WO2021036433A1 - 含氮化合物、光电转化器件及电子装置 - Google Patents

含氮化合物、光电转化器件及电子装置 Download PDF

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WO2021036433A1
WO2021036433A1 PCT/CN2020/096880 CN2020096880W WO2021036433A1 WO 2021036433 A1 WO2021036433 A1 WO 2021036433A1 CN 2020096880 W CN2020096880 W CN 2020096880W WO 2021036433 A1 WO2021036433 A1 WO 2021036433A1
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nitrogen
carbon atoms
containing compound
photoelectric conversion
group
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PCT/CN2020/096880
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English (en)
French (fr)
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马天天
杨敏
杨雷
冯震
孙占义
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陕西莱特光电材料股份有限公司
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Priority to JP2021570830A priority Critical patent/JP7152816B2/ja
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    • 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
    • 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
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • 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
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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 field of optoelectronic technology, specifically, to a nitrogen-containing compound, a photoelectric conversion device, and an electronic device.
  • organic electroluminescent devices OLED, Organic electroluminescent devices
  • OLED Organic electroluminescent devices
  • Common organic electroluminescence devices are composed of an anode, a cathode, and an organic layer arranged between the cathode and the anode.
  • the two electrodes When a voltage is applied to the cathode and the anode, the two electrodes generate an electric field.
  • the electrons on the cathode side and the holes on the anode side move to the functional layer at the same time, and they combine in the functional layer to form excitons, which are excited
  • the state releases energy to the outside, and the process of changing from the excited state to the ground state emits light to the outside. Therefore, it is very important to improve the recombination of electrons and holes in OLED devices.
  • the photoelectric conversion device is often provided with an electron blocking layer and an electron transport layer to improve the lifetime of the device.
  • current devices have a problem of low efficiency. Therefore, how to design new materials with better performance to be used in electrical barrier layers or electron transport layers, so that all devices can achieve the effects of reducing voltage, improving photoelectric conversion efficiency and lifespan, has always been an urgent problem for those skilled in the art. .
  • the purpose of this application is to overcome the above-mentioned shortcomings in the prior art and provide a nitrogen-containing compound and a photoelectric conversion device, which can improve the photoelectric conversion efficiency and extend the life of the device.
  • a nitrogen-containing compound is provided, and the general structural formula of the nitrogen-containing compound is shown in Formula I:
  • Ar 1 and Ar 2 are independently selected from substituted or unsubstituted aryl groups with 6-30 carbon atoms; the substituents of Ar 1 and Ar 2 are the same or different, and are independently selected from : Deuterium, tritium, halogen, cyano, amino, hydroxyl, nitro, alkyl with 1-20 carbon atoms, cycloalkyl with 3-20 carbon atoms, aryl with 6-30 carbon atoms .
  • the Ar 1 and the Ar 2 are each independently selected from: substituted or unsubstituted aryl groups having 6-20 ring carbon atoms;
  • the substituents of the Ar 1 and the Ar 2 are the same or different, and are each independently selected from: deuterium, tritium, halogen, cyano, amino, hydroxyl, nitro, alkyl with 1-20 carbon atoms, A cycloalkyl group having 3-20 carbon atoms and an aryl group having 6-30 carbon atoms.
  • the Ar 1 and the Ar 2 are the same or different, and are independently selected from the following groups:
  • * means that the above groups are used in formula I Group bonding.
  • a photoelectric conversion device which includes an anode and a cathode arranged oppositely, and a functional layer arranged between the anode and the cathode;
  • the functional layer includes the nitrogen-containing compound.
  • the functional layer includes an electron blocking layer, and the electron blocking layer includes the nitrogen-containing compound.
  • the functional layer further includes:
  • the light-emitting layer is provided on the side of the electron blocking layer away from the anode;
  • the hole transport layer is provided on the side of the electron blocking layer away from the light-emitting layer;
  • the electron transport layer is provided between the light-emitting layer and the cathode.
  • the photoelectric conversion device is an organic electroluminescence device.
  • an electronic device including the photoelectric conversion device described in any one of the above.
  • the photoelectric conversion device is a solar cell.
  • the nitrogen-containing compound, photoelectric conversion device, and electronic device provided by the present application can shorten the distance between the nitrogen atoms by connecting the nitrogen atom of the carbazole and the nitrogen atom of the triarylamine through a phenylene group, and thus can shorten the distance between the nitrogen atoms.
  • the vertical configuration of the fused ring connection method can increase the molecular space volume and reduce the crystallization effect caused by the intermolecular stacking, thereby reducing the work of the device Voltage to extend the life of the device.
  • FIG. 1 is a schematic diagram of the structure of an organic electroluminescent device according to an embodiment of the application.
  • Fig. 2 is a hydrogen spectrum test chart of Compound 1 according to the embodiment of the application.
  • Fig. 3 is a hydrogen spectrum test chart of compound 5 according to the embodiment of the application.
  • Figure 4 is the HOMO energy level diagram of Compound 1 of the application.
  • Figure 5 is the HOMO energy level diagram of Compound A of the application.
  • Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted aryl groups with 6-30 carbon atoms;
  • the substituents of the Ar 1 and the Ar 2 are the same or different, and are each independently selected from: deuterium, tritium, halogen, cyano, amino, hydroxyl, nitro, alkyl with 1-20 carbon atoms, A cycloalkyl group having 3-20 carbon atoms and an aryl group having 6-30 carbon atoms.
  • the nitrogen-containing compound provided by this application can shorten the distance between the nitrogen atoms by connecting the nitrogen atom of the carbazole and the nitrogen atom of the triarylamine through a phenylene group, thereby reducing the plane of the triarylamine and the carbazole
  • the HOMO energy level of the material can be distributed on the triarylamine and carbazole groups at the same time through conjugation, thereby increasing the hole mobility of the material, thereby increasing the photoelectric conversion efficiency of the device; on the other hand, it can be Through different branch lengths, the symmetry of the molecules is reduced, and the amorphous arrangement of the material is further strengthened.
  • each q is independently 0, 1, 2 or 3
  • each R independently selected from hydrogen, fluorine, and chlorine in the description
  • formula Q-1 represents that there are q substituents R on the benzene ring ", each R” can be the same or different, and the options of each R" do not affect each other
  • formula Q-2 means that there are q substituents R" on each benzene ring of biphenyl, and the two benzene rings
  • the number q of R" substituents may be the same or different, and each R" may be the same or different, and the options of each R" do not affect each other.
  • substituted or unsubstituted means that it has no substituents or is substituted by one or more substituents.
  • the substituents include, but are not limited to, deuterium, halogen groups (F, Cl, Br), cyano, alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, aryloxy, arylsulfide Group, alkylamino group, arylamino group, cycloalkyl group, heterocyclic group, trialkylsilyl group, alkyl group, cycloalkyl group, alkoxy group, alkylthio group.
  • the non-positioned connection key in this application refers to the single bond extending from the ring system or 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. It includes any possible connection modes shown in formula (X'-1) to formula (X'-4).
  • Ar 1 and Ar 2 may be independently selected from substituted or unsubstituted aryl groups with 6-30 carbon atoms. It should be noted that 1 or 2 in Ar 1 and Ar 2 is only used as a mark, and is not used to limit the number.
