WO2021136197A1 - 含氮化合物、电子元件和电子装置 - Google Patents

含氮化合物、电子元件和电子装置 Download PDF

Info

Publication number
WO2021136197A1
WO2021136197A1 PCT/CN2020/140289 CN2020140289W WO2021136197A1 WO 2021136197 A1 WO2021136197 A1 WO 2021136197A1 CN 2020140289 W CN2020140289 W CN 2020140289W WO 2021136197 A1 WO2021136197 A1 WO 2021136197A1
Authority
WO
WIPO (PCT)
Prior art keywords
nitrogen
transport layer
hole transport
containing compound
layer
Prior art date
Application number
PCT/CN2020/140289
Other languages
English (en)
French (fr)
Inventor
马天天
杨雷
Original Assignee
陕西莱特光电材料股份有限公司
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 陕西莱特光电材料股份有限公司 filed Critical 陕西莱特光电材料股份有限公司
Priority to US17/622,744 priority Critical patent/US11535602B1/en
Publication of WO2021136197A1 publication Critical patent/WO2021136197A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • 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
    • 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
    • H10K85/657—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/156—Hole transporting layers comprising a multilayered structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • This application relates to the technical field of organic materials, in particular to a nitrogen-containing compound, an electronic component and an electronic device containing the nitrogen-containing compound.
  • Such electronic components such as organic electroluminescent devices or photoelectric conversion devices, usually include a cathode and an anode disposed oppositely, and a functional layer disposed between the cathode and the anode.
  • the functional layer is composed of multiple organic or inorganic film layers, and generally includes an energy conversion layer, a hole transport layer between the energy conversion layer and the anode, and an electron transport layer between the energy conversion layer and the cathode.
  • the electronic element when it is an organic electroluminescence device, it generally includes an anode, a hole transport layer, an organic light-emitting layer as an energy conversion layer, an electron transport layer, and a cathode that are stacked in sequence.
  • anode When voltage is applied to the cathode and anode, the two electrodes generate an electric field. Under the action of the electric field, the electrons on the cathode side move to the organic light-emitting layer, and the holes on the anode side also move to the organic light-emitting layer. The electrons and holes are combined in the organic light-emitting layer.
  • Excitons the excitons are in an excited state and release energy to the outside, so that the organic light-emitting layer emits light to the outside.
  • the purpose of this application is to provide a nitrogen-containing compound, an electronic component and an electronic device, which can improve the performance of the electronic component.
  • a nitrogen-containing compound is provided, and the structure of the nitrogen-containing compound is shown in Chemical Formula 1:
  • L 1 is And in L 1 , "#" represents the connection point of the phenylene group of L 1 and N, and “##” represents the connection point of the phenylene group of L 1 and ⁇ ;
  • L 2 is And in L 2 , "#” represents the connection point between the phenylene group of L 2 and N, and "##” represents the connection point between the phenylene group of L 2 and R 4;
  • R 1 is selected from methyl or phenyl
  • R 2 is selected from methyl or phenyl
  • R 3 is selected from the group represented by H, CA1 ⁇ CA10;
  • R 4 is selected from phenyl group, the substituent represented by CA1 ⁇ CA10; and
  • R 3 and R 4 have one and only one selected from the group represented by CA1 ⁇ CA10 Base;
  • the structure of CA1 ⁇ CA10 is as follows:
  • an electronic component including an anode and a cathode disposed oppositely, and a functional layer provided between the anode and the cathode; the functional layer includes the first aspect of the present application The nitrogen-containing compound.
  • an electronic device includes the electronic component described in the second aspect of the present application.
  • the hole transport layer can inject holes into the organic light-emitting layer as the energy conversion layer more smoothly, or it can make the photoelectric conversion layer as the energy conversion layer inject holes into the electron transport layer more smoothly.
  • the nitrogen-containing compound has good hole transport efficiency, and the introduction of dibenzofuran group or dibenzothiophene group may increase the conjugation plane of the nitrogen-containing compound of the present application, and may cause intermolecular Stacking and crystallization lead to reduced device life.
  • the stacking effect of the compound can be effectively reduced, and the film-forming performance of the nitrogen-containing compound can be improved.
  • the introduction of specific substituents at the ortho position of the nitrogen atom on the aryl group reduces the planarity of the triarylamine core group itself, which can further increase the HOMO energy level and reduce the intermolecular Stacking effect. Therefore, the nitrogen-containing compound of the present application is suitable for use in the hole transport layer of organic electroluminescent devices, especially the second hole transport layer suitable for organic electroluminescent devices, which can reduce the driving voltage of organic electroluminescent devices. Reduce, improve the current efficiency, power efficiency and external quantum efficiency of the organic electroluminescent device, and increase the life of the organic electroluminescent device.
  • FIG. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present application.
  • Fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
  • FIG. 3 is a schematic structural diagram of a photoelectric conversion device according to an embodiment of the present application.
  • FIG. 4 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
  • Figure 5 is a hydrogen spectrum of compound 392.
  • Figure 6 is a synthetic route diagram of compound 1.
  • Anode; 200 cathode; 300, functional layer; 310, hole injection layer; 320, hole transport layer; 321, first hole transport layer; 322, second hole transport layer; 330, organic light emitting layer 340, electron transport layer; 350, electron injection layer; 360, photoelectric conversion layer; 400, electronic device; 500, electronic device.
  • an aryl group refers to an optional functional group or substituent derived from an aromatic hydrocarbon ring.
  • the aryl group can be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group can be a monocyclic aryl group, a condensed ring aryl group, two or more monocyclic aryl groups conjugated by a carbon-carbon bond, through A monocyclic aryl group and a fused ring aryl group conjugated by carbon-carbon bonds, and two or more fused ring aryl groups conjugated by a carbon-carbon bond. That is, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in the present application.
  • the aryl group does not contain heteroatoms such as B, N, O, S, or P.
  • biphenyl, terphenyl, etc. are aryl groups.
  • aryl groups include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, pyrenyl, Base and so on.
  • the heteroaryl group may be a heteroaryl group including at least one of B, O, N, P, Si, and S as a heteroatom.
  • the heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group.
  • the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated through carbon-carbon bonds, and any aromatic
  • the ring system is an aromatic monocyclic ring or an aromatic fused ring.
  • heteroaryl groups include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, three Azinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyridine Azinopyrazinyl, isoquinolyl, indolyl, carbazolyl, N-phenylcarbazolyl, N-pyridylcarbazolyl, N-methylcarbazolyl, benzoxazolyl, benzene Bisimidazolyl, benzothiazo
  • each... are independently” and “... are independently” and “... are independently selected from” are interchangeable, and should be understood in a broad sense, which can be either It means that in different groups, the specific options expressed between the same symbols do not affect each other, or it can mean that the specific options expressed between the same symbols do not affect each other in the same group.
  • the non-positioned link in this application refers to the single bond extending from the ring system It means that one end of the link can be connected to any position in the ring system that the bond penetrates, and the other end is connected to the rest of the compound molecule.
  • the phenanthryl group represented by the formula (X') is connected to other positions of the molecule through a non-positional linkage extending from the middle of the benzene ring on one side, and
  • the meaning includes any possible connection modes shown in formula (X'-1) to formula (X'-4).
  • this application provides a nitrogen-containing compound whose structure is as follows:
  • L 1 is And in L 1 , "#" represents the connection point of the phenylene group of L 1 and N, and "##" represents the connection point of the phenylene group of L 1 and ⁇ ;
  • L 2 is And in L 2 , "#" represents the connection point between the phenylene group of L 2 and N, and "##" represents the connection point between the phenylene group of L 2 and R 4;
  • R 1 is selected from methyl or phenyl
  • R 2 is selected from methyl or phenyl
  • R 3 is selected from the group represented by H, CA1 ⁇ CA10;
  • R 4 is selected from phenyl group, the substituent represented by CA1 ⁇ CA10; and
  • R 3 and R 4 have one and only one selected from the group represented by CA1 ⁇ CA10 Base;
  • the structure of CA1 ⁇ CA10 is as follows:
  • a dibenzofuran group or a dibenzothiophene group a dibenzofuran group or a dibenzothiophene group has a strong electron dissociation energy, so it can effectively reduce the content of
  • the HOMO energy level of the nitrogen compound allows the hole transport layer to inject holes into the organic light-emitting layer as the energy conversion layer more smoothly, or it can make the photoelectric conversion layer as the energy conversion layer inject holes into the electron transport layer more smoothly , So that the nitrogen-containing compound has a good hole transport efficiency.
  • the voltage performance and efficiency performance of the electronic component using the nitrogen-containing compound can be effectively improved, for example, the luminous efficiency of the organic electroluminescent device can be improved and the driving voltage can be reduced, and the photoelectric efficiency of the photoelectric conversion device can also be improved and the open circuit can be improved.
  • Voltage The introduction of dibenzofuran groups or dibenzothiophene groups may increase the conjugation plane of the nitrogen-containing compound of the present application, and may cause intermolecular stacking and crystallization, resulting in reduced device life. In order to overcome diphenyl The possible adverse effects of the parafuran group or the dibenzothiophene group. Some of the nitrogen-containing compounds in this application also introduce a large sterically hindered cycloalkane structure.
  • the cycloalkane group can effectively reduce the nitrogen-containing compound of the application. Stacking effect, and can improve the film-forming performance of nitrogen-containing compounds.
  • the preparation and test results of organic electroluminescent devices show that the introduction of cycloalkane groups improves the life of organic electroluminescent devices, which shows that it overcomes the adverse effects of dibenzofuran groups or dibenzothiophene groups and Effectively improve the film-forming performance of the nitrogen-containing compound, reduce the flatness of the nitrogen-containing compound itself, especially reduce the intermolecular stacking effect of the nitrogen-containing compound, which makes the life of the electronic component using the nitrogen-containing compound of the present application prolonged .
  • the nitrogen-containing compound of the present application has better hole transport performance, lower HOMO energy level, lower intermolecular stacking effect and better film-forming performance, and can improve photoelectric conversion devices and electroluminescent devices, etc. Voltage performance, efficiency performance and life performance of electronic components.
  • the introduction of specific substituents at the ortho position of the nitrogen atom on the aryl group reduces the planarity of the triarylamine core group itself, which can further increase the HOMO energy level and reduce the intermolecular Stacking effect. Therefore, the nitrogen-containing compound of the present application is suitable for use in the hole transport layer of organic electroluminescent devices, especially the second hole transport layer suitable for organic electroluminescent devices, which can reduce the driving voltage of organic electroluminescent devices. Reduce, improve the current efficiency, power efficiency and external quantum efficiency of the organic electroluminescent device, and increase the life of the organic electroluminescent device.
  • Ar is selected from 2-DBF, 3-DBF, 2-DBT, 3-DBT; wherein, the structural formulas of 2-DBF, 3-DBF, 2-DBT, and 3-DBT are as follows:
  • the nitrogen-containing compound is selected from the group consisting of various compounds listed in Table 1:
  • Ar of compound 1294 is 3-DBT, and L 1 is L 2 is R 3 is H and R 4 is CA10. Then, the structural formula of compound 1294 is:
  • the present application also provides an electronic component.
  • the electronic component includes an anode and a cathode disposed oppositely, and a functional layer provided between the anode and the cathode; the functional layer includes the one provided in the first aspect of the application Of nitrogen-containing compounds.
  • the nitrogen-containing compound provided in the present application can be used to form at least one organic film layer in the functional layer to improve the voltage characteristics, efficiency characteristics, and life characteristics of electronic components.
