh) 化合物、显示面板以及显示装置
KR20130024521A (ko) 유기전기소자용 신규 화합물, 이를 이용하는 유기전기소자 및 그 전자 장치
CN111170974B (zh) 一种主体化合物和使用该化合物的电致发光器件
KR20120054154A (ko) 화합물 및 이를 이용한 유기전기소자, 그 단말
KR20110129767A (ko) 헤테로 원자를 포함하는 카바졸과 플루오렌이 융합된 화합물 및 이를 이용한 유기전기소자, 그 단말
US10991890B2 (en) Compound containing a 5-membered heterocycle and organic light-emitting diode using same, and terminal for same
KR20220115617A (ko) 화합물, 이의 응용 및 이를 포함하는 유기 전계 발광 소자
WO2021103728A1 (zh) 一种有机化合物和使用该化合物的有机电致发光器件
KR20130102669A (ko) 사이클로 펜타 페난트렌을 포함하는 유기전기소자용 화합물, 이를 포함하는 유기전기소자 및 그 전자 장치
KR102201028B1 (ko) 유기전자소자용 화합물, 이를 포함하는 유기전자소자 및 유기전자소자를 포함하는 표시장치
KR20120112257A (ko) 신규한 화합물 및 이를 포함하는 유기전계발광소자
KR102118688B1 (ko) 유기전자소자용 화합물, 이를 포함하는 유기전자소자 및 유기전자소자를 포함하는 표시장치
CN114560870B (zh) 一种含硫多环芳香族化合物及其应用
CN115160273A (zh) 一种含有二苯并杂环的化合物及其制备方法和应用
CN113004262B (zh) 一种有机材料及其应用
JP6860765B6 (ja) 化合物及びこれを含む有機発光素子
CN109734607B (zh) 一种有机化合物及其有机电致器件和有机发光器件
KR20130102428A (ko) 아민 유도체를 포함하는 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200310

RJ01 Rejection of invention patent application after publication