  • an aryl group refers to an optional functional group or substituent derived from an aromatic carbocyclic 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 fused ring aryl group may include, for example, a bicyclic fused aryl group (for example, a naphthyl group), a tricyclic fused aryl group (for example, a phenanthryl group, a fluorenyl group, an anthryl group), and the like.
  • the aryl group does not contain heteroatoms such as B, N, O, S, P, Se, and Si.
  • biphenyl, terphenyl, etc. are aryl groups.
  • aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, benzo[9,10] Phenanthryl, pyrenyl, benzofluoranthene, Base and so on.
  • the "aryl group” in the present application can contain 6-20 carbon atoms. In some embodiments, the number of carbon atoms in the aryl group can be 6-18. In other embodiments, the number of carbon atoms in the aryl group can be It is 6-12. For example, the number of carbon atoms of the aryl group can be 6, 12, 13, 15, 18, or 20. Of course, the number of carbon atoms can also be other numbers, which will not be listed here.
  • the substituted aryl group may be one or more of two hydrogen atoms in the aryl group, such as deuterium, tritium, halogen, cyano, amino, hydroxyl, nitro, and alkyl with 1-20 carbon atoms.
  • Cycloalkyl groups with 3-20 carbon atoms, aryl groups with 6-30 carbon atoms and other groups are substituted.
  • the number of carbon atoms of a substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group.
  • a substituted aryl group with 18 carbon atoms refers to an aryl group and its The total number of carbon atoms of the substituent is 18.
  • alkyl may include linear or branched alkyl.
  • Alkyl groups can have 1 to 20 carbon atoms.
  • numerical ranges such as “1 to 20” refer to individual integers in the given range, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12; for another example, "an alkyl group of 1 to 12 carbon atoms” means that it can contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5
  • the alkyl group may also be a medium-sized alkyl group having 1 to 10 carbon atoms.
  • the alkyl group may also be a lower alkyl group having 1 to 6 carbon atoms.
  • the alkyl group contains 1-4 carbon atoms; in some embodiments, the alkyl group contains 1-3 carbon atoms.
  • the alkyl group may be optionally substituted with one or more substituents described in this invention.
  • alkyl groups include, but are not limited to, methyl (Me, -CH 3 ), ethyl (Et, -CH 2 CH 3 ), n-propyl (n-Pr, -CH 2 CH 2 CH 3 ), isopropyl (i-Pr, -CH(CH 3 ) 2 ), n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ), isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ), sec-butyl (s-Bu, -CH(CH 3 )CH 2 CH 3 ), tert-butyl (t-Bu, -C(CH 3 ) 3 ), etc.
  • the alkyl group may be substituted or unsubstituted.
  • Ar 1 and Ar 2 may be independently selected from substituted or unsubstituted aryl groups having 6-20 ring carbon atoms.
  • the number of ring-forming carbon atoms can be 6, 10, 14, 16 or 20. Of course, the number of ring-forming carbon atoms can also be other, which will not be listed here.
  • substitution means that at least one hydrogen atom in Ar 1 and Ar 2 may be substituted by a substituent.
  • the substituents of Ar 1 and Ar 2 may be the same or different, and Ar 1 and Ar 2 may be independently selected from: deuterium, tritium, halogen, cyano, amino, hydroxyl, nitro, and the number of carbon atoms is 1- 20 alkyl groups, 3-20 cycloalkyl groups, and 6-30 aryl groups.
  • an aryl group with 6-20 ring carbon atoms means that the number of carbon atoms in the aromatic ring in the aryl group is 6-20, and the number of carbon atoms in the substituents on the aryl group Not counted.
  • the number of ring-forming carbon atoms in the aryl group of the present invention is 6-20; in still other embodiments of the present invention, the number of ring-forming carbon atoms in the aryl group of the present invention is 6-12, but not limited to this.
  • the fluorenyl group is an aryl group having 13 ring carbon atoms, and the 9,9-dimethylfluorenyl group is a substituted 15-carbon aryl group.
  • the substituents on Ar 1 and Ar 2 are each independently selected from: deuterium, tritium, fluorine, chlorine, bromine, cyano, methyl, ethyl, isopropyl , Tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, 9,9-dimethylfluorenyl.
  • the Ar 1 and the Ar 2 are each independently selected from the group consisting of the following general formulas:
  • each of A 1 to A 19 is independently selected from deuterium, tritium, fluorine, chlorine, bromine, cyano, alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, and carbon An aryl group having 6 to 15 atoms;
  • b 1 ⁇ b 19 to b k denotes, A 1 ⁇ A 19 to A k expressed, k is a variable, represents any integer of 1 to 19, b k A k represents the number of substituents is, when b k is greater than 1, The corresponding substituents Ak are the same or different;
  • b k is selected from 0, 1, 2, 3, 4 or 5;
  • b k is selected from 0, 1, 2, 3 or 4;
  • b k is selected from 0, 1, 2 or 3;
  • b k is selected from 1, 2, 3, 4, 5 or 6;
  • b k is selected from 0, 1, 2, 3, 4, 5, 6 or 7;
  • b k is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.
  • the Ar 1 and the Ar 2 are each independently selected from: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl , Substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylene, substituted Or unsubstituted Fluorenyl group or substituted or unsubstituted fluorenyl group, wherein the substitution refers to being independently selected from deuterium, tritium, fluorine, chlorine, bromine, cyano, methyl, ethyl, isopropyl, tert-butyl, benzene Substituent group or naph
  • the Ar 1 and the Ar 2 are each independently selected from the following groups:
  • Ar 1 and Ar 2 may be the same or different, and Ar 1 and Ar 2 may be independently selected from the following groups:
  • * means that the above groups are used in formula I Group bonding.
  • Ar 1 and Ar 2 can also be selected from other groups, which are not specifically limited here.
  • Ar 1 and Ar 2 in Formula I are not at the same time Group.
  • the nitrogen-containing compound may be selected from the following compounds:
  • nitrogen-containing compounds are only exemplary nitrogen-containing compounds, and may also include other nitrogen-containing compounds, which will not be listed here.
  • MS Low-resolution mass spectrometry
  • Agilent 6120 quadrupole HPLC-M column model: Zorbax SB-C18, 2.1 ⁇ 30mm, 3.5 microns, 6min, flow rate 0.5mL/min; mobile phase: 5%-95% (The proportion of CH 3 CN containing 0.1% formic acid in H 2 O containing 0.1% formic acid), using electrospray ionization (ESI), and detecting with UV at 210nm/254nm).
  • ESI electrospray ionization
  • Proton nuclear magnetic resonance spectrum Bruker 400MHz nuclear magnetic instrument, at room temperature, with CD 2 Cl 2 or CDCl 3 as the solvent (in ppm), and TMS (0 ppm) as the reference standard.
  • the solution was cooled to room temperature, dichloromethane and water were added to extract the reaction solution, the organic phases were combined, the organic phases were dried with anhydrous magnesium sulfate, filtered to obtain the filtrate, and concentrated; the crude product was purified by silica gel column chromatography to obtain the intermediate Body-A-1 (30.45 g, yield 75%).
  • the solution was cooled to room temperature, dichloromethane and water were added to extract the reaction solution, the organic phases were combined, the organic phases were dried with anhydrous magnesium sulfate, filtered to obtain the filtrate, and concentrated; the crude product was purified by silica gel column chromatography to obtain the intermediate Body-B-1 (27.31g, yield 75%).