  • the organic film layer containing the nitrogen-containing compound of the present application is located between the anode and the energy conversion layer of the electronic element, so as to improve the transport of holes between the anode and the energy conversion layer.
  • the functional layer includes a hole transport layer
  • the hole transport layer includes the nitrogen-containing compound provided in the present application.
  • the hole transport layer may be composed of the nitrogen-containing compound provided in the present application, or may be composed of the nitrogen-containing compound provided in the present application and other materials.
  • the hole transport layer includes a first hole transport layer and a second hole transport layer, and the first hole transport layer is closer to the surface of the anode than the second hole transport layer; the first hole transport The layer and/or the second hole transport layer include the nitrogen-containing compound provided in the present application.
  • the first hole transport layer and the second hole transport layer may contain the nitrogen-containing compound provided by the present application, or both the first hole transport layer and the second hole transport layer may contain the present application The nitrogen-containing compounds provided.
  • the first hole transport layer and the second hole transport layer may or may not contain other materials.
  • the second hole transport layer is composed of the nitrogen-containing compound.
  • the electronic component may be an organic electroluminescence device.
  • the organic electroluminescent device may include an anode 100, a first hole transport layer 321, a second hole transport layer 322, an organic light emitting layer 330 as an energy conversion layer, an electron transport layer 340, and a cathode 200 that are sequentially stacked.
  • the nitrogen-containing compound provided in this application can be applied to the second hole transport layer 322 of an organic electroluminescent device to increase the life of the organic electroluminescent device, increase the luminous efficiency of the organic electroluminescent device, and reduce the organic electroluminescent device.
  • the driving voltage is not limited to increase the driving voltage.
  • the anode 100 includes an anode material, which is preferably a material with a large work function (work function) that facilitates injection of holes into the functional layer.
  • anode materials include, but are not limited to: metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combined metals and oxides such as ZnO: Al or SnO 2 : Sb; or conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-di (Oxy)thiophene] (PEDT), polypyrrole and polyaniline. It is preferable to include a transparent electrode containing indium tin oxide (ITO) as an anode.
  • ITO indium tin oxide
  • the first hole transport layer 321 may include one or more hole transport materials, and the hole transport materials may be selected from carbazole polymers, carbazole-linked triarylamine compounds or other types of compounds.
  • the application does not impose special restrictions on this.
  • the first hole transport layer 321 may be composed of the compound NPB.
  • the organic light-emitting layer 330 may be composed of a single light-emitting material, and may also include a host material and a guest material.
  • the organic light-emitting layer 330 is composed of a host material and a guest material. The holes injected into the organic light-emitting layer 330 and the electrons injected into the organic light-emitting layer 330 can recombine in the organic light-emitting layer 330 to form excitons. The energy is transferred to the host material, and the host material transfers energy to the guest material, so that the guest material can emit light.
  • the host material of the organic light-emitting layer 330 may be a metal chelate compound, a bisstyryl derivative, an aromatic amine derivative, a dibenzofuran derivative or other types of materials, which are not particularly limited in this application.
  • the host material of the organic light-emitting layer 330 may be CBP.
  • the guest material of the organic light-emitting layer 330 can be a compound with a condensed aryl ring or a derivative thereof, a compound with a heteroaryl ring or a derivative thereof, an aromatic amine derivative or other materials, and this application does not make any special considerations for this. limit.
  • the guest material of the organic light-emitting layer 330 may be a green phosphorescent material, for example, Ir(ppy) 3 or the like.
  • the electron transport layer 340 can be a single-layer structure or a multi-layer structure, and it can include one or more electron transport materials.
  • the electron transport materials can be selected from, but not limited to, benzimidazole derivatives and oxadiazole derivatives. , Quinoxaline derivatives or other electron transport materials.
  • the electron transport layer 340 may be composed of DBimiBphen and LiQ.
  • the cathode 200 includes a cathode material, which is a material with a small work function that facilitates the injection of electrons into the functional layer.
  • cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or their alloys; or multilayer materials such as LiF/Al , Liq/Al, LiO 2 /Al, LiF/Ca, LiF/Al and BaF 2 /Ca. It is preferable to include a metal electrode containing aluminum as a cathode.
  • a hole injection layer 310 may be further provided between the anode 100 and the first hole transport layer 321 to enhance the ability of injecting holes into the first hole transport layer 321.
  • the hole injection layer 310 can be selected from benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives or other materials, which are not particularly limited in this application.
  • the hole injection layer 310 may be composed of m-MTDATA.
  • an electron injection layer 350 may be further provided between the cathode 200 and the electron transport layer 340 to enhance the ability to inject electrons into the electron transport layer 340.
  • the electron injection layer 350 may include inorganic materials such as alkali metal sulfides and alkali metal halides, or may include complexes of alkali metals and organic substances.
  • the electron injection layer 350 may include LiQ.
  • the electronic component may be a photoelectric conversion device.
  • the photoelectric conversion device may include an anode 100 and a cathode 200 disposed oppositely, and a functional layer 300 disposed between the anode 100 and the cathode 200; the functional layer 300 includes the nitrogen-containing compound provided in the present application.
  • the functional layer 300 includes a hole transport layer 320, and the hole transport layer 320 includes the nitrogen-containing compound of the present application.
  • the hole transport layer 320 may be composed of the nitrogen-containing compound provided in the present application, or may be composed of the nitrogen-containing compound provided in the present application and other materials.
  • the hole transport layer 320 may further include inorganic doping materials to improve the hole transport performance of the hole transport layer 320.
  • the photoelectric conversion device may include an anode 100, a hole transport layer 320, a photoelectric conversion layer 360, an electron transport layer 340, and a cathode 200 which are sequentially stacked and arranged.
  • the photoelectric conversion device may be a solar cell, especially an organic thin film solar cell.
  • the solar cell may include an anode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode that are sequentially stacked, wherein the hole transport layer includes the Nitrogen-containing compounds.
  • an embodiment of the present application also provides an electronic device, which includes any one of the electronic components described in the embodiment of the electronic component provided in the second aspect of the present application. Since the electronic device has any one of the electronic components described in the above-mentioned electronic component embodiments, it has the same beneficial effects, which will not be repeated here in this application.
  • the present application provides an electronic device 400, which includes any one of the organic electroluminescent devices described in the foregoing organic electroluminescent device embodiments.
  • the electronic device 400 may be a display device, a lighting device, an optical communication device or other types of electronic devices, such as but not limited to computer screens, mobile phone screens, televisions, electronic paper, emergency lighting, light modules, etc. Since the electronic device 400 has any one of the organic electroluminescent devices described in the foregoing organic electroluminescent device embodiments, it has the same beneficial effects, which will not be repeated here in this application.
  • the present application provides an electronic device 500, which includes any one of the photoelectric conversion devices described in the foregoing photoelectric conversion device embodiments.
  • the electronic device 500 may be a solar power generation device, a light detector, a fingerprint identification device, an optical module, a CCD camera, or other types of electronic devices. Since the electronic device 500 has any one of the photoelectric conversion devices described in the foregoing photoelectric conversion device embodiments, it has the same beneficial effects, which will not be repeated here in this application.
  • synthesis examples 2 to 22 respectively synthesize the compounds listed in Table 2, except that reactant A is used instead of reactant 1, reactant B is used instead of reactant 2, and reactant C is used instead of reactant 3. , Replace reactant 4 with reactant D.
  • Table 2 shows the structural formulas of reactants and corresponding compounds, the yield of the compound, the yield of the last step, and the mass spectrometry characterization results.
  • the ITO thickness is The ITO substrate (manufactured by Corning) was cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (thickness).
  • the photolithography process was used to prepare it into an experimental substrate with cathode, anode and insulating layer patterns. Surface treatment with ozone and O 2 :N 2 plasma to increase the work function of the anode (experimental substrate) and remove scum;
  • M-MTDATA was vacuum-evaporated on the experimental substrate (anode) to form a thickness of Hole injection layer (HIL), and vacuum evaporation of NPB on the hole injection layer to form a thickness of ⁇ first hole transport layer;
  • HIL Hole injection layer
  • Compound 1 was evaporated on the first hole transport layer to form a thickness of ⁇ second hole transport layer;
  • DBimiBphen and LiQ are mixed in a weight ratio of 1:1 and formed by evaporation Thick electron transport layer (ETL);
  • EIL electron injection layer
  • Magnesium (Mg) and silver (Ag) were mixed at an evaporation rate of 1:9, and vacuum evaporated on the electron injection layer to form a thickness of The cathode.
  • the vapor deposition thickness on the above cathode is CP-1, prepared a green organic electroluminescent device.
  • the green organic electroluminescent device was prepared according to the method of Example 1. The difference is that in Examples 2-22, the compounds listed in Table 3 were used to replace the material of the second hole transport layer of Example 1 (namely compound 1). , So as to prepare the corresponding green organic electroluminescent device. For example, in Example 2, Compound 51 was used instead of Compound 1 of Example 1, and a green organic electroluminescent device was prepared according to the same method as that of Example 1.
  • Example 1 The compound 1 in Example 1 was replaced with the compound TCTA, and the green organic electroluminescence device was prepared according to the same method as in Example 1. Among them, the structural formula of TCTA is:
  • the driving voltage of the organic electroluminescent device of Examples 1-22 is reduced by about 4% to 14%, and the current efficiency is increased by about 24%.
  • the power efficiency is increased by about 36% to 81%
  • the external quantum efficiency is increased by about 3.1% to 66%
  • the life span is increased by about 39% to 79%.
  • the organic electroluminescent devices of Examples 4 to 5, 11 to 14, 18, and 21 to 22 also have higher lifespan and efficiency, for example, the lifespan is increased by up to 28%, and the current efficiency is The highest increase is 34%.
  • Part of the nitrogen-containing compound structure of the present application introduces three-dimensional cycloalkanes and dibenzofuran/thiophene into the triarylamine basic structure at the same time; the dibenzofuran/thiophene group has a strong electron dissociation energy, which can be effective Reducing the HOMO energy level of the material makes the injection of holes into the green light-emitting layer smoother, effectively reducing the driving voltage of the organic electroluminescent device and improving the luminous efficiency.
  • this type of structure has a large conjugate plane, which may cause intermolecular stacking and crystallization, leading to a decrease in device life.
  • the preferred method of the present application introduces specific substituents at the ortho position of the nitrogen atom on the aryl group, which reduces the planarity of the triarylamine core group itself, can further increase the HOMO energy level and reduce the intermolecular stacking effect. Therefore, the nitrogen-containing compound of the present application is suitable for use in the hole transport layer of organic electroluminescent devices, especially the second hole transport layer suitable for organic electroluminescent devices, which can reduce the driving voltage of organic electroluminescent devices. Reduce, improve the current efficiency, power efficiency and external quantum efficiency of the organic electroluminescent device, and increase the life of the organic electroluminescent device.

