CN110655486A - Compound with dibenzosuberene as core and application thereof - Google Patents

Compound with dibenzosuberene as core and application thereof Download PDF

Info

Publication number
CN110655486A
CN110655486A CN201810701467.7A CN201810701467A CN110655486A CN 110655486 A CN110655486 A CN 110655486A CN 201810701467 A CN201810701467 A CN 201810701467A CN 110655486 A CN110655486 A CN 110655486A
Authority
CN
China
Prior art keywords
thickness
general formula
compound
layer
group
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.)
Withdrawn
Application number
CN201810701467.7A
Other languages
Chinese (zh)
Inventor
李崇
王芳
张兆超
徐浩杰
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.)
Jiangsu Sanyue Optoelectronic Technology Co Ltd
Original Assignee
Jiangsu Sanyue Optoelectronic 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 Jiangsu Sanyue Optoelectronic Technology Co Ltd filed Critical Jiangsu Sanyue Optoelectronic Technology Co Ltd
Priority to CN201810701467.7A priority Critical patent/CN110655486A/en
Publication of CN110655486A publication Critical patent/CN110655486A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • 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
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/056—Ortho-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/14—Ortho-condensed systems
    • C07D491/147—Ortho-condensed systems the condensed system containing one ring with oxygen as ring hetero atom and two rings with nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/14—Ortho-condensed systems
    • 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
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Landscapes

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

Abstract

The invention discloses a compound taking dibenzosuberene as a core and application thereof, belonging to the technical field of semiconductors. The structure of the compound provided by the invention is shown as a general formula (1):
Figure DDA0001714582310000011
the invention also discloses application of the compound. The compound contains a dibenzosuberene structure, has higher glass transition temperature and molecular thermal stability and proper HOMO and LUMO energy levels, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.