  • the hydrogen spectrum of compound 1 is: 1 H NMR (400MHz, CDCl 3 ) (ppm): 8.17 (d, 2H), 8.07 (d, 1H), 8.01 (d, 1H), 7.93 (d , 2H), 7.88(t, 2H), 7.76(d, 2H), 7.71(d, 2H), 7.60(d, 2H), 7.56(t, 2H), 7.53-7.44(m, 16H), 7.43( d, 2H), 7.40 (d, 2H), 7.31 (t, 2H).
  • the solution was cooled to room temperature, dichloromethane and water were added to extract the reaction solution, the organic phases were combined, the organic phases were dried with anhydrous magnesium sulfate, filtered to obtain the filtrate, and concentrated; the crude product was purified by silica gel column chromatography to obtain the intermediate Body-D-1 (29.79g, yield 70%).
  • 9-phenanthrene boronic acid (30g, 135.12mmol), 4-bromoaniline (28.57g, 166.12mmol), tetrakis(triphenylphosphine) palladium (9.59g, 8.30mmol), potassium carbonate (45.92g, 332.24mmol), Tetrabutylammonium chloride (1.89g, 8.31mmol), toluene (240mL), ethanol (120mL) and deionized water (36mL) were put into a three-necked flask, heated to 75°C ⁇ 80°C under nitrogen protection, heated under reflux and stirred for 4h .
  • the solution was cooled to room temperature, dichloromethane and water were added to extract the reaction solution, the organic phases were combined, the organic phases were dried with anhydrous magnesium sulfate, filtered to obtain the filtrate, and concentrated; the crude product was purified by silica gel column chromatography to obtain the intermediate Body-B-2 (27.29 g, 75% yield).
  • reaction solution was cooled to room temperature, the reaction solution was extracted with dichloromethane and water. The organic layer was dried with anhydrous magnesium sulfate and filtered. After filtration, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure. A dichloromethane/n-heptane system was used. The crude product was purified by recrystallization to obtain Intermediate-C-2 (39.10 g, yield 75%).
  • the hydrogen spectrum of compound 5 is: 1 H NMR (400MHz, CD 2 Cl 2 ) (ppm): 8.81 (d, 1H), 8.75 (d, 1H), 8.16 (d, 2H), 8.10 (d, 1H), 7.94 (d, 1H), 7.77 (s, 1H), 7.75-7.61 (m, 12H), 7.56 (d, 2H), 7.52 (t, 4H), 7.49-7.44 (m, 6H) ), 7.42 (d, 4H), 7.37 (t, 1H), 7.30 (t, 2H).
  • the photoelectric conversion device may include an anode 1 and a cathode 5 arranged oppositely, and a functional layer 3 arranged between the anode 1 and the cathode 5.
  • the functional layer 3 The nitrogen-containing compound of any of the above-mentioned embodiments may be included.
  • the anode 1 may be a material that facilitates hole injection into the functional layer 3, and the material may have a large work function (work function).
  • the anode 1 material can be metal, alloy or metal oxide, etc., for example, it can be nickel, platinum, vanadium, chromium, copper, zinc, gold or their alloys, or zinc oxide, indium oxide, Indium tin oxide (ITO) and indium zinc oxide (IZO); of course, the anode 1 material can also be other, for example, it can also be a composition, such as: ZnO: Al, SnO 2 : Sb, conductive polymer (poly(3) -Methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole and polyaniline).
  • the anode 1 material is not limited to this, but can also be Other materials will not be listed here.
  • the anode 1 material may be indium tin oxide (ITO).
  • the cathode 5 may be a material that facilitates injection of electrons into the functional layer 3, and the material may have a smaller work function.
  • the material of the cathode 5 can be a metal or alloy material, for example, it can be magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead or their alloys. It can be a multilayer material, such as: LiF/Al, Liq/Al, LiO 2 /Al, LiF/Ca, LiF/Al, and BaF 2 /Ca.
  • the cathode 5 material is not limited to this, but can also be other materials. This will not be listed one by one.
  • the material of the cathode 5 may be aluminum.
  • the photoelectric conversion device may be a solar cell, or an organic electroluminescence device, of course, it may also be other photoelectric conversion devices, which will not be listed here.
  • the functional layer 3 can be used for the transport of electrons and holes, and can provide a place for recombination or separation of electrons and holes.
  • the electrons and holes can recombine in the functional layer 3 to generate excitons, which has achieved the effect of light emission.
  • the nitrogen-containing compound of any embodiment of the present application can be used to form one or more layers of the functional layer 3 to reduce the working voltage of the photoelectric conversion device, increase the luminous efficiency, and prolong the service life of the device.
  • the functional layer 3 may include an electron blocking layer 32
  • the electron blocking layer 32 may include the nitrogen-containing compound according to any embodiment of the present application.
  • the nitrogen-containing compound can be used to block the transmission of electrons to the anode 1, that is, the nitrogen-containing compound of any embodiment of the present application can be used as an electron blocking material.
  • the functional layer 3 can also include a light-emitting layer 33, a hole transport layer 31, and an electron transport layer 34.
  • the light-emitting layer 33 can be provided on the side of the electron blocking layer 32 away from the anode 1; the hole transport layer 31 can be provided on The electron blocking layer 32 is away from the side of the light emitting layer 33; the electron transport layer 34 may be provided between the light emitting layer 33 and the cathode 5.
  • the photoelectric conversion device may include an anode 1, a hole transport layer 31, a light emitting layer 33, an electron transport layer 34, and a cathode 5 arranged in a stack.
  • the photoelectric conversion device of the embodiment of the present application may further include a hole injection layer 2 and an electron injection layer 4, wherein: the hole injection layer 2 may be provided between the anode 1 and the hole transport layer 31; the electron injection layer 4 may It is provided between the cathode 5 and the electron transport layer 34.
  • the photoelectric conversion device may be an organic electroluminescence device.
  • the anode 1 is prepared by the following process: the thickness of ITO is The ITO substrate is cut into a size of 40mm (length) ⁇ 40mm (width) ⁇ 0.7mm (thickness), and the photolithography process is used to prepare it into an experimental substrate with cathode 5, anode 1 and insulating layer patterns, and can use ultraviolet light Ozone and O 2 :N 2 plasma are used for surface treatment to increase the work function of anode 1, and organic solvents can be used to clean the surface of the ITO substrate to remove impurities and grease on the surface of the ITO substrate. It should be noted that the ITO substrate can also be cut into other sizes according to actual needs, and the size of the ITO substrate in this application is not specifically limited here.
  • m-MTDATA (4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine) was vacuum-evaporated on the experimental substrate (anode 1) (the structural formula can be seen below) to form The thickness is Hole injection layer 2 (HIL), and NPB (N,N'-diphenyl-N,N'-(1-naphthyl)-1,1) is vacuum-evaporated on the hole injection layer 2 (HIL) '-Biphenyl-4,4'-diamine) (the structural formula can be seen below) to form a thickness of The hole transport layer 31 (HTL).
  • HIL Hole injection layer 2
  • NPB N,N'-diphenyl-N,N'-(1-naphthyl)-1,1
  • Compound 1 was vapor-deposited on the hole transport layer 31 (HTL) to form a thickness of The electron blocking layer 32 (EBL).
  • EBL electron blocking layer 32
  • the thickness of the electron blocking layer 32 (EBL) can be or Of course, it can also be other thicknesses, which are not listed here.
  • the light-emitting layer 33 (EML).