Landscapes

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

Abstract

本申请属于有机材料技术领域，提供了一种含氮化合物、电子元件和电子装置。该含氮化合物的结构如化学式1所示。该含氮化合物能够提高电子元件的性能。其中，Ar为 II 且X选自O或S；L 1为 III 且在L 1中，"#"表示L 1的亚苯基与N的连接点，"##"表示L 1的亚苯基与 IV 的连接点；L 2为 V 且在L 2中，"#"表示L 2的亚苯基与N的连接点，"##"表示L 2的亚苯基与R 4的连接点。

Description

含氮化合物、电子元件和电子装置
相关申请的交叉引用
本申请要求于2019年12月30日递交的申请号为CN201911404298.1的中国专利申请的优先权，在此引用上述中国专利申请的内容全文以作为本申请的一部分。
技术领域
本申请涉及有机材料技术领域，尤其涉及一种含氮化合物、包含有该含氮化合物的电子元件和电子装置。
背景技术
随着电子技术的发展和材料科学的进步，用于实现电致发光或者光电转化的电子元件的应用范围越来越广泛。该类电子元件，例如有机电致发光器件或者光电转化器件，通常包括相对设置的阴极和阳极，以及设置于阴极和阳极之间的功能层。该功能层由多层有机或者无机膜层组成，且一般包括能量转化层、位于能量转化层与阳极之间的空穴传输层、位于能量转化层与阴极之间的电子传输层。
举例而言，当电子元件为有机电致发光器件时，其一般包括依次层叠设置的阳极、空穴传输层、作为能量转化层的有机发光层、电子传输层和阴极。当阴阳两极施加电压时，两电极产生电场，在电场的作用下，阴极侧的电子向有机发光层移动，阳极侧的空穴也向有机发光层移动，电子和空穴在有机发光层结合形成激子，激子处于激发态向外释放能量，进而使得有机发光层对外发光。
尽管已经有了可以应用于有机电致发光器件的空穴传输层的材料，依然有必要继续研发新型的材料，以进一步提高电子元件的性能。
所述背景技术部分公开的上述信息仅用于加强对本申请的背景的理解，因此它可以包括不构成对本领域普通技术人员已知的现有技术的信息。
发明内容
本申请的目的在于提供一种含氮化合物、电子元件和电子装置，该含氮化合物能提高电子元件的性能。
为实现上述发明目的，本申请采用如下技术方案：
根据本申请的第一个方面，提供一种含氮化合物，所述含氮化合物的结构如化学式1所示：
Figure PCTCN2020140289-appb-000001
其中，Ar为
Figure PCTCN2020140289-appb-000002
且X选自O或S；
L 1为
Figure PCTCN2020140289-appb-000003
且在L 1中，“#”表示L 1的亚苯基与N的连接点，“##”表示L 1的亚苯基与
Figure PCTCN2020140289-appb-000004
的连接点；L 2为
Figure PCTCN2020140289-appb-000005
且在L 2中，“#”表示L 2的亚苯基与N的连接点，“##”表示L 2的亚苯基与R 4的连接点；
R 1选自甲基或苯基；R 2选自甲基或苯基；
R 3选自H、CA1～CA10所示的基团；R 4选自苯基、CA1～CA10所示的取代基；且R 3和R 4有且只有一个选自CA1～CA10所示的取代基；其中，CA1～CA10的结构如下：
Figure PCTCN2020140289-appb-000006
根据本申请的第二个方面，提供一种电子元件，包括相对设置的阳极和阴极，以及设于所述阳极和所述阴极之间的功能层；所述功能层包含本申请第一方面所述的含氮化合物。
根据本申请的第三个方面，提供一种电子装置，所述电子装置包括本申请第二方面所述的电子元件。
本申请的化合物中，具有二苯并呋喃基团或者二苯并噻吩基团，二苯并呋喃基团或者二苯并噻吩基团具有较强的电子解离能，因此可以有效降低含氮化合物的HOMO能级，从而使得空穴传输层向作为能量转化层的有机发光层注入空穴更为流畅，或者可以使得作为能量转化层的光电转化层向电子传输层注入空穴更为顺畅，如此使得含氮化合物具有良好的空穴传输效率，而二苯并呋喃基团或者二苯并噻吩基团的引入可能会增加本申请的含氮化合物的共轭平面，并有可能会引起分子间的堆叠和结晶而导致器件寿命降低，通过引入了大空间位阻的环烷烃结构，可以有效降低化合物的堆叠效应，并可以提升含氮化合物的成膜性能。更重要地是，本申请的化合物中，于氮原子在芳基上的邻位引入特定的取代基，降低了三芳基胺核心基团自身的平面性，可以进一步提高HOMO能级并降低分子间堆叠效应。因此，本申请的含氮化合物适宜用于有机电致发光器件的空穴传输层，尤其是适用于有机电致发光器件的第二空穴传输层，其可以降低有机电致发光器件的驱动电压降，提高有机电致发光器件的电流效、功率效率和外量子效率，并提高有机电致发光器件的寿命。
附图说明
通过参照附图详细描述其示例实施方式，本申请的上述和其它特征及优点将变得更加明显。
图1是本申请实施方式的一种有机电致发光器件的结构示意图。
图2是本申请实施方式的一种电子装置的结构示意图。
图3是本申请实施方式的一种光电转化器件的结构示意图。
图4是本申请实施方式的一种电子装置的结构示意图。
图5是化合物392的氢谱图。
图6是化合物1的合成路线图。
图中主要元件附图标记说明如下：
100、阳极；200、阴极；300、功能层；310、空穴注入层；320、空穴传输层；321、第一空穴传输层；322、第二空穴传输层；330、有机发光层；340、电子传输层；350、电子注入层；360、光电转化层；400、电子装置；500、电子装置。
具体实施方式
现在将参考附图更全面地描述示例实施例。然而，示例实施例能够以多种形式实施，且不应被理解为限于在此阐述的范例；相反，提供这些实施例使得本申请将更加全面和完整，并将示例实施例的构思全面地传达给本领域的技术人员。所描述的特征、结构或特性可以以任何合适的方式结合在一个或更多实施例中。在下面的描述中，提供许多具体细节从而给出对本申请的实施例的充分理解。
在图中，为了清晰，可能夸大了区域和层的厚度。在图中相同的附图标记表示相同或类似的结构，因而将省略它们的详细描述。
在本申请中，芳基指的是衍生自芳香烃环的任选官能团或取代基。芳基可以是单环芳基或多环芳基，换言之，芳基可以是单环芳基、稠环芳基、通过碳碳键共轭连接的两个或者更多个单环芳基、通过碳碳键共轭连接的单环芳基和稠环芳基、通过碳碳键共轭连接的两个或者更多个稠环芳基。即，通过碳碳键共轭连接的两个或者多个芳香基团也可以视为本申请的芳基。其中，芳基中不含有B、N、O、S或P等杂原子。举例而言，在本申请中，联苯基、三联苯基等为芳基。芳基的示例包括但不限于，苯基、萘基、芴基、蒽基、菲基、联苯基、三联苯基、四联苯基、芘基、
Figure PCTCN2020140289-appb-000007
基等。
在本申请中，杂芳基可以是包括B、O、N、P、Si和S中的至少一个作为杂原子的杂芳基。杂芳基可以是单环杂芳基或多环杂芳基，换言之，杂芳基可以是单个芳香环体系，也可以是通过碳碳键共轭连接的多个芳香环体系，且任一芳香环体系为一个芳香单环或者一个芳香稠环。杂芳基的具体实例包括但不限于，噻吩基、呋喃基、吡咯基、咪唑基、噻唑基、噁唑基、噁二唑基、三唑基、吡啶基、联吡啶基、嘧啶基、三嗪基、吖啶基、哒嗪基、吡嗪基、喹啉基、喹唑啉基、喹喔啉基、吩噁嗪基、酞嗪基、吡啶并嘧啶基、吡啶并吡嗪基、吡嗪并吡嗪基、异喹啉基、吲哚基、咔唑基、N-苯基咔唑基、N-吡啶基咔唑基、N-甲基咔唑基、苯并噁唑基、苯并咪唑基、苯并噻唑基、苯并咔唑基、苯并噻吩基、二苯并噻吩基、噻吩并噻吩基、苯并呋喃基、菲咯啉基、异噁唑基、噻二唑基、苯并噻唑基、吩噻嗪基、二苯并甲硅烷基、二苯并呋喃基、苯基取代的二苯并呋喃基、二苯并呋喃基取代的苯基等。