Description

Compound with dibenzosuberene as core and application thereof
Technical Field
The invention relates to a compound taking dibenzosuberene as a core and application thereof, belonging to the technical field of semiconductors.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials sandwiched between different electrode film layers, and various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
Currently, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will be further extended to large-size application fields such as televisions, however, the performance of the OLED device, such as light emitting efficiency and service life, is yet to be further improved compared with the application requirements of the product. The research on improving the performance of the OLED light emitting device mainly includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the structure and the manufacturing process of the OLED device need to be innovated, but also the photoelectric functional material of the OLED needs to be continuously researched and innovated, so as to create the functional material of the OLED with higher performance. The photoelectric functional materials of the OLED applied to the OLED device can be roughly classified into two types from the use point of view, i.e., charge injection transport materials and light emitting materials, the charge injection transport materials can be further classified into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials include host light emitting materials and doping materials. High performance OLED light emitting devices require that various organic functional materials have good optoelectronic properties, for example, as charge transport materials, good carrier mobility, high glass transition temperature, etc., and host materials of the light emitting layer have good ambipolarity and appropriate HOMO/LUMO energy levels.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual requirements of the current OLED display illumination industry, the development of the current OLED material is far behind the requirements of panel manufacturing enterprises, and it is very important to develop higher-performance organic functional materials as a material enterprise.
Disclosure of Invention
One of the objects of the present invention is to provide a dibenzosuberene-based compound. The compound contains a dibenzosuberene structure, has higher glass transition temperature and molecular thermal stability and proper HOMO and LUMO energy levels, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.
The technical scheme for solving the technical problems is as follows:
a dibenzosuberene-based compound is characterized in that the structure of the compound is shown as a general formula (1):
in the general formula (1), Ar is1、Ar2、Ar3、Ar4Each independently represents a single bond, substituted or unsubstituted C6-C30One of arylene, 5-to 30-membered heteroarylene substituted or unsubstituted with one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur; ar (Ar)1、Ar2、Ar3、Ar4The same or different;
x represents a single bond, -O-, -S-, -C (R)9)(R10)-、-N(R11) -or-Si (R)12)(R13)-；
Z is represented by C-R14Or a nitrogen atom; and Z at the bonding site represents a carbon atom;
m, n, p and q are respectively and independently expressed as a number 0 or 1, and m + n + p + q is 1;
the R is1、R2、R3、R4Each independently represents a hydrogen atom or a structure represented by the general formula (2);
Figure BDA0001714582290000031
in the general formula (2), Y represents C-R15Or a nitrogen atom;
said X1Is represented by a single bond, -O-, -S-, -C (R)16)(R17)-、-N(R18) -or-Si (R)19)(R20)-；
The R is5、R6Independently represent a hydrogen atom, a structure represented by general formula (3), general formula (4), general formula (5) or general formula (6); r5、R6The same or different; r5、R6Not hydrogen at the same time;
Figure BDA0001714582290000032
in the general formulae (3) and (4), X is2、X3、X4Independently represent-O-, -S-, -C (R)21)(R22)-、-N(R23) -or-Si (R)24)(R25)-；
Said Y is1Is represented by C-R26Or a nitrogen atom;
general formula (3), general formula (4) and general formula (5) are represented by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL'2-CL’3Key, CL’3-CL’4A bond and a fused ring of formula (2), and Y at the point of attachment represents a carbon atom;
in the general formula (6), R is7、R8Each independently represents substituted or unsubstituted C6-30Aryl, substituted or not with one or more hetero atomsOne of substituted 5-30 membered heteroaryl; the heteroatom is nitrogen, oxygen or sulfur;
the R is9-R13、R16-R25Are each independently represented by C1-C20Alkyl, substituted or unsubstituted C6-C30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r9And R10、R12And R13、R16And R17、R19And R20、R21And R22、R24And R25Can be bonded to each other to form a ring;
the R is14、R15Or R26Each independently represents a hydrogen atom, C1-C20Alkyl, substituted or unsubstituted C6-C30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R14、R15Or R26Can be bonded to each other to form a ring;
the substituent is halogen, cyano, C1-C10Alkyl of (C)6--C30Aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms.
Preferred embodiment, said Ar1、Ar2、Ar3、Ar4Each independently represents a single bond, phenylene, naphthylene, biphenylene, or pyridylene;
the R is7、R8Each independently represents one of phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl or anthryl; wherein the hydrogen in the phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl, or anthracenyl group is optionally substituted with a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl groupPentyl, phenyl, naphthyl, biphenyl or pyridyl;
the R is9-R13、R16-R25Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl; wherein R is9And R10、R12And R13、R16And R17、R19And R20、R21And R22、R24And R25Can be bonded to each other to form a ring;
the R is14、R15Or R26Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group or a furyl group; two or more adjacent R14、R15Or R26May be bonded to each other to form a ring.
Preferably, the structure of the general formula (1) is any one of formulas (i) to (ii):
Figure BDA0001714582290000041
preferably, the structure of the general formula (2) is any one of formulas (1-1) to (1-4):
Figure BDA0001714582290000051
preferably, the structure of the general formula (2) is any one of formulas (1-5) to (1-9):