  • the thickness of the light-emitting layer 33 (EML) may be or Of course, it can also be other thicknesses, which will not be listed here.
  • DBimiBphen (structure formula can be seen below) and LiQ (structure formula can be seen below) are mixed in a weight ratio of 1:1, and can be formed by evaporation process Thick electron transport layer 34 (ETL), for example, the thickness of the electron transport layer 34 can be or Of course, it can also be other thicknesses, which are not listed here.
  • Thick electron transport layer 34 ETL
  • LiQ was vapor-deposited on the electron transport layer 34 to form a thickness of The electron injection layer 4 (EIL), for example, the thickness of the electron injection layer 4 can be or Of course, it can also be other thicknesses, which will not be listed here.
  • magnesium (Mg) and silver (Ag) were mixed at a vapor deposition rate of 1:9, and vacuum vapor deposited on the electron injection layer 4 (EIL) to form a thickness of The cathode 5.
  • the vapor deposition thickness on the cathode 5 is CP-1 (the structural formula can be seen below) to form a cover layer (CPL) to complete the manufacture of organic light-emitting devices.
  • Example 2 uses compound 2 as one or more layers of the functional layer 3 to make an organic electroluminescence device;
  • Example 3 uses compound 3 as one or more layers of the functional layer 3 to make an organic electroluminescence device Device;
  • Example 4 uses compound 4 as one or more layers in the functional layer 3 to make an organic electroluminescence device;
  • Example 5 uses compound 5 as one or more layers in the functional layer 3 to make an organic electroluminescence device Device;
  • Example 6 uses compound 6 as one or more layers in the functional layer 3 to make an organic electroluminescence device;
  • Example 7 uses compound 7 as one or more layers in the functional layer 3 to make an organic electroluminescence device Device;
  • Example 8 uses compound 8 as one or more layers of the functional layer 3 to produce an organic electroluminescent device; and the performance parameters of each device are shown in Table 1.
  • the organic electroluminescence device can be manufactured by the same method as in Example 1, except that Compound A to Compound D can be used as the electron blocking layer 32 (EBL) instead of the compound, respectively.
  • EBL electron blocking layer 32
  • the structures of compound A to compound D are as follows:
  • Comparative Example 1 uses Compound A to manufacture organic electroluminescent devices
  • Comparative Example 2 uses Compound B to manufacture organic electroluminescent devices
  • Comparative Example 3 uses Compound C to manufacture organic electroluminescent devices
  • Comparative Example 4 uses Compound D to manufacture organic electroluminescent devices.
  • Luminescent device; the performance of each device prepared is shown in Table 1. Wherein, IVL (current, voltage, luminance) data in contrast to the test results at 2 10mA / cm, T95 life test results at 20mA / cm 2 current density.
  • Example 1 Example 2, Example 3, Example 4, Example 5, Example 6, and Example 7 using Compound 1 to Compound 8 as the electron blocking layer 32 (EBL)
  • Comparative Example 1 Comparative Example 1
  • Comparative Example 2 Comparative Example 3
  • Comparative Example 4 Comparative Example 4 using Compound A to Compound D
  • the luminous efficiency and device life of Example 8 are greatly improved.
  • the organic electroluminescence device prepared by using compound 5 as the electron blocking layer 32 (EBL) in Example 5 of this application has an increase in luminous efficiency (Cd/A) by 54.7%, and an external quantum efficiency by at least 56.5%.
  • the life span is prolonged by 42 hours, an increase of 75.4%. Therefore, it can be seen that the luminous efficiency and lifetime performance of the organic electroluminescent device of the embodiment of the present application are significantly improved.
  • Compounds 1 to 8 of the present application have significant improvements in both efficiency and life span; specifically, the nitrogen atom of the carbazole and the triaryl
  • the nitrogen atoms of the base amines are connected by phenylene groups, which can shorten the distance between the nitrogen atoms, thereby reducing the angle between the triarylamine and the carbazole plane, so that the HOMO energy level of the material can be simultaneously distributed in the triarylamine through conjugation.
  • compounds 1 to 8 of the present application have significantly improved efficiency and life span; compounds 1 to 8 of the present application can introduce large planar fused ring groups into the other two branches of triarylamine The group can effectively disperse the electron cloud density of the triarylamine and avoid the cleavage of the CN bond.
  • the vertical configuration of the fused ring connection method can increase the molecular space volume and reduce the crystallization effect caused by the intermolecular stacking. The working voltage of the device can be reduced, and the life of the device can be prolonged.
  • the HOMO energy level of compound 1 of the present application is simultaneously distributed on the triarylamine and the carbazole group through conjugation.
  • the nitrogen atom of the carbazole and the nitrogen atom of the triarylamine are connected by a phenylene group, shortening
  • the distance between the nitrogen atoms increases the hole mobility of the material, thereby increasing the photoelectric conversion efficiency of the device.
  • the present application also provides an electronic device, which may include the photoelectric conversion device of any of the foregoing embodiments, and the beneficial effects and specific details of the photoelectric conversion device can be referred to the foregoing photoelectric conversion device, which will not be repeated here.
  • the electronic device may be a display, an array substrate, a photovoltaic module, etc., of course, it may also be other devices, which will not be listed here.