在本申请中，所采用的描述方式“各……独立地为”与“……分别独立地为”和“……独立地选自”可以互换，均应做广义理解，其既可以是指在不同基团中，相同符号之间所表达的具体选项之间互相不影响，也可以表示在相同的基团中，相同符号之间所表达的具体选项之间互相不影响。
本申请中的不定位连接键，是指从环体系中伸出的单键
Figure PCTCN2020140289-appb-000008
其表示该连接键的一端可以连接该键所贯穿的环体系中的任意位置，另一端连接化合物分子其余部分。举例而言，下式(X’)中所示的，式(X’)所表示的菲基通过一个从一侧苯环中间伸出的不定位连接键与分子其他位置连接，其所表示的含义，包括如式(X’-1)～式(X’-4)所示出的任一可能的连接方式。
Figure PCTCN2020140289-appb-000009
第一方面，本申请提供一种含氮化合物，结构如下所示：
Figure PCTCN2020140289-appb-000010
其中，Ar为
Figure PCTCN2020140289-appb-000011
且X选自O或S；即，Ar为
Figure PCTCN2020140289-appb-000012
L 1为
Figure PCTCN2020140289-appb-000013
且在L 1中，“#”表示L 1的亚苯基与N的连接点，“##”表示L 1的亚苯基与
Figure PCTCN2020140289-appb-000014
的连接点；
L 2为
Figure PCTCN2020140289-appb-000015
且在L 2中，“#”表示L 2的亚苯基与N的连接点，“##”表示L 2的亚苯基与R 4的连接点；
R 1选自甲基或苯基；R 2选自甲基或苯基；
R 3选自H、CA1～CA10所示的基团；R 4选自苯基、CA1～CA10所示的取代基；且R 3和R 4有且只有一个选自CA1～CA10所示的取代基；其中，CA1～CA10的结构如下：
Figure PCTCN2020140289-appb-000016
举例而言，在化合物
Figure PCTCN2020140289-appb-000017
中，Ar为
Figure PCTCN2020140289-appb-000018
L 1为
Figure PCTCN2020140289-appb-000019
L 2为
Figure PCTCN2020140289-appb-000020
R 1为苯基，R 2为甲基，R 3为H，R 4为
Figure PCTCN2020140289-appb-000021
本申请的含氮化合物中，具有二苯并呋喃基团或者二苯并噻吩基团，二苯并呋喃基团或者二苯并噻吩基团具有较强的电子解离能，因此可以有效降低含氮化合物的HOMO能级，从而使得空穴传输层向作为能量转化层的有机发光层注入空穴更为流畅，或者可以使得作为能量转化层的光电转化层向电子传输层注入空穴更为顺畅，如此使得含氮化合物具有良好的空穴传输效率。如此，可以有效改善应用该含氮化合物的电子元件的电压性能和效率性能，例如可以提高有机电致发光器件的发光效率并降低其驱动电压，也可以提高光电转化器件的光电效率并提高其开路电压。二苯并呋喃基团或者二苯并噻吩基团的引入可能会增加本申请的含氮化合物的共轭平面，并有可能会引起分子间的堆叠和结晶而导致器件寿命降低，为了克服二苯并呋喃基团或者二苯并噻吩基团可能产生的不利影响，本申请的部分含氮化合物还引入了大空间位阻的环烷烃结构，环烷烃基团可以有效降低本申请的含氮化合物的堆叠效应，并可以提升含氮化合物的成膜性能。有机电致发光器件的制备和测试结果表明，环烷烃基团的引入提升了有机电致发光器件的寿命，这表明其克服了二苯并呋喃基团或者二苯并噻吩基团的不利影响并有效提升了含氮化合物的成膜性能，降低了含氮化合物自身的平面性，尤其是降低了含氮化合物的分子间堆叠效应，这使得应用本申请的含氮化合物的电子元件的寿命得以提升。因此，本申请的含氮化合物具有更好的空穴传输性能、更低的HOMO能级、更低的分子间堆叠效应和更佳的成膜性能，能够提升光电转化器件和电致发光器件等电子元件的电压性能、效率性能和寿命性能。
更重要地是，本申请的化合物中，于氮原子在芳基上的邻位引入特定的取代基，降低了三芳基胺核心基团自身的平面性，可以进一步提高HOMO能级并降低分子间堆叠效应。因此，本申请的含氮化合物适宜用于有机电致发光器件的空穴传输层，尤其是适用于有机电致发光器件的第二空穴传输层，其可以降低有机电致发光器件的驱动电压降，提高有机电致发光器件的电流效、功率效率和外量子效率，并提高有机电致发光器件的寿命。
可选地，Ar选自2-DBF、3-DBF、2-DBT、3-DBT；其中，2-DBF、3-DBF、2-DBT、3-DBT的结构式如下：
Figure PCTCN2020140289-appb-000022
可选地，所述含氮化合物选自表1所列的各个化合物所组成的组：
表1
Figure PCTCN2020140289-appb-000023
Figure PCTCN2020140289-appb-000024
Figure PCTCN2020140289-appb-000025
Figure PCTCN2020140289-appb-000026
Figure PCTCN2020140289-appb-000027
Figure PCTCN2020140289-appb-000028
Figure PCTCN2020140289-appb-000029
Figure PCTCN2020140289-appb-000030
Figure PCTCN2020140289-appb-000031
Figure PCTCN2020140289-appb-000032
Figure PCTCN2020140289-appb-000033
Figure PCTCN2020140289-appb-000034
Figure PCTCN2020140289-appb-000035
Figure PCTCN2020140289-appb-000036
Figure PCTCN2020140289-appb-000037
Figure PCTCN2020140289-appb-000038
Figure PCTCN2020140289-appb-000039
Figure PCTCN2020140289-appb-000040
Figure PCTCN2020140289-appb-000041
Figure PCTCN2020140289-appb-000042
举例而言，根据表1可知，化合物1294的Ar为3-DBT，L 1为
Figure PCTCN2020140289-appb-000043
L 2为
Figure PCTCN2020140289-appb-000044
R 3为H，R 4为CA10。则，化合物1294的结构式为：
Figure PCTCN2020140289-appb-000045
第二方面，本申请还提供一种电子元件，电子元件包括相对设置的阳极和阴极，以及设于所述阳极和所述阴极之间的功能层；所述功能层包含本申请第一方面提供的含氮化合物。
本申请所提供的含氮化合物可以用于形成功能层中的至少一个有机膜层，以改善电子元件的电压特性、效率特性和寿命特性。
可选地，包含有本申请的含氮化合物的有机膜层位于阳极和电子元件的能量转化层之间，以便改善空穴在阳极与能量转化层之间的传输。
可选地，功能层包括空穴传输层，空穴传输层包含本申请所提供的含氮化合物。其中，空穴传输层既可以由本申请所提供的含氮化合物组成，也可以由本申请所提供的含氮化合物和其他材料共同组成。