Figure BDA0001714582290000052
further, the structure of the general formula (1) is any one of T1-T202:
Figure BDA0001714582290000053
Figure BDA0001714582290000071
Figure BDA0001714582290000081
further, R is1、R2、R3、R4Has a structure of any one of H1-H133:
Figure BDA0001714582290000082
Figure BDA0001714582290000091
Figure BDA0001714582290000101
further, the specific structural formula of the compound is:
Figure BDA0001714582290000102
Figure BDA0001714582290000111
Figure BDA0001714582290000121
Figure BDA0001714582290000141
Figure BDA0001714582290000151
Figure BDA0001714582290000161
Figure BDA0001714582290000171
Figure BDA0001714582290000181
Figure BDA0001714582290000191
one kind of (1).
The second objective of the present invention is to provide an organic electroluminescent device. When the compound is applied to an OLED device, the stability of a film layer formed by the material can be kept, and the service life of the OLED device is prolonged.
The technical scheme for solving the technical problems is as follows: an organic electroluminescent device, at least one functional layer contains the dibenzosuberene-based compound.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the functional layer is a light emitting layer and/or an electron blocking layer and/or a hole transport layer.
It is a further object of the present invention to provide an illumination or display device. After the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
The technical scheme for solving the technical problems is as follows: a lighting or display element comprising an organic electroluminescent device as described above.
The invention has the beneficial effects that:
1. the compound takes dibenzo cycloheptene as a framework and is connected with a carbazole derivative long branched chain structure, because the electron donating capability of branched chain groups is different, the HOMO energy level of the whole structure of the compound can be freely adjusted, and the compound with shallow HOMO energy level can be used as a hole transport layer/electron blocking layer material; the material with deep HOMO energy level can be used as the host material of the hole bias type light-emitting layer.
In addition, the dibenzosuberene group is a bipolar group, and the branched chain is a long-chain structure, so that the symmetry of the molecular structure is destroyed, and the intermolecular aggregation effect is avoided; dibenzosuberene is used as a mother nucleus, so that free rotation of the group is avoided, the rigidity of the central mother nucleus group is enhanced, and a branched chain group of the compound also has very strong rigidity, so that molecules are not easy to aggregate and crystallize, and the compound has good film-forming property, higher glass transition temperature and thermal stability. Therefore, when the compound is applied to an OLED device, the stability of a film layer formed by the material can be kept, and the service life of the OLED device is prolonged.
2. The compound of the invention has high triplet state energy level, can effectively block energy loss and is beneficial to energy transfer. Therefore, after the compound is used as an organic electroluminescent functional layer material to be applied to an OLED device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
Drawings
FIG. 1 is a schematic diagram of a device structure to which the compound of the present invention is applied, wherein the components represented by the respective reference numerals are as follows:
1. transparent substrate layer, 2, ITO anode layer, 3, hole injection layer, 4, hole transport layer, 5, electron blocking layer, 6, luminescent layer, 7, hole blocking/electron transport layer, 8, electron injection layer, 9, cathode reflection electrode layer.
Fig. 2 is a graph of efficiency measured at different temperatures for an OLED device of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Taking the synthesis example of intermediate A1:
Figure BDA0001714582290000201
1) adding 0.05mol of bromobiphenyl and 0.05mol of Mg powder and 60ml of tetrahydrofuran into a 250ml three-neck flask in the atmosphere of introducing nitrogen, heating to 70 ℃, carrying out reflux reaction for 4 hours, and completely reacting to generate a Grignard reagent; adding 0.05mol of 2-bromo-5-dibenzocycloheptenone and 50ml of tetrahydrofuran into a 250ml three-neck flask in the atmosphere of introducing nitrogen, stirring and dissolving, dropwise adding the Grignard reagent, reacting at 60 ℃ for 24 hours to generate a large amount of white precipitate, and finally adding saturated NHCl4Converting the grignard salt to an alcohol; after the reaction is finished, extracting with diethyl ether, drying and rotary steaming, and mixing petroleum ether: purifying the dichloromethane mixed solvent (3:2) by a silica gel column to obtain solid tertiary alcohol with yellowish color, wherein the HPLC purity is 98.9 percent, and the yield is 85.1 percent;
elemental analysis Structure (molecular formula C)27H19BrO): theoretical value C, 73.81; h, 4.36; br, 18.19; o, 3.64; test values are: c, 73.83; h, 4.34; br, 18.18; and O, 3.65. HPLC-MS: the molecular weight of the material is 439.35, and the measured molecular weight is 439.46.
2) 0.04mol of the tertiary alcohol and 100ml of dichloromethane are mixed with stirring, 8ml of boron trifluoride-diethyl ether complex is added dropwise at room temperature, the reaction is carried out for 30 minutes, 20ml of ethanol and 20ml of water are added for quenching, the reaction is extracted by dichloromethane (20ml × 3), drying and rotary evaporation are carried out, the petroleum ether silica gel column is used for purification, and the reaction product is purified by ethanol: recrystallizing dichloromethane (volume ratio is 1:1) to obtainIntermediate a1, HPLC purity 99.2%, yield 74.3%; elemental analysis Structure (molecular formula C)27H17Br): theoretical value C, 76.97; h, 4.07; br, 18.96; test values are: c, 77.02; h, 4.13; br, 18.99.
HPLC-MS: the molecular weight of the material is 421.34, and the measured molecular weight is 421.37.
Intermediate a was prepared by the synthetic method of intermediate a1, the specific structure is shown in table 1.
TABLE 1
Figure BDA0001714582290000211
Example 1: synthesis of Compound 1
Figure BDA0001714582290000222