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Abstract

提供一种含氮化合物、光电转换器件及电子装置，属于光电技术领域。该含氮化合物的结构通式如式I所示，其中，Ar1和Ar2分别独立的选自取代或未取代的碳原子数为6-30的芳基；Ar1和Ar2的取代基相同或不同，且分别独立地选自：氘、氚、卤素、氰基、氨基、羟基、硝基、碳原子数为1-20的烷基、碳原子数为3-20的环烷基、碳原子数为6-30的芳基。该含氮化合物及光电转换器件可提高器件的光电转化效率，延长器件寿命。

Description

含氮化合物、光电转化器件及电子装置
相关申请的交叉引用
本申请要求于2019年8月23日递交的、申请号为CN201910785145.X的中国专利申请的优先权，在此引用上述中国专利申请公开的内容全文以作为本公开的一部分。
技术领域
本申请涉及光电技术领域，具体而言，涉及一种含氮化合物、光电转化器件及电子装置。
背景技术
近年来，有机电致发光器件(OLED，Organic electroluminescent device)作为新一代显示技术逐渐进入人们的视野。常见的有机电致发光器件是由阳极、阴极以及设于阴极和阳极之间的有机层构成。当向阴极和阳极施加电压时，两电极产生电场，在电场的作用下，阴极侧的电子与阳极侧的空穴同时向功能层移动，且其在功能层结合形成激子，激子处于激发态向外释放能量，从激发态变为基态的过程对外发光。因此，提高OLED器件中电子和空穴的再结合性是至关重要的。
光电转化器件中常设置有电子阻挡层及电子传输层等，以改善器件的寿命。但是，目前的器件存在低效率的问题。因此，如何设计新的性能更好的材料应用于电阻挡层或电子传输层等，以至于所有器件能够达到降低电压、提高光电转化效率和寿命的效果，一直是本领域技术人员亟待解决的问题。
现有技术文献也对此进行了研究，例如：CN102224150B、专利文献CN103827257B、专利文献CN105061371B以及专利文献CN108137500A。
需要说明的是，在上述背景技术部分公开的信息仅用于加强对本申请的背景的理解，因此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
本申请的目的在于克服上述现有技术中的不足，提供一种含氮化合物及光电转化器件，可提高光电转化效率，延长器件寿命。
根据本申请的一个方面，提供一种含氮化合物，所述含氮化合物的结构通式如式I所示：
Figure PCTCN2020096880-appb-000001
其中，Ar 1和Ar 2分别独立的选自取代或未取代的碳原子数为6-30的芳基；所述Ar 1和所述Ar 2 的取代基相同或不同，且分别独立地选自：氘、氚、卤素、氰基、氨基、羟基、硝基、碳原子数为1-20的烷基、碳原子数为3-20的环烷基、碳原子数为6-30的芳基。
在本申请的一些实施方案中，所述Ar 1和所述Ar 2分别独立地选自：取代或未取代的成环碳原子数为6-20的芳基；
所述Ar 1和所述Ar 2的取代基相同或不同，且分别独立地选自：氘、氚、卤素、氰基、氨基、羟基、硝基、碳原子数为1-20的烷基、碳原子数为3-20的环烷基、碳原子数为6-30的芳基。
在本申请的一些实施方案中，所述Ar 1和所述Ar 2相同或不同，且分别独立的选自如下基团：
Figure PCTCN2020096880-appb-000002
其中，*表示上述基团用于与式I中
Figure PCTCN2020096880-appb-000003
基团结合。
根据本申请的一个方面，提供一种光电转化器件，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；
所述功能层包含所述的含氮化合物。
在本申请的一些实施方案中，所述功能层包括电子阻挡层，所述电子阻挡层包含所述的含氮化合物。
在本申请的一些实施方案中，所述功能层还包括：
发光层，设于所述电子阻挡层远离所述阳极的一侧；
空穴传输层，设于所述电子阻挡层远离所述发光层的一侧；
电子传输层，设于所述发光层与所述阴极之间。
在本申请的一些实施方案中，所述光电转化器件为有机电致发光器件。
根据本申请的一个方面，提供一种电子装置，包括上述任意一项所述的光电转化器件。
在本申请的一些实施方案中，所述光电转化器件为太阳能电池。
本申请提供的含氮化合物、光电转化器件及电子装置，一方面，可通过将咔唑的氮原子和三芳基胺的氮原子通过亚苯基相连，可缩短氮原子之间的距离，进而可缩小三芳胺和咔唑平面的夹角，从 而可将材料的HOMO能级通过共轭作用同时分布在三芳胺以及咔唑基团上，从而提高材料的空穴迁移率，进而提高器件的光电转化效率；另一方面，可通过不同的分支长度，降低分子的对称性，进一步加强材料的无定形排列，还可通过在三芳基胺的另两个分支引入大平面稠环基团，可有效分散对三芳基胺的电子云密度，避免C-N键的裂解，同时，可通过垂直构型的稠环连接方式，增大分子空间体积，降低分子间堆叠带来的结晶效应，进而可降低器件的工作电压，延长器件寿命。
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本申请。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本申请的实施例，并与说明书一起用于解释本申请的原理。显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施方式有机电致发光器件的结构示意图。
图2为本申请实施方式化合物1的氢谱测试图。
图3为本申请实施方式化合物5的氢谱测试图。
图4为本申请化合物1的HOMO能级图。
图5为本申请化合物A的HOMO能级图。
图中：1、阳极；2、空穴注入层；3、功能层；31、空穴传输层；32、电子阻挡层；33、发光层；34、电子传输层；4、电子注入层；5、阴极。
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。
用语“该”和“所述”用以表示存在一个或多个要素/组成部分/等；用语“包括”和“具有”用以表示开放式的包括在内的意思并且是指除了列出的要素/组成部分/等之外还可存在另外的要素/组成部分/等。
本申请实施方式提供了一种含氮化合物，该含氮化合物的结构通式如式I所示：
Figure PCTCN2020096880-appb-000004
其中，Ar 1和Ar 2分别独立的选自取代或未取代的碳原子数为6-30的芳基；
所述Ar 1和所述Ar 2的取代基相同或不同，且分别独立地选自：氘、氚、卤素、氰基、氨基、羟基、硝基、碳原子数为1-20的烷基、碳原子数为3-20的环烷基、碳原子数为6-30的芳基。
本申请提供的含氮化合物，一方面，可通过将咔唑的氮原子和三芳基胺的氮原子通过亚苯基相连，可缩短氮原子之间的距离，进而可缩小三芳胺和咔唑平面的夹角，从而可将材料的HOMO能级通过共轭作用同时分布在三芳胺以及咔唑基团上，从而提高材料的空穴迁移率，进而提高器件的光电转化效率；另一方面，可通过不同的分支长度，降低分子的对称性，进一步加强材料的无定形排列，还可通过在三芳基胺的另两个分支引入大平面稠环基团，可有效分散对三芳基胺的电子云密度，避免C-N键的裂解，同时，可通过垂直构型的稠环连接方式，增大分子空间体积，降低分子间堆叠带来的结晶效应，进而可降低器件的工作电压，延长器件寿命。
下面对本申请实施方式含氮化合物的各部分进行详细说明：
在本申请中，
Figure PCTCN2020096880-appb-000005
和
Figure PCTCN2020096880-appb-000006
含义一样，均是指与其他取代基或结合位置结合的位置。
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。举例而言：在“
Figure PCTCN2020096880-appb-000007
其中，各q独立地为0、1、2或3，各R”独立地选自氢、氟、氯”的描述中，其含义是：式Q-1表示苯环上有q个取代基R”，各个R”可以相同也可以不同，每个R”的选项之间互不影响；式Q-2表示联苯的每一个苯环上有q个取代基R”，两个苯环上的R”取代基的个数q可以相同或不同，各个R”可以相同也可以不同，每个R”的选项之间互不影响。
在本申请中，术语“取代或未取代的”是指没有取代基或者被一个或多个取代基取代。所述取代基包括但不限于，氘、卤素基团(F、Cl、Br)、氰基、烷基、烯基、炔基、卤代烷基、芳基、杂芳基、芳氧基、芳硫基、烷胺基、芳胺基、环烷基、杂环基、三烷基硅基、烷基、环烷基、烷氧基、烷硫基。