按照一种实施方式，空穴传输层包括第一空穴传输层和第二空穴传输层，且第一空穴传输层相对第二空穴传输层更靠近阳极的表面；第一空穴传输层和/或第二空穴传输层包含本申请所提供的含氮化合物。换言之，既可以第一空穴传输层和第二空穴传输层中的一层包含本申请所提供的含氮化合物，也可以第一空穴传输层和第二空穴传输层均含有本申请所提供的含氮化合 物。可以理解地是，第一空穴传输层、第二空穴传输层还可以含有其他材料，也可以不含有其他材料。可选地，所述第二空穴传输层由所述含氮化合物组成。
按照一种优选的实施方式，如图1所示，电子元件可以为有机电致发光器件。有机电致发光器件可以包括依次层叠设置的阳极100、第一空穴传输层321、第二空穴传输层322、作为能量转化层的有机发光层330、电子传输层340和阴极200。本申请提供的含氮化合物可以应用于有机电致发光器件的第二空穴传输层322，以提高有机电致发光器件的寿命、提高有机电致发光器件的发光效率、降低有机电致发光器件的驱动电压。
本申请中，阳极100包括阳极材料，其优选是有助于空穴注入至功能层中的具有大逸出功(功函数，work function)材料。阳极材料的具体实例包括但不限于：金属如镍、铂、钒、铬、铜、锌和金或它们的合金；金属氧化物如氧化锌、氧化铟、氧化铟锡(ITO)和氧化铟锌(IZO)；组合的金属和氧化物如ZnO:Al或SnO 2:Sb；或导电聚合物如聚(3-甲基噻吩)、聚[3,4-(亚乙基-1,2-二氧基)噻吩](PEDT)、聚吡咯和聚苯胺。优选包括包含氧化铟锡(铟锡氧化物，indium tin oxide)(ITO)作为阳极的透明电极。
可选地，第一空穴传输层321可以包括一种或者多种空穴传输材料，空穴传输材料可以选自咔唑多聚体、咔唑连接三芳胺类化合物或者其他类型的化合物，本申请对此不做特殊的限定。例如，第一空穴传输层321可以由化合物NPB组成。
可选地，有机发光层330可以由单一发光材料组成，也可以包括主体材料和客体材料。一种具体的实施方式中，有机发光层330由主体材料和客体材料组成，注入有机发光层330的空穴和注入有机发光层330的电子可以在有机发光层330复合而形成激子，激子将能量传递给主体材料，主体材料将能量传递给客体材料，进而使得客体材料能够发光。
有机发光层330的主体材料可以为金属螯合类化合物、双苯乙烯基衍生物、芳香族胺衍生物、二苯并呋喃衍生物或者其他类型的材料，本申请对此不做特殊的限制。在本申请的一种实施方式中，有机发光层330的主体材料可以为CBP。
有机发光层330的客体材料可以为具有缩合芳基环的化合物或其衍生物、具有杂芳基环的化合物或其衍生物、芳香族胺衍生物或者其他材料，本申请对此不做特殊的限制。在本申请的一种实施方式中，有机发光层330的客体材料可以为绿色磷光材料，例如可以为Ir(ppy) 3等。
电子传输层340可以为单层结构，也可以为多层结构，其可以包括一种或者多种电子传输材料，电子传输材料可以选自但不限于，苯并咪唑衍生物、恶二唑衍生物、喹喔啉衍生物或者其他电子传输材料。在本申请的一种实施方式中，电子传输层340可以由DBimiBphen和LiQ组成。
本申请中，阴极200包括阴极材料，其是有助于电子注入至功能层中的具有小逸出功的材料。阴极材料的具体实例包括但不限于，金属如镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡和铅或它们的合金；或多层材料如LiF/Al、Liq/Al、LiO 2/Al、LiF/Ca、LiF/Al和BaF 2/Ca。优选包括包含铝的金属电极作为阴极。
可选地，如图1所示，在阳极100和第一空穴传输层321之间还可以设置有空穴注入层310，以增强向第一空穴传输层321注入空穴的能力。空穴注入层310可以选用联苯胺衍生物、星爆状芳基胺类化合物、酞菁衍生物或者其他材料，本申请对此不做特殊的限制。例如，空穴注入层310可以由m-MTDATA组成。
可选地，如图1所示，在阴极200和电子传输层340之间还可以设置有电子注入层350，以增强向电子传输层340注入电子的能力。电子注入层350可以包括有碱金属硫化物、碱金属卤化物等无机材料，或者可以包括碱金属与有机物的络合物。例如，电子注入层350可以包括LiQ。
按照另一种优选的实施方式，电子元件可以为光电转化器件。如图3所示，该光电转化器件可以包括相对设置的阳极100和阴极200，以及设于阳极100和阴极200之间的功能层300；功能层300包含本申请所提供的含氮化合物。
按照一种实施方式，如图3所示，所述功能层300包括空穴传输层320，所述空穴传输层320包含本申请的含氮化合物。其中，空穴传输层320既可以为本申请所提供的含氮化合物组成，也可以由本申请所提供的含氮化合物和其他材料共同组成。
可选地，空穴传输层320还可以包括无机掺杂材料，以提高空穴传输层320的空穴传输性能。
按照一种具体的实施方式，如图3所示，光电转化器件可包括依次层叠设置的阳极100、空穴传输层320、光电转化层360、电子传输层340和阴极200。
可选地，光电转化器件可以为太阳能电池，尤其是可以为有机薄膜太阳能电池。举例而言，在本申请的一种实施方式中，太阳能电池可以包括依次层叠设置的阳极、空穴传输层、光电转化层、电子传输层和阴极，其中，空穴传输层包含有本申请的含氮化合物。
第三方面，本申请实施方式还提供一种电子装置，该电子装置包括本申请第二方面提供的电子元件实施方式所描述的任意一种电子元件。由于该电子装置具有上述电子元件实施方式所描述的任意一种电子元件，因此具有相同的有益效果，本申请在此不再赘述。
举例而言，如图2所示，本申请提供一种电子装置400，该电子装置400包括上述有机电致发光器件实施方式所描述的任意一种有机电致发光器件。该电子装置400可以为显示装置、照明装置、光通讯装置或者其他类型的电子装置，例如可以包括但不限于电脑屏幕、手机屏幕、电视机、电子纸、应急照明灯、光模块等。由于该电子装置400具有上述有机电致发光器件实施方式所描述的任意一种有机电致发光器件，因此具有相同的有益效果，本申请在此不再赘述。
再举例而言，如图4所示，本申请提供一种电子装置500，该电子装置500包括上述光电转化器件实施方式所描述的任意一种有光电转化器件。该电子装置500可以为太阳能发电设备、光检测器、指纹识别设备、光模块、CCD相机或则其他类型的电子装置。由于该电子装置500具有上述光电转化器件实施方式所描述的任意一种光电转化器件，因此具有相同的有益效果，本申请在此不再赘述。
以下，通过实施例对本申请进一步详细说明。但是，下述实施例仅是本申请的例示，而并非限定本申请。
以下合成例1至22用于说明化合物及其制备方法。
合成例1
按照图6所示合成路线图，合成化合物1：
将反应物1(50.0g,520mmol)和三氟乙酸(TFA)(400mL)加入1L圆底烧瓶中，搅拌条件下加入浓硝酸(1.5g)，升温至45～50℃，于空气氛围内搅拌16小时；减压除去三氟乙酸，向剩余混合物中加入10wt％氢氧化钾的乙醇溶液(500mL)，搅拌3小时；减压除去乙醇，向瓶中加入二氯甲烷，有机相水洗两次，使用无水硫酸镁干燥有机相，减压除去有机相中的溶剂得到粗品；使用二氯甲烷/正庚烷作为洗脱液对所得粗品进行硅胶柱色谱法提纯，得到白色粉末状中间体1(19.4g，收率为33％)。
将中间体1(19.0g,169mmol)、反应物2(39.5g,169mmol)和二氯甲烷(MC)(250mL)加入500mL圆底烧瓶中，氮气保护条件下，于-15至-20℃滴加三氟甲磺酸(HOTf)(38.1g,254mmol)；滴加完毕后，保持低温搅拌8小时，升至室温(25℃)，向反应液中缓慢滴加10wt％ 氢氧化钠水溶液至中性；分离有机相，有机相使用水洗两次，有机相使用无水硫酸镁干燥，减压除去有机相中的溶剂得到粗品；使用正庚烷作为洗脱液对所得粗品进行硅胶柱色谱法提纯，得到白色固体中间体2(34.4g，收率为62％)。