Adding 0.01mol of intermediate A1, 0.012mol of raw material B1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, then adding 0.03mol of sodium tert-butoxide, 5 multiplied by 10-5mol Pd2(dba)3，5×10-5Heating the mol tri-tert-butylphosphine to 105 ℃, carrying out reflux reaction for 24 hours, sampling a point plate, and indicating that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and passing through a neutral silica gel column to obtain a target product, wherein the HPLC purity is 99.1%, and the yield is 82.7%;
elemental analysis Structure (molecular formula C)48H33N): theoretical value C, 92.42; h, 5.33; n, 2.25; test values are: c, 92.45; h, 5.35; and N, 2.28. ESI-MS (M/z) (M)+): theoretical value is 623.80, found 623.87.
Example 2: synthesis of Compound 5
Figure BDA0001714582290000231
Adding 0.01mol of intermediate A1, 0.012mol of raw material B2 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, then adding 0.03mol of sodium tert-butoxide, 5 multiplied by 10-5mol Pd2(dba)3，5×10-5Heating the mol tri-tert-butylphosphine to 105 ℃, carrying out reflux reaction for 24 hours, sampling a point plate, and indicating that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and passing through a neutral silica gel column to obtain a target product, wherein the HPLC purity is 99.3%, and the yield is 82.7%;
elemental analysis Structure (molecular formula C)51H32N2): theoretical value C, 91.04; h, 4.79; n, 4.16; test values are: c, 91.08; h, 4.83; n, 4.22. ESI-MS (M/z) (M)+): theoretical value is 672.83, found 672.88.
Example 3: synthesis of Compound 27
Figure BDA0001714582290000232
Compound 27 was prepared as in example 1, except intermediate a2 was used in place of intermediate a1 and starting material B3 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)45H27NO): theoretical value C, 90.43; h, 4.55; n, 2.34; o, 2.68; test values are: c, 90.47; h, 4.59; n, 2.37; o, 2.72. ESI-MS (M/z) (M)+): theoretical value is 597.72, found 597.76.
Example 4: synthesis of Compound 36
Figure BDA0001714582290000241
Compound 36 was prepared as in example 1, except intermediate a2 was substituted for intermediate a1 and intermediate B4 was substituted for starting material B1.
Elemental analysis Structure (molecular formula C)44H26N2O): theoretical value C, 88.27; h, 4.38; n, 4.68; o, 2.67; test values are: c, 88.32; h, 4.42; n, 4.73; o, 2.73. ESI-MS (M/z) (M)+): theoretical value is 598.70, found 598.77.
Example 5: synthesis of compound 37:
Figure BDA0001714582290000242
compound 40 was prepared as in example 1, except intermediate a2 was used in place of intermediate a1 and starting material B5 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)48H33N): theoretical value C, 92.42; h, 5.33; n, 2.25; test values are: c, 92.47; h, 5.38; and N, 2.29. ESI-MS (M/z) (M)+): theoretical value is 623.80, found 623.87.
Example 6: synthesis of Compound 49
Figure BDA0001714582290000243
Compound 49 was prepared as in example 1, except intermediate A3 was used in place of intermediate a 1.
Elemental analysis Structure (molecular formula C)48H33N): theoretical value C, 92.42; h, 5.33; n, 2.25; test values are: c, 92.45; h, 5.37; and N, 2.29. ESI-MS (M/z) (M)+): theoretical value is 623.80, found 623.87.
Example 7: synthesis of Compound 53
Figure BDA0001714582290000251
Compound 60 was prepared as in example 1, except intermediate A3 was used in place of intermediate a1 and starting material B2 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)51H32N2): theoretical value C, 91.04; h, 4.79; n, 4.16; test values are: c, 91.07; h, 4.83; and N, 4.25. ESI-MS (M/z) (M)+): theoretical value is 672.83, found 672.88.
Example 8: synthesis of Compound 68
Compound 68 was prepared as in example 1, except that starting material B6 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)51H34N2): theoretical value C, 90.77; h, 5.08; n, 4.15; test values are: c, 90.79; h, 5.13; n, 4.19. ESI-MS (M/z) (M)+): theoretical value is 674.85, found 674.92.
Example 9: synthesis of Compound 81
Figure BDA0001714582290000253
Compound 80 was prepared as in example 1, except intermediate a4 was used in place of intermediate a1 and starting material B7 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)48H33N): theoretical value C, 92.42; h, 5.33; n, 2.25; test values are: c, 92.47; h, 5.38; and N, 2.29. ESI-MS (M/z) (M)+): theoretical value is 623.80, found 623.84.
Example 10: synthesis of Compound 89
Figure BDA0001714582290000261
Compound 89 was prepared as in example 1, except that intermediate a4 was used in place of intermediate a1 and starting material B8 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)45H27NO): theoretical value C, 90.43; h, 4.55; n, 2.34; o, 2.68; test values are: c, 90.48; h, 4.57; n, 2.37; o, 2.72. ESI-MS (M/z) (M)+): theoretical value is 597.72, found 597.78.
Example 11: synthesis of compound 97:
compound 97 was prepared as in example 1, except intermediate a5 was used in place of intermediate a1 and starting material B9 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)47H32N2): theoretical value C, 90.35; h, 5.16; n, 4.48; test values are: c, 90.38; h, 5.19; n, 4.53. ESI-MS (M/z) (M)+): theoretical value is 624.79, found 624.83.
Example 12: synthesis of Compound 102
Figure BDA0001714582290000263
Compound 102 is prepared as in example 1, except that intermediate A1 is replaced with intermediate A6 and starting material B1 is replaced with starting material B3
Elemental analysis Structure (molecular formula C)45H27NO): theoretical value C, 90.43; h, 4.55; n, 2.34; o, 2.68; test values are: c, 90.47; h, 4.58; n, 2.37; o, 2.73. ESI-MS (M/z) (M)+): theoretical value is 597.72, found 597.79.
Example 13: synthesis of Compound 118
Figure BDA0001714582290000271
Compound 118 is prepared as in example 1, except that intermediate A6 is substituted for intermediate A1 and intermediate B10 is substituted for the starting material B1
Elemental analysis Structure (molecular formula C)47H32N2): theoretical value C, 90.35; h, 5.16; n, 4.48; test values are: c, 90.37; h, 5.18; n, 4.52. ESI-MS (M/z) (M)+): theoretical value is 624.79, found 624.83.
Example 14: synthesis of Compound 126
Figure BDA0001714582290000272