本申请中的不定位连接键，是指从环体系中伸出的单键
Figure PCTCN2020096880-appb-000008
或
Figure PCTCN2020096880-appb-000009
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。例如，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 PCTCN2020096880-appb-000010
本申请的含氮化合物的结构通式如式I所示：
Figure PCTCN2020096880-appb-000011
其中，Ar 1和Ar 2可分别独立的选自取代或未取代的碳原子数为6-30的芳基。需要说明的是，Ar 1及Ar 2中的1或2仅作为标记使用，不用来限定数量。
本申请中，芳基指的是衍生自芳香碳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更多个芳香基团也可以视为本申请的芳基。其中，稠环芳基例如可以包括双环稠合芳基(例如萘基)、三环稠合芳基(例如菲基、芴基、蒽基)等。其中，芳基中不含有B、N、O、S、P、Se和Si等杂原子。举例而言，在本申请中，联苯基、三联苯基等为芳基。芳基的实例可以包括但不限于，苯基、萘基、芴基、蒽基、菲基、联苯基、三联苯基、四联苯基、五联苯基、苯并[9,10]菲基、芘基、苯并荧蒽基、
Figure PCTCN2020096880-appb-000012
基等。本申请的“芳基”可含有6-20个碳原子，在一些实施例中，芳基中的碳原子数可以是6-18个，在另一些实施例中芳基中的碳原子数可以是6-12个。举例而言，芳基的碳原子数量可以是6个、12个、13个、15个、18个或20个，当然，碳原子数还可以是其他数量，在此不再一一列举。
在本申请中，取代的芳基可以是芳基中的一个或者两个以上氢原子被诸如氘、氚、卤素、氰基、氨基、羟基、硝基、碳原子数为1-20的烷基、碳原子数为3-20的环烷基、碳原子数为6-30的芳基等基团取代。应当理解地是，取代的芳基的碳原子数，指的是芳基和芳基上的取代基的碳原子总数，例如碳原子数为18的取代的芳基，指的是芳基及其取代基的总碳原子数为18。
在本申请中，“烷基”可以包括直链烷基或支链烷基。烷基可具有1至20个碳原子，在本申请中，诸如“1至20”的数值范围是指给定范围中的各个整数，例如1、2、3、4、5、6、7、8、9、10、11和12；再例如，“1至12个碳原子的烷基”是指可包含1个碳原子、2个碳原子、3个碳原子、4个碳原子、5个碳原子、6个碳原子、7个碳原子、8个碳原子、9个碳原子、10个碳原子、11个碳原子或12个碳原子的烷基。烷基还可为具有1至10个碳原子的中等大小烷基。烷基还可为具有1至6个碳原子的低级烷基。在另一些实施方案中，烷基基团含有1-4个碳原子；还在一些实施方案中，烷基基团含有1-3个碳原子。所述烷基基团可以任选地被一个或多个本发明描述的取代基所取代。烷基基团的实例包含，但并不限于，甲基(Me、-CH 3)，乙基(Et、-CH 2CH 3)，正丙基(n-Pr、-CH 2CH 2CH 3)，异丙基(i-Pr、-CH(CH 3) 2)，正丁基(n-Bu、-CH 2CH 2CH 2CH 3)，异丁基(i-Bu、-CH 2CH(CH 3) 2)，仲丁基(s-Bu、-CH(CH 3)CH 2CH 3)，叔丁基(t-Bu、-C(CH 3) 3)等。此外，烷基可为取代的或未取代的。
在一实施方式中，Ar 1和Ar 2可分别独立地选自：取代或未取代的成环碳原子数为6-20的芳基。
举例而言，其成环碳原子数可以是6个，10个，14个，16个或20个，当然，成环碳原子数还可以是其他，在此不再一一列举。其中，取代是指Ar 1和Ar 2中至少一个氢原子可被取代基取代。Ar 1和Ar 2的取代基可以相同也可以不同，且Ar 1和Ar 2均可分别独立地选自：氘、氚、卤素、氰基、氨基、羟基、硝基、碳原子数为1-20的烷基、碳原子数为3-20的环烷基、碳原子数为6-30的芳基。在本申请中，“成环碳原子数为6-20的芳基”指的是芳基中位于芳香环上的碳原子数是6-20个，芳基上的取代基中的碳原子数不计算在内。在本发明的一些实施方案中，本发明的芳基中的成环碳原子数为6-20个；在本发明的又一些实施方案中，本发明的芳基中的成环碳原子数为6-12个，但不限于此。示例地，芴基属于成环碳原子数为13的芳基，9,9-二甲基芴基属于取代的15个碳原子的芳基。
在本申请的一些实施方案中，所述Ar 1和所述Ar 2上的取代基各自独立地选自：氘、氚、氟、氯、溴、氰基、甲基、乙基、异丙基、叔丁基、苯基、萘基、二联苯基、三联苯基、芴基、9,9-二甲基芴基。
在本申请的一些实施方案中，所述Ar 1和所述Ar 2各自独立地选自如下通式所组成的组：
Figure PCTCN2020096880-appb-000013
其中，各A 1～A 19分别独立地选自氘、氚、氟、氯、溴、氰基、碳原子数为1～4的烷基、碳原子数为3～10的环烷基、碳原子数为6～15的芳基；
b 1～b 19以b k表示，A 1～A 19以A k表示，k为变量，表示1～19的任意整数，b k表示取代基A k的个数，当b k大于1时，相应的取代基A k相同或不同；
其中，当k选自1、3、6、14、15、17或19时，b k选自0、1、2、3、4或5；
当k选自2、4、9、11、13或18时，b k选自0、1、2、3或4；
当k选自5、12、16时，b k选自0、1、2或3；
当k选自10时，b k选自1、2、3、4、5或6；
当k选自7时，b k选自0、1、2、3、4、5、6或7；
当k选自8时，b k选自0、1、2、3、4、5、6、7、8或9。
在本申请的一些实施方案中，所述Ar 1和所述Ar 2各自独立地选自：取代或未取代的苯基、取代或未取代的二联苯基、取代或未取代的三联苯基、取代或未取代的萘基、取代或未取代的蒽基、取代或未取代的菲基、取代或未取代的菲基、取代或未取代的芘基、取代或未取代的苝基、取代或未取代的
Figure PCTCN2020096880-appb-000014
基或取代或未取代的芴基，其中，所述取代是指被独立地选自氘、氚、氟、氯、溴、氰基、甲基、乙基、异丙基、叔丁基、苯基或萘基的取代基所取代。
在本申请的一些实施方案中，所述Ar 1和所述Ar 2分别独立地选自以下基团：
Figure PCTCN2020096880-appb-000015
在一些实施方式中，Ar 1和Ar 2可以相同，也可以不同，且Ar 1和Ar 2可分别独立的选自如下基团：
Figure PCTCN2020096880-appb-000016
其中，*表示上述基团用于与式I中
Figure PCTCN2020096880-appb-000017
基团结合。当然，Ar 1和Ar 2还可选自其他基团，在此不做特殊限定。
在一些实施方式中，，在式I中Ar 1和Ar 2不同时为
Figure PCTCN2020096880-appb-000018
基团。
在一实施方式中，含氮化合物可选自如下化合物：
Figure PCTCN2020096880-appb-000019
需要说明的是，以上含氮化合物仅为示例性的含氮化合物，还可以包含其他含氮化合物，在此不再一一列举。
实施例
下面，通过实施例对本申请的含氮化合物的合成过程进行详细说明。但是，下述实施例仅是本申请的例示，而并非限定本申请。
在本说明书中，除非另有说明，实施例中所用试剂和原料均购买于商品供应商。
低分辨率质谱(MS)：Agilent 6120四级杆HPLC-M(柱子型号：Zorbax SB-C18，2.1×30mm，3.5微米，6min，流速为0.5mL/min；流动相：5％-95％(含0.1％甲酸的CH 3CN在含0.1％甲酸的H 2O中的比例)，采用电喷雾电离(ESI)，在210nm/254nm下，用UV检测)。
核磁共振氢谱：布鲁克(Bruker)400MHz核磁仪，室温条件下，以CD 2Cl 2或CDCl 3为溶剂(以ppm为单位)，用TMS(0ppm)作为参照标准。
化合物1的合成：
Figure PCTCN2020096880-appb-000020
将4’-氯联苯-4-硼酸(30.00g，129.04mmol)、1-溴萘(26.72g，129.04mmol)、四(三苯基膦)钯(7.45g，6.45mmol)、碳酸钾(35.67g，258.09mmol)、四丁基氯化铵(1.47g，6.45mmol)、甲苯(240mL)、乙醇(120mL)和去离子水(36mL)加入三口烧瓶中，氮气保护下升温至75℃～80℃，加热回流搅拌4h。反应结束后，溶液冷却至室温，加入二氯甲烷和水萃取反应液，合并有机相，采用无水硫酸镁干燥有机相，过滤得到滤液，将其浓缩；粗品利用硅胶柱色谱进行提纯，得到中间体-A-1(30.45g，收率为75％)。