将反应物3(10.0g,64mmol)、反应物4(2-氨基二苯并呋喃)(12.8g,70mmol)、三(二亚苄基丙酮)二钯(Pd 2(dba) 3)(0.6g,0.6mmol)、2-二环己基磷-2',4',6'-三异丙基联苯(XPhos)(0.6g,1.3mmol)以及叔丁醇钠(tBuONa)(9.2g,96mmol)加入甲苯(150mL)中，氮气保护下加热至105-110℃，搅拌1小时；冷却至室温，反应液使用水洗两次，加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，过柱液减压除去溶剂得粗品；使用二氯甲烷/乙醇体系对所得粗品进行重结晶提纯，得到浅褐色固体中间体3(13.2g，收率为80％)。
将中间体2(4.0g,12.2mmol)、中间体3(3.2g,12.2mmol)、三(二亚苄基丙酮)二钯(0.1g,0.1mmol)、2-二环己基磷-2',6'-二甲氧基联苯(SPhos)(0.1g,0.2mmol)以及叔丁醇钠(1.8g,18.3mmol)加入甲苯(40mL)中，氮气保护下加热至105-110℃，搅拌16小时；而后冷却至室温，反应液使用水洗后加入硫酸镁干燥，过滤后将滤液通过短硅胶柱，过柱液减压除去溶剂得粗品；使用二氯甲烷/正庚烷体系对所得粗品进行重结晶提纯，得到白色固体化合物1(2.3g，收率为37％)。质谱：m/z＝506.2[M+H] +。
合成例2至22
参照化合物1的方法，合成例2至22分别合成表2所列举的化合物，不同的是，以反应物A代替反应物1，以反应物B代替反应物2，以反应物C代替反应物3，以反应物D代替反应物4，其中，反应物以及相应的化合物的结构式，化合物产量、最后一步收率及质谱表征结果如表2所示。
表2：各个化合物的结构、原料、收率和质谱表征
Figure PCTCN2020140289-appb-000046
Figure PCTCN2020140289-appb-000047
Figure PCTCN2020140289-appb-000048
Figure PCTCN2020140289-appb-000049
化合物392的核磁图谱，如图5所示， 1H NMR(CDCl 3,400MHz)：7.80(d,1H),7.59(d,1H),7.49-7.45(m,3H),7.41-7.33(m,9H),7.28(t,1H),7.19(d,2H),7.09-7.03(m,4H),6.96(d,2H),6.90(d,1H),2.12(s,3H),1.95(s,6H),1.82-1.76(m,6H)。
以下实施例用于说明本申请的化合物在有机电致发光器件上的应用。
实施例1
通过如下方法制备绿色有机电致发光器件
将ITO厚度为
Figure PCTCN2020140289-appb-000050
的ITO基板(康宁制造)切割成40mm(长)×40mm(宽)×0.7mm(厚)的尺寸，采用光刻工序，将其制备成具有阴极、阳极以及绝缘层图案的实验基板，利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极(实验基板)的功函数的和清除浮渣；
在实验基板(阳极)上真空蒸镀m-MTDATA以形成厚度为
Figure PCTCN2020140289-appb-000051
的空穴注入层(HIL)，并且在空穴注入层上真空蒸镀NPB，以形成厚度为
Figure PCTCN2020140289-appb-000052
的第一空穴传输层；
在第一空穴传输层上蒸镀化合物1，形成厚度为
Figure PCTCN2020140289-appb-000053
的第二空穴传输层；
按照膜厚比100:8同时蒸镀作为主体材料的CBP和作为客体材料的Ir(ppy) 3，形成厚度为
Figure PCTCN2020140289-appb-000054
的发光层(EML)；
将DBimiBphen和LiQ以1:1的重量比进行混合并蒸镀形成
Figure PCTCN2020140289-appb-000055
厚的电子传输层(ETL)；
将LiQ蒸镀在电子传输层上以形成厚度为
Figure PCTCN2020140289-appb-000056
的电子注入层(EIL)；
将镁(Mg)和银(Ag)以1:9的蒸镀速率混合，真空蒸镀在电子注入层上，形成厚度为
Figure PCTCN2020140289-appb-000057
的阴极。
在上述阴极上蒸镀厚度为
Figure PCTCN2020140289-appb-000058
的CP-1，制备出绿色有机电致发光器件。
其中，m-MTDATA、NPB、CBP、Ir(ppy) 3、DBimiBphen、LiQ、CP-1的结构式如下：
Figure PCTCN2020140289-appb-000059
实施例2-实施例22
按照实施例1的方法制备绿色有机电致发光器件，不同的是，实施例2-22中，分别以表3所列举的化合物代替实施例1的第二空穴传输层材料(即化合物1)，从而制得相应的绿色有机电致发光器件。举例而言，在实施例2中，以化合物51代替实施例1的化合物1，按照与实施例1相同的方法制备绿色有机电致发光器件。
对比例1
将实施例1中的化合物1替换为化合物TCTA，按照与实施例1相同的方法，制备绿色有机电致发光器件。其中，TCTA的结构式为：
Figure PCTCN2020140289-appb-000060
对实施例1-22和对比例1制备所得的绿色有机电致发光器件，在10mA/cm 2的条件下测试器件的性能，T95器件寿命在恒定电流密度20mA/cm 2下进行测试，测试结果展示在表3中。
表3：有机电致发光器件的性能测试结果
Figure PCTCN2020140289-appb-000061
Figure PCTCN2020140289-appb-000062
结合表3可知，相较于对比例1所制备的有机电致发光器件，实施例1～22的有机电致发光器件的驱动电压降低了约4％～14％，电流效率提高了约24％～67％，功率效率提高了约36％～81％，外量子效率约提高了3.1％～66％，寿命约提高了39％～79％。另外，相比于其它实施例，实施例4～5、11～14、18和21～22的有机电致发光器件也具有更高的寿命和效率，例如，寿命最高提高了28％，电流效率最高提高了34％。
本申请的部分含氮化合物结构将具有立体结构的环烷烃与二苯并呋喃/噻吩同时引入三芳基胺基础结构当中；二苯并呋喃/噻吩基团具有较强的电子解离能，可以有效降低材料的HOMO能级从而使得空穴向绿色发光层的注入更为流畅，有效降低有机电致发光器件的驱动电压并提升发光效率。但该类型结构具有较大的共轭平面，可能会引起分子间的堆叠和结晶导致器件寿命下降，而具有大位阻的立体环烷烃的引入，则有效降低了该堆叠效应，大幅度提升了材料的成膜性，使得器件的寿命不但未下降，反而得到了提升。另外，本申请的优选方式于氮原子在芳基上的邻位引入特定的取代基，降低了三芳基胺核心基团自身的平面性，可以进一步提高HOMO能级并降低分子间堆叠效应。因此，本申请的含氮化合物适宜用于有机电致发光器件的空穴传输层，尤其是适用于有机电致发光器件的第二空穴传输层，其可以降低有机电致发光器件的驱动电压降，提高有机电致发光器件的电流效、功率效率和外量子效率，并提高有机电致发光器件的寿命。
应可理解的是，本申请不将其应用限制到本说明书提出的部件的详细结构和布置方式。本申请能够具有其他实施方式，并且能够以多种方式实现并且执行。前述变形形式和修改形式落在本申请的范围内。应可理解的是，本说明书公开和限定的本申请延伸到文中和/或附图中提到或明显的两个或两个以上单独特征的所有可替代组合。所有这些不同的组合构成本申请的多个可替代方面。本说明书所述的实施方式说明了已知用于实现本申请的最佳方式，并且将使本领域技术人员能够利用本申请。