At 250mIn a three-necked flask, 0.01mol of intermediate A6, 0.012mol of raw material B13 and 150ml of toluene were added under nitrogen protection, stirred and mixed, and then 0.02mol of sodium carbonate and 1X 10 mol of sodium carbonate were added-4mol Pd(PPh3)4Heating to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and passing through a neutral silica gel column to obtain a target product, wherein the HPLC purity is 99.35%, and the yield is 78.1%; elemental analysis Structure (molecular formula C)51H31NO): theoretical value C, 90.91; h, 4.64; n, 2.08; o, 2.37; test values are: c, 90.93; h, 4.63; n, 2.09; o, 2.35. ESI-MS (M/z) (M)+): theoretical value is 673.81, found 673.97.
Example 15: synthesis of Compound 136
Figure BDA0001714582290000281
Compound 136 was prepared as in example 14, except intermediate A3 was used in place of intermediate a6 and starting material B14 was used in place of starting material B13.
Elemental analysis Structure (molecular formula C)54H37N): theoretical value C, 92.67; h, 5.33; n, 2.00; test values are: c, 92.65; h, 5.33; and N, 2.03. ESI-MS (M/z) (M)+): theoretical value is 699.90, found 700.11.
Example 16: synthesis of Compound 140
Figure BDA0001714582290000282
Compound 140 was prepared as in example 14, except intermediate A3 was used in place of intermediate a6 and starting material B15 was used in place of starting material B13.
Elemental analysis Structure (molecular formula C)57H36N2): theoretical value C, 91.41; h, 4.85; n, 3.74; test values are: c, 91.42; h, 4.84; n, 3.74. ESI-MS (M/z) (M)+): theoretical value is 748.93, found 749.11.
Example 17: synthesis of Compound 151
Figure BDA0001714582290000283
Compound 151 was prepared as in example 1, except intermediate a4 was used in place of intermediate a1 and starting material B12 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)49H31N): theoretical value C, 92.86; h, 4.93; n, 2.21; test values are: c, 92.91; h, 4.97; and N, 2.25. ESI-MS (M/z) (M)+): theoretical value is 633.79, found 633.84.
Example 18: synthesis of Compound 168
Figure BDA0001714582290000291
Compound 168 was prepared as in example 1, except intermediate A8 was used in place of intermediate a1 and starting material B8 was used in place of starting material B1.
Elemental analysis Structure (molecular formula C)49H35NO): theoretical value C, 90.01; h, 5.40; n, 2.14; o, 2.45; test values are: c, 90.08; h, 5.43; n, 2.17; o, 2.53. ESI-MS (M/z) (M)+): theoretical value is 653.82, found 653.87.
Example 19: synthesis of Compound 193
Figure BDA0001714582290000292
Compound 193 was prepared as in example 1, except intermediate a9 was used instead of intermediate a1 and starting material B5 was used instead of starting material B1.
Elemental analysis Structure (molecular formula C)56H49N): theoretical value C, 91.39; h, 6.71; n, 1.90; test values are: c, 91.43; h, 6.76; and N, 1.96. ESI-MS (M/z) (M)+): theoretical value is 736.01, found 736.09.
Example 20: synthesis of Compound 220
Figure BDA0001714582290000301
Compound 220 was prepared as in example 14, except intermediate a9 was used in place of intermediate a6 and starting material B16 was used in place of starting material B13.
Elemental analysis Structure (molecular formula C)62H53N): theoretical value C, 91.70; h, 6.58; n, 1.72; test values are: c, 91.72; h, 6.57; n, 1.71. ESI-MS (M/z) (M)+): theoretical value is 812.11, found 812.24.
The organic compound is used in a light-emitting device, has high glass transition temperature (Tg) and triplet state energy level (T1), and suitable HOMO and LUMO energy levels, and can be used as a material of a hole transport layer/an electron blocking layer and a material of a light-emitting layer. The thermal performance, T1 energy level and HOMO energy level of the compound of the present invention and the existing material were measured, respectively, and the results are shown in table 1.
TABLE 1
Figure BDA0001714582290000302
Figure BDA0001714582290000311
Note: the triplet state energy level T1 is measured by Hitachi F4600 fluorescence spectrometer, and the test condition of the material is 2X 10-5A toluene solution of (4); the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the highest occupied molecular orbital HOMO energy level and the lowest occupied molecular orbital LUMO energy level were measured by a photoelectron emission spectrometer (AC-2 type PESA) in an atmospheric environment.
As can be seen from the data in the table above, compared with currently applied NPB, CBP and TPAC materials, the organic compound of the invention has high glass transition temperature, can improve the phase stability of the film material, and further improve the service life of the device; the material and the application material have similar HOMO energy levels and high triplet state energy levels (T1), and can block energy loss of a light-emitting layer, so that the light-emitting efficiency of the device is improved. Therefore, after the organic material containing dibenzosuberene is applied to different functional layers of an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.
The application effect of the synthesized OLED material of the present invention in the device is detailed by device examples 1-20 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2-20 and the device comparative example 1 of the present invention have the same manufacturing process, and adopt the same substrate material and electrode material, and the film thickness of the electrode material is also kept consistent, except that the device embodiments 1-10 change the material of the light emitting layer in the device; device examples 11-20 were prepared by changing the hole transport layer/electron blocking layer materials of the devices, and the results of the performance tests of the devices obtained in each example are shown in table 2.
Device example 1
As shown in fig. 1, a method for manufacturing an electroluminescent device includes the following steps:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes;
b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3;
c) evaporating a hole transport material NPB (N-propyl bromide) on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 60nm, and the hole transport layer is a hole transport layer 4;
d) evaporating an electron blocking material TPAC (thermoplastic vulcanizate) on the hole transport layer 4 in a vacuum evaporation mode, wherein the thickness of the electron blocking material TPAC is 20nm, and the electron blocking layer 5 is formed on the hole transport layer;
e) a luminescent layer 6 is evaporated on the electron blocking layer 5, the host materials are the compound 1 and the compound GH prepared in the embodiment of the invention, and the doping material is Ir (ppy)3Compound 1, GHN and Ir (ppy)3The mass ratio of the three is 50:50:10, and the thickness is 30 nm;