Figure PCTCN2020096880-appb-000021
将1-萘硼酸(30g，174.42mmol)、4-溴苯胺(28.57g，166.12mmol)、四(三苯基膦)钯(9.59g，8.30mmol)、碳酸钾(45.92g，332.24mmol)、四丁基氯化铵(1.89g，8.31mmol)、甲苯(240mL)、乙醇(120mL)和去离子水(36mL)加入三口烧瓶中，氮气保护下升温至75℃～80℃，加热回流搅拌4h。反应结束后，溶液冷却至室温，加入二氯甲烷和水萃取反应液，合并有机相，采用无水硫酸镁干燥有机相，过滤得到滤液，将其浓缩；粗品利用硅胶柱色谱进行提纯，得到中间体-B-1 (27.31g，收率为75％)。
Figure PCTCN2020096880-appb-000022
将中间体-B-1(27.31g，124.53mmol)、9-(4-溴苯基)咔唑(40.12g，124.53mmol)、三(二亚苄基丙酮)二钯(1.14g，1.24mmol)、2-双环己基膦-2,4,6-三异丙基联苯(1.19g，2.50mmol)、叔丁醇钠(17.95g，186.81mmol)加入溶剂甲苯(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到中间体-C-1(43.02g，收率为76％)。
Figure PCTCN2020096880-appb-000023
将中间体-C-1(10.00g，21.71mmol)、中间体-A-1(6.83g，21.71mmol)、三(二亚苄基丙酮)二钯(0.20g，0.22mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入溶剂甲苯(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合物1(11.12g，收率为70％)。质谱：m/z＝738.93(M+H) +。如图2所示，化合物1的氢谱为： 1H NMR(400MHz，CDCl 3)(ppm)：8.17(d，2H)，8.07(d，1H)，8.01(d，1H)，7.93(d，2H)，7.88(t，2H)，7.76(d，2H)，7.71(d，2H)，7.60(d，2H)，7.56(t，2H)，7.53-7.44(m，16H)，7.43(d，2H)，7.40(d，2H)，7.31(t，2H)。
化合物2的合成：
Figure PCTCN2020096880-appb-000024
将中间体-C-1(10.00g，21.71mmol)、4-溴对三联苯(6.65g，21.52mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入溶剂甲苯(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合物2(10.43g，收率为70％)。质谱：m/z＝692.90(M+H) +。
化合物3的合成：
Figure PCTCN2020096880-appb-000025
将9-溴菲(30g，116.67mmol)、4’-氯联苯-4-硼酸(27.12g，116.67mmol)、四(三苯基膦)钯(7.45g，6.45mmol)、碳酸钾(35.67g，258.09mmol)、四丁基氯化铵(1.47g，6.45mmol)、甲苯(240mL)、乙醇(120mL)和去离子水(36mL)加入三口烧瓶中，氮气保护下升温至75℃～80℃，加热回流搅拌4h。反应结束后，溶液冷却至室温，加入二氯甲烷和水萃取反应液，合并有机相，采用无水硫酸镁干燥有机相，过滤得到滤液，将其浓缩；粗品利用硅胶柱色谱进行提纯，得到中间体-D-1(29.79g，收率为70％)。
Figure PCTCN2020096880-appb-000026
将中间体-C-1(10.00g，21.71mmol)、中间体-D-1(8.81g，21.52mmol)、三(二亚苄基丙酮)二钯(0.20g，0.22mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合物3(12.11g，收率为71％)。质谱：m/z＝793.02(M+H) +。
化合物4的合成：
Figure PCTCN2020096880-appb-000027
将9-菲硼酸(30g，135.12mmol)、4-溴苯胺(28.57g，166.12mmol)、四(三苯基膦)钯(9.59g，8.30mmol)、碳酸钾(45.92g，332.24mmol)、四丁基氯化铵(1.89g，8.31mmol)、甲苯(240mL)、乙醇(120mL)和去离子水(36mL)加入三口烧瓶中，氮气保护下升温至75℃～80℃，加热回流搅拌4h。反应结束后，溶液冷却至室温，加入二氯甲烷和水萃取反应液，合并有机相，采用无水硫酸镁干燥有机相，过滤得到滤液，将其浓缩；粗品利用硅胶柱色谱进行提纯，得到中间体-B-2(27.29g，收率为75％)。
Figure PCTCN2020096880-appb-000028
将中间体-B-2(27.29g，101.32mmol)、9-(4-溴苯基)咔唑(40.12g，124.53mmol)、三(二亚苄基丙酮)二钯(1.14g，1.24mmol)、2-双环己基膦-2,4,6-三异丙基联苯(1.19g，2.50mmol)、叔丁醇钠(17.95g，186.81mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到中间体-C-2(39.10g，收率为75％)。
Figure PCTCN2020096880-appb-000029
将中间体-C-2(10.00g，19.42mmol)、中间体-D-1(7.09g，19.43mmol)、三(二亚苄基丙酮)二钯(0.20g，0.22mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。 反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合物4(12.11g，收率为71％)。质谱：m/z＝793.02(M+H) +。
化合物5的合成：
Figure PCTCN2020096880-appb-000030
将中间体-C-2(10.00g，19.42mmol)、4-溴对三联苯(6.00g，19.42mmol)、三(二亚苄基丙酮)二钯(0.20g，0.22mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合物5(10.25g，收率为70％)。质谱：m/z＝742.96(M+H) +。如图3所示，化合物5的氢谱为： 1H NMR(400MHz，CD 2Cl 2)(ppm)：8.81(d，1H)，8.75(d，1H)，8.16(d，2H)，8.10(d，1H)，7.94(d，1H)，7.77(s，1H)，7.75-7.61(m，12H)，7.56(d，2H)，7.52(t，4H)，7.49-7.44(m，6H)，7.42(d，4H)，7.37(t，1H)，7.30(t，2H)。
化合物6的合成：
Figure PCTCN2020096880-appb-000031
将中间体-C-2(10.00g，19.42mmol)、中间体-A-1(6.11g，19.42mmol)、三(二亚苄基丙酮)二钯(0.20g，0.22mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合 物6(10.93g，收率为71％)。质谱：m/z＝788.99(M+H) +。
化合物7的合成：
Figure PCTCN2020096880-appb-000032
将对苯基苯胺(30.39g，179.59mmol)、9-(4-溴苯基)咔唑(40.12g，124.53mmol)、三(二亚苄基丙酮)二钯(1.14g，1.24mmol)、2-双环己基膦-2,4,6-三异丙基联苯(1.19g，2.50mmol)、叔丁醇钠(17.95g，186.81mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105-110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到中间体-C-3(50.62g，收率为69％)。
Figure PCTCN2020096880-appb-000033