Claims (9)

  1. 一种含氮化合物，其特征在于，所述含氮化合物的结构如化学式1所示：
    Figure PCTCN2020140289-appb-100001
    其中，Ar为
    Figure PCTCN2020140289-appb-100002
    且X选自O或S；L 1为
    Figure PCTCN2020140289-appb-100003
    且在L 1中，“#”表示L 1的亚苯基与N的连接点，“##”表示L 1的亚苯基与
    Figure PCTCN2020140289-appb-100004
    的连接点；L 2为
    Figure PCTCN2020140289-appb-100005
    且在L 2中，“#”表示L 2的亚苯基与N的连接点，“##”表示L 2的亚苯基与R 4的连接点；
    R 1选自甲基或苯基；R 2选自甲基或苯基；
    R 3选自H、CA1～CA10所示的基团；R 4选自苯基、CA1～CA10所示的取代基；且R 3和R 4有且只有一个选自CA1～CA10所示的取代基；其中，CA1～CA10的结构如下：
    Figure PCTCN2020140289-appb-100006
  2. 根据权利要求1所述的含氮化合物，其特征在于，Ar选自2-DBF、3-DBF、2-DBT、3-DBT；其中，2-DBF、3-DBF、2-DBT、3-DBT的结构式如下：
    Figure PCTCN2020140289-appb-100007
  3. 根据权利要求2所述的含氮化合物，其特征在于，所述含氮化合物选自以下表格所列的各个化合物所组成的组：
    Figure PCTCN2020140289-appb-100008
    Figure PCTCN2020140289-appb-100009
    Figure PCTCN2020140289-appb-100010
    Figure PCTCN2020140289-appb-100011
    Figure PCTCN2020140289-appb-100012
    Figure PCTCN2020140289-appb-100013
    Figure PCTCN2020140289-appb-100014
    Figure PCTCN2020140289-appb-100015
    Figure PCTCN2020140289-appb-100016
    Figure PCTCN2020140289-appb-100017
    Figure PCTCN2020140289-appb-100018
    Figure PCTCN2020140289-appb-100019
    Figure PCTCN2020140289-appb-100020
    Figure PCTCN2020140289-appb-100021
    Figure PCTCN2020140289-appb-100022
    Figure PCTCN2020140289-appb-100023
    Figure PCTCN2020140289-appb-100024
    Figure PCTCN2020140289-appb-100025
    Figure PCTCN2020140289-appb-100026
  4. 一种电子元件，其特征在于，包括相对设置的阳极和阴极，以及设于所述阳极和所述阴极之间的功能层；
    所述功能层包含权利要求1～3任一项所述的含氮化合物。
  5. 根据权利要求4所述的电子元件，其特征在于，所述功能层包括空穴传输层，所述空穴传输层包含所述含氮化合物。
  6. 根据权利要求5所述的电子元件，其特征在于，所述空穴传输层包括第一空穴传输层和第二空穴传输层，且所述第一空穴传输层设于所述第二空穴传输层靠近所述阳极的表面；所述第一空穴传输层或所述第二空穴传输层包含所述含氮化合物。
  7. 根据权利要求6所述的电子元件，其特征在于，所述第二空穴传输层由所述含氮化合物组成。
  8. 根据权利要求6所述的电子元件，其特征在于，所述电子元件为光电转化器件或者有机电致发光器件。
  9. 一种电子装置，其特征在于，包括权利要求4～8任一项所述的电子元件。
PCT/CN2020/140289 2019-12-30 2020-12-28 含氮化合物、电子元件和电子装置 WO2021136197A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/622,744 US11535602B1 (en) 2019-12-30 2020-12-28 Nitrogen-containing compound, electronic element and electronic apparatus