f) an electron transport material TPBI is evaporated on the light-emitting layer 6 in a vacuum evaporation mode, the thickness of the TPBI is 40nm, and the organic material of the TPBI layer is used as a hole blocking/electron transport layer 7;
g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 7, wherein the layer is an electron injection layer 8;
h) vacuum evaporating cathode Al (100nm) on the electron injection layer 8, which is a cathode reflection electrode layer 9;
after the electroluminescent device was fabricated according to the above procedure, the driving voltage and current efficiency of the device were measured, and the results are shown in table 2. The molecular structural formula of the related material is shown as follows:
Figure BDA0001714582290000321
device example 2
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: Compound 5 prepared in the example of the present invention and Ir (ppy)3Mixed in a weight ratio of 88: 12)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 3
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: Compound 53 prepared in the example of the present invention and Ir (ppy)3Mixed and doped in a weight ratio of 92: 8)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 4
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light-emitting layer 6 (thickness: 60 nm)Degree: 40nm, material: compounds 68, GH and Ir (ppy) prepared in the examples of the invention3A mixed composition of 45:45:10 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 5
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: Compound 89, GH and Ir (ppy) prepared in the example of the present invention)3Blended in a weight ratio of 46:46: 8)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 6
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: Compound 97, GH and Ir (ppy) prepared in the example of the present invention)3A mixed composition of 45:45:10 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 7
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: Compound 102, GH and Ir (ppy) prepared in the example of the present invention)3A mixed composition of 47:47:6 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 8
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron-blocking layerBarrier layer 5 (thickness: 20nm, material: TAPC)/light-emitting layer 6 (thickness: 40nm, material: Compound 126, GH and Ir (ppy) prepared in the examples of the present invention)3A mixed composition of 45:45:10 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 9
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: Compound 140, GH and Ir (ppy) prepared in the example of the present invention)3A mixed composition of 45:45:10 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 10
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: Compound 151, GH and Ir (ppy) prepared in the example of the present invention)3A mixed composition of 45:45:10 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 11
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 27 prepared in example of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 12
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/voidHole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 36 prepared in the examples of the present invention)/light emitting layer 6 (thickness: 40nm, materials: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 13
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 37 prepared in the example of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 14
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 49 prepared in example of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 15
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 81 prepared in the examples of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP, GH and Ir (ppy)3A mixed composition of 47:47:6 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 16
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness):10 nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: compound 118 prepared in the present example)/light-emitting layer 6 (thickness: 40nm, material: CBP, GH and Ir (ppy)3A mixed composition of 45:45:10 by weight ratio)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 17
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 136 prepared in the example of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP, GH and Ir (ppy)3Blended in a weight ratio of 46:46: 8)/hole blocking/electron transporting layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 18
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 168 prepared in the example of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 19
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 193 prepared in example of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device example 20
ITO anode layer2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: Compound 220 prepared in example of the present invention)/light-emitting layer 6 (thickness: 40nm, materials: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
Device comparative example 1
ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 60nm, material: NPB)/electron blocking layer 5 (thickness: 20nm, material: TAPC)/light emitting layer 6 (thickness: 40nm, material: CBP and Ir (ppy)3Mixed and doped at a weight ratio of 90: 10)/hole blocking/electron transport layer 7 (thickness: 35nm, material: TPBI)/electron injection layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100 nm).
The inspection data of the obtained electroluminescent device are shown in Table 2.
TABLE 2
Numbering Current efficiency (cd/A) Color(s) LT95 Life (Hr) @5000nits
Device example 1 57.8 Green light 45.2
Device example 2 53.2 Green light 42.7
Device example 3 49.7 Green light 39.3
Device example 4 58.2 Green light 41.8
Device example 5 60.8 Green light 44.1
Device example 6 58.9 Green light 40.5
Device example 7 52.1 Green light 39.4
Device example 8 59.7 Green light 41.8
Device example 9 60.5 Green light 44.7
Device example 10 57.6 Green light 39.9
Device example 11 50.7 Green light 38.4
Device example 12 49.3 Green light 36.1
Device example 13 47.9 Green light 37.9
Device example 14 49.2 Green light 39.1
Device example 15 50.8 Green light 39.7
Device example 16 49.5 Green light 39.9