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911404298.1A CN111153880B (zh) 2019-12-30 2019-12-30 含氮化合物、电子元件和电子装置
CN201911404298.1 2019-12-30

Publications (1)

Publication Number Publication Date
WO2021136197A1 true WO2021136197A1 (zh) 2021-07-08

Family

ID=70559613

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/140289 WO2021136197A1 (zh) 2019-12-30 2020-12-28 含氮化合物、电子元件和电子装置

Country Status (3)

Country Link
US (1) US11535602B1 (zh)
CN (1) CN111153880B (zh)
WO (1) WO2021136197A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110317141A (zh) * 2019-07-01 2019-10-11 陕西莱特光电材料股份有限公司 一种有机电致发光材料及其合成方法和应用
CN111018721A (zh) * 2019-10-31 2020-04-17 陕西莱特光电材料股份有限公司 含氮化合物、电子元件和电子装置
CN111153880B (zh) * 2019-12-30 2021-02-12 陕西莱特光电材料股份有限公司 含氮化合物、电子元件和电子装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180078177A (ko) * 2016-12-29 2018-07-09 머티어리얼사이언스 주식회사 유기 화합물 및 이를 포함하는 유기전계발광소자
CN110183332A (zh) * 2019-06-17 2019-08-30 陕西莱特光电材料股份有限公司 一种包含多环烷烃的芳香族衍生物及包含该衍生物的有机电致发光器件
CN110885320A (zh) * 2019-10-31 2020-03-17 陕西莱特光电材料股份有限公司 叔胺化合物的制备方法
CN111153880A (zh) * 2019-12-30 2020-05-15 陕西莱特光电材料股份有限公司 含氮化合物、电子元件和电子装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180078177A (ko) * 2016-12-29 2018-07-09 머티어리얼사이언스 주식회사 유기 화합물 및 이를 포함하는 유기전계발광소자
CN110183332A (zh) * 2019-06-17 2019-08-30 陕西莱特光电材料股份有限公司 一种包含多环烷烃的芳香族衍生物及包含该衍生物的有机电致发光器件
CN110885320A (zh) * 2019-10-31 2020-03-17 陕西莱特光电材料股份有限公司 叔胺化合物的制备方法
CN111153880A (zh) * 2019-12-30 2020-05-15 陕西莱特光电材料股份有限公司 含氮化合物、电子元件和电子装置

Also Published As

Publication number Publication date
CN111153880A (zh) 2020-05-15
CN111153880B (zh) 2021-02-12
US11535602B1 (en) 2022-12-27

Similar Documents

Publication Publication Date Title
EP3845522A1 (en) Nitrogen-containing compound, electronic element and electronic device
WO2021213109A1 (zh) 一种芳胺化合物、使用其的电子元件及电子装置
WO2021218491A1 (zh) 含氮化合物、电子元件和电子装置
WO2022206055A1 (zh) 有机电致发光材料、电子元件及电子装置
WO2020248943A1 (zh) 含氮化合物、电子元件和电子装置
CN113683519B (zh) 一种有机化合物及包含其的电子元件和电子装置
WO2022088865A1 (zh) 含氮化合物、电子元件和电子装置
WO2021136197A1 (zh) 含氮化合物、电子元件和电子装置
WO2023011028A1 (zh) 有机化合物、电子元件及电子装置
WO2022213905A1 (zh) 有机化合物以及使用其的电子元件和电子装置
WO2021083030A1 (zh) 含氮化合物、电子元件及电子装置
CN114133333B (zh) 含氮化合物、电子元件和电子装置
CN113861044A (zh) 有机化合物及包含其的电子元件和电子装置
CN113121408A (zh) 含氮化合物、电子元件和电子装置
WO2022100194A1 (zh) 含氮化合物、有机电致发光器件和电子装置
CN113214280B (zh) 有机化合物及包含其的电子器件和电子装置
WO2023231531A1 (zh) 含氮化合物、有机电致发光器件和电子装置
WO2023216669A1 (zh) 有机化合物、有机电致发光器件和电子装置
WO2023202198A1 (zh) 有机材料、电子元件和电子装置
WO2023185078A1 (zh) 有机化合物和电子元件及电子装置
WO2023179094A1 (zh) 有机化合物及包含其的电子元件和电子装置
WO2023134228A1 (zh) 含氮化合物及包含其的有机电致发光器件和电子装置
CN113896720B (zh) 有机化合物、电子元件及电子装置
CN113651703B (zh) 有机化合物、电子元件和电子装置
CN114133351B (zh) 含氮化合物及包含其的电子元件和电子装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20910891

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20910891

Country of ref document: EP

Kind code of ref document: A1