Device example 17 48.7 Green light 35.2
Device example 18 50.2 Green light 32.3
Device example 19 53.1 Green light 37.3
Device example 20 50.7 Green light 31.8
Device comparative example 1 32.5 Green light 14.3
From the results in table 2, it can be seen that the organic compound of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative examples, the efficiency and lifetime of the organic compound are greatly improved compared with those of the known OLED materials, especially the lifetime of the organic compound is greatly prolonged.
The efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, and the results of efficiency tests of device examples 1, 9 and 18 and device comparative example 1 at-10-80 ℃ are shown in Table 3 and FIG. 2.
TABLE 3
As can be seen from the data in table 3, device examples 1, 9, and 18 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is steadily increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A dibenzosuberene-based compound is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0001714582280000011
in the general formula (1), Ar is1、Ar2、Ar3、Ar4Each independently represents a single bond, substituted or unsubstituted C6-C30One of arylene, 5-to 30-membered heteroarylene substituted or unsubstituted with one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur; ar (Ar)1、Ar2、Ar3、Ar4The same or different;
x represents a single bond, -O-, -S-, -C (R)9)(R10)-、-N(R11) -or-Si (R)12)(R13)-；
Z is represented by C-R14Or a nitrogen atom; and Z at the bonding site represents a carbon atom;
m, n, p and q are respectively and independently expressed as a number 0 or 1, and m + n + p + q is 1;
the R is1、R2、R3、R4Respectively independent representationIs a hydrogen atom or a structure represented by the general formula (2);
Figure FDA0001714582280000012
in the general formula (2), Y represents C-R15Or a nitrogen atom;
said X1Is represented by a single bond, -O-, -S-, -C (R)16)(R17)-、-N(R18) -or-Si (R)19)(R20)-；
The R is5、R6Independently represent a hydrogen atom, a structure represented by general formula (3), general formula (4), general formula (5) or general formula (6); r5、R6The same or different; r5、R6Not hydrogen at the same time;
Figure FDA0001714582280000013
in the general formulae (3) and (4), X is2、X3、X4Independently represent-O-, -S-, -C (R)21)(R22)-、-N(R23) -or-Si (R)24)(R25)-；
Said Y is1Is represented by C-R26Or a nitrogen atom;
general formula (3), general formula (4) and general formula (5) are represented by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL'2-CL’3Key, CL’3-CL’4A bond and a fused ring of formula (2), and Y at the point of attachment represents a carbon atom;
in the general formula (6), R is7、R8Each independently represents substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms; the heteroatom is nitrogen, oxygen or sulfur;
the R is9-R13、R16-R25Are each independently represented by C1-C20Alkyl, substituted or unsubstituted C6-C30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; r9And R10、R12And R13、R16And R17、R19And R20、R21And R22、R24And R25Can be bonded to each other to form a ring;
the R is14、R15Or R26Each independently represents a hydrogen atom, C1-C20Alkyl, substituted or unsubstituted C6-C30One of an aryl group and a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms; two or more adjacent R14、R15Or R26Can be bonded to each other to form a ring;
the substituent is halogen, cyano, C1-C10Alkyl of (C)6-C30Aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms; the heteroatom is selected from oxygen, nitrogen or sulfur.
2. The dibenzocycloheptene-based compound of claim 1, wherein Ar is Ar1、Ar2、Ar3、Ar4Each independently represents a single bond, phenylene, naphthylene, biphenylene, or pyridylene;
the R is7、R8Each independently represents one of phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl or anthryl; wherein the hydrogen in the phenyl, biphenyl, naphthyl, carbazolyl, benzofuranyl, benzothienyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-spirofluorenyl, pyridyl, quinolyl, isoquinolyl, pyrimidyl, phenanthryl, or anthracenyl group is optionally substituted with a fluorine atom, cyano, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, or pyridylSubstituted with one or more of;
the R is9-R13、R16-R25Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl; wherein R is9And R10、R12And R13、R16And R17、R19And R20、R21And R22、R24And R25Can be bonded to each other to form a ring;
the R is14、R15Or R26Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a biphenyl group, a pyridyl group or a furyl group; two or more adjacent R14、R15Or R26May be bonded to each other to form a ring.
3. The dibenzocycloheptene-based compound of claim 1, wherein the structure of the general formula (1) is any one of formulae (i) to (ii):
Figure FDA0001714582280000031
4. the dibenzocycloheptene-based compound of claim 1, wherein the structure of the general formula (2) is any one of formulae (1-1) to (1-4):
Figure FDA0001714582280000032
5. the dibenzocycloheptene-based compound of claim 1, wherein the structure of the general formula (2) is any one of formulae (1-5) to (1-9):
Figure FDA0001714582280000041
6. the dibenzosuberene-cored compound of claim 1, wherein the compound has the following structure:
Figure FDA0001714582280000042
Figure FDA0001714582280000051
Figure FDA0001714582280000061
Figure FDA0001714582280000091
Figure FDA0001714582280000101
Figure FDA0001714582280000111
Figure FDA0001714582280000121
Figure FDA0001714582280000122
one kind of (1).
7. An organic electroluminescent device, characterized in that at least one functional layer contains a dibenzocycloheptene-based compound according to any one of claims 1 to 6.
8. An organic electroluminescent device according to claim 7, wherein the functional layer is a light-emitting layer and/or an electron-blocking layer and/or a hole-transporting layer.
9. A lighting or display element comprising the organic electroluminescent device according to claim 7 or 8.
CN201810701467.7A 2018-06-29 2018-06-29 Compound with dibenzosuberene as core and application thereof Withdrawn CN110655486A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810701467.7A CN110655486A (en) 2018-06-29 2018-06-29 Compound with dibenzosuberene as core and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810701467.7A CN110655486A (en) 2018-06-29 2018-06-29 Compound with dibenzosuberene as core and application thereof

Publications (1)

Publication Number Publication Date
CN110655486A true CN110655486A (en) 2020-01-07

Family

ID=69026829

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810701467.7A Withdrawn CN110655486A (en) 2018-06-29 2018-06-29 Compound with dibenzosuberene as core and application thereof

Country Status (1)

Country Link
CN (1) CN110655486A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109265399A (en) * 2018-08-09 2019-01-25 石家庄诚志永华显示材料有限公司 Compound and organic electroluminescent device
CN110655471A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Compound taking spiro dibenzosuberene fluorene as core and application of compound in organic electroluminescent device
CN116332828A (en) * 2021-12-10 2023-06-27 四川大学 Dibenzocycloheptanone derivatives and application thereof in OLED (organic light emitting diode) device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106467740A (en) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 A kind of organic electroluminescence fluorescent chemicalses and its application in electroluminescent device
CN106467510A (en) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 A kind of electroluminescent organic material and its application
CN106467469A (en) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 A kind of organic electroluminescent compounds and its application
CN110416422A (en) * 2018-04-28 2019-11-05 江苏三月光电科技有限公司 Organic electroluminescence device and display including it

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106467740A (en) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 A kind of organic electroluminescence fluorescent chemicalses and its application in electroluminescent device
CN106467510A (en) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 A kind of electroluminescent organic material and its application
CN106467469A (en) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 A kind of organic electroluminescent compounds and its application
CN110416422A (en) * 2018-04-28 2019-11-05 江苏三月光电科技有限公司 Organic electroluminescence device and display including it

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655471A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Compound taking spiro dibenzosuberene fluorene as core and application of compound in organic electroluminescent device
CN109265399A (en) * 2018-08-09 2019-01-25 石家庄诚志永华显示材料有限公司 Compound and organic electroluminescent device
CN109265399B (en) * 2018-08-09 2022-05-13 石家庄诚志永华显示材料有限公司 Compound and organic electroluminescent device
CN116332828A (en) * 2021-12-10 2023-06-27 四川大学 Dibenzocycloheptanone derivatives and application thereof in OLED (organic light emitting diode) device

Similar Documents

Publication Publication Date Title
CN107021926B (en) Compound containing azaspirofluorene and nitrogen-containing six-membered heterocycle and application of compound in OLED
CN107586261B (en) Organic compound containing spiro dibenzosuberene fluorene and application thereof
KR102144446B1 (en) Organic Compound for organic light emitting diode and an organic light emitting diode including the same with long life
CN110964021A (en) Compound with fluorene as core, preparation method and application thereof
CN111662225A (en) Organic compound containing pyrene and application thereof
CN110551135A (en) Compound containing aza five-membered fused ring and application thereof in organic electroluminescent device
CN111662258A (en) Organic compound containing pyrene and application thereof in OLED
KR20140072295A (en) Deuteriated organometallic complex and organic light-emitting diode including the same
CN110835318B (en) Organic compound with azafluorene as core and preparation method and application thereof
CN107602397B (en) Compound with dibenzosuberene as core and application thereof
CN110835304A (en) Compound with spirofluorene structure as core, preparation method and application thereof
CN110885338A (en) Organic compound with triarylamine as core, preparation method and application thereof
CN111377957A (en) Boron-containing compound and application thereof in organic electroluminescent device
CN110655486A (en) Compound with dibenzosuberene as core and application thereof
KR20190086895A (en) Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof
CN110577523B (en) Compound containing triarylamine structure and organic electroluminescent device prepared from compound
CN110642732B (en) Organic compound containing spirofluorene anthrone structure and application thereof
CN109796450B (en) Compound with pyridoindole as core and application thereof in electroluminescent device
CN109574908B (en) Compound containing spirodimethyl anthracene fluorene and application thereof in organic electroluminescent device
CN110294735B (en) Compound with anthracene and phenanthrene as core and application of compound in organic electroluminescent device
CN110963904A (en) Compound with ketone and fluorene as cores, preparation method and application thereof
CN110835305B (en) Organic compound containing dibenzosuberene, preparation method and application thereof
KR102118688B1 (en) Compound for organic light emitting diode, organic light emitting diode having the same, and display apparatus having organic light emitting diode
CN110734381B (en) Compound with triarylamine as core and preparation method and application thereof
CN110577545B (en) Triarylamine compound and application thereof in organic electroluminescent device

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
CB02 Change of applicant information

Address after: 214112 No. 210, Xinzhou Road, Wuxi, Jiangsu

Applicant after: Jiangsu March Technology Co.,Ltd.

Address before: 214112 No. 210, Xinzhou Road, Wuxi, Jiangsu

Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd.

CB02 Change of applicant information
WW01 Invention patent application withdrawn after publication

Application publication date: 20200107

WW01 Invention patent application withdrawn after publication