将中间体-C-3(6.11g，19.42mmol)、中间体-A-1(6.83g，21.71mmol)、三(二亚苄基丙酮)二钯(0.20g，0.22mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合物7(11.69g，收率为70％)。质谱：m/z＝692.90(M+H) +。
化合物8的合成：
Figure PCTCN2020096880-appb-000034
将中间体-C-3(6.11g，19.42mmol)、中间体-D-1(8.88g，24.12mmol)、三(二亚苄基丙酮)二钯(0.20g，0.22mmol)、2-双环己基膦-2',6'-二甲氧基联苯(0.18g，0.43mmol)、叔丁醇钠(3.13g，32.56mmol)加入甲苯溶剂(260mL)中，氮气保护下升温至105℃～110℃，加热回流搅拌10h。反应液冷却至室温后，二氯甲烷和水萃取反应溶液，采用无水硫酸镁干燥有机层，过滤，过滤后将滤液通过短硅胶柱，减压除去溶剂，使用二氯甲烷/正庚烷体系对粗品进行重结晶提纯，得到化合物8(12.72g，收率为71％)。质谱：m/z＝742.96(M+H) +。
本申请还提供一种光电转化器件，如图1所示，该光电转换器件可以包括相对设置的阳极1和阴极5，以及设于阳极1和阴极5之间的功能层3，该功能层3可以包含上述任一实施方式的含氮化合物。
阳极1可以是有助于空穴注入至功能层3的材料，该材料可具有大逸出功(功函数，work function)。举例而言，阳极1材料可以是金属、合金或金属氧化物等，例如，其可以是镍、铂、钒、铬、铜、锌、金或它们的合金，也可以是氧化锌、氧化铟、氧化铟锡(ITO)和氧化铟锌(IZO)；当然，阳极1材料还可以是其他，例如，还可以是组合物，如：ZnO:Al、SnO 2:Sb、导电聚合物(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)，当然，阳极1材料不仅限于此，还可以是其他材料，在此不再一一列举。优选地，阳极1材料可以是氧化铟锡(ITO，indium tin oxide)。
阴极5可以是有助于电子注入至功能层3的材料，该材料可具有较小的逸出功。举例而言，阴极5材料可以是金属或合金材料，例如，其可以是镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡、铅或它们的合金，也可以是多层材料，如：LiF/Al、Liq/Al、LiO 2/Al、LiF/Ca、LiF/Al和BaF 2/Ca，当然，阴极5材料不仅限于此，还可以是其他材料，在此不再一一列举。优选地，阴极5材料可以是铝。举例而言，该光电转化器件可以是太阳能电池，也可以是有机电致发光器件，当然，还可以是其他光电转化器件，在此不再一一列举。
功能层3可用于电子及空穴的传输，并可为电子和空穴提供复合或分离的场所，电子和空穴可在功能层3复合产生激子，已达到发光的效果。
在一实施方式中，本申请任一实施方式的含氮化合物均可用于形成功能层3中的一层或多层，以降低光电转化器件的工作电压、提高发光效率、延长器件使用寿命。举例而言，功能层3可以包括电子阻挡层32，该电子阻挡层32可以包含本申请任一实施方式的含氮化合物。该含氮化合物可用于阻挡电子向阳极1传输，即：本申请任一实施方式的含氮化合物均可作为电子阻挡材料。
功能层3还可以包括发光层33、空穴传输层31及电子传输层34，其中：发光层33可设于电子阻挡层32远离所述阳极1的一侧；空穴传输层31可设于电子阻挡层32远离所述发光层33的一侧；电子传输层34可设于发光层33与所述阴极5之间。光电转化器件可以包括叠层设置的阳极1、空穴传输层31、发光层33、电子传输层34及阴极5。
同时，本申请实施方式的光电转化器件还可以包括空穴注入层2和电子注入层4，其中：空穴注入层2可设于阳极1与空穴传输层31之间；电子注入层4可设于阴极5和电子传输层34之间。举例而言，该光电转化器件可以是有机电致发光器件。
下面，以有机电致发光器件为例，通过实施例对本申请的有机电致发光器件进行详细说明。但是，下述实施例仅是本申请的例示，而并非限定本申请。
有机电致发光器件的制作及评估实施例
实施例1：蓝色有机电致发光器件的制作
通过以下过程制备阳极1：将ITO厚度为
Figure PCTCN2020096880-appb-000035
的ITO基板切割成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5、阳极1以及绝缘层图案的实验基板，并可利用紫外臭氧以及O 2:N 2等离子进行表面处理，以增加阳极1的功函数，并可采用有机溶剂清洗ITO基板表面，以清除ITO基板表面的杂质及油污。需要说明的是，ITO基板还可以根据实际需要切割成其他尺寸，在此不对本申请中ITO基板的尺寸做特殊限定。
在实验基板(阳极1)上真空蒸镀m-MTDATA(4,4',4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺)(结构式可见下文)以形成厚度为
Figure PCTCN2020096880-appb-000036
的空穴注入层2(HIL)，并且在空穴注入层2(HIL)上真空蒸镀NPB(N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺)(结构式可见下文)，以形成厚度为
Figure PCTCN2020096880-appb-000037
的空穴传输层31(HTL)。
在空穴传输层31(HTL)上蒸镀化合物1，形成厚度为
Figure PCTCN2020096880-appb-000038
的电子阻挡层32(EBL)。举例而言，电子阻挡层32(EBL)的厚度可以是
Figure PCTCN2020096880-appb-000039
或
Figure PCTCN2020096880-appb-000040
当然，还可以是其他厚度，在此不再一一列举。
将α,β-ADN(结构式可见下文)作为主体，按照100:3的膜厚比同时掺杂BD-1(结构式可见下文)，形成了厚度为
Figure PCTCN2020096880-appb-000041
的发光层33(EML)。举例而言，发光层33(EML)的厚度可以是
Figure PCTCN2020096880-appb-000042
Figure PCTCN2020096880-appb-000043
或
Figure PCTCN2020096880-appb-000044
当然，还可以是其他厚度，在此不再一一列举。
将DBimiBphen(结构式可见下文)和LiQ(结构式可见下文)以1:1的重量比进行混合，并可通过蒸镀工艺形成
Figure PCTCN2020096880-appb-000045
厚的电子传输层34(ETL)，举例而言，电子传输层34的厚度可以是
Figure PCTCN2020096880-appb-000046
Figure PCTCN2020096880-appb-000047
或
Figure PCTCN2020096880-appb-000048
当然，还可以是其他厚度，在此不再一一列举。随后，将LiQ蒸镀在电子传输层34上以形成厚度为
Figure PCTCN2020096880-appb-000049
的电子注入层4(EIL)，举例而言，电子注入层4的厚度可以是
Figure PCTCN2020096880-appb-000050
或
Figure PCTCN2020096880-appb-000051
当然，还可以是其他厚度，在此不再一一列举。然后，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4(EIL)上，形成厚度为
Figure PCTCN2020096880-appb-000052
的阴极5。
此外，在上述阴极5上蒸镀厚度为
Figure PCTCN2020096880-appb-000053
的CP-1(结构式可见下文)，形成覆盖层(CPL)，从而完成有机发光器件的制造。
Figure PCTCN2020096880-appb-000054
Figure PCTCN2020096880-appb-000055
实施例2～8
除了在形成电子阻挡层32(EBL)时各自使用化合物2～8替代化合物1之外，采用与实施例1相同的方法制作有机电致发光器件。
即：实施例2采用化合物2作为功能层3中的一层或多层，制作有机电致发光器件；实施例3采用化合物3作为功能层3中的一层或多层，制作有机电致发光器件；实施例4采用化合物4作为功能层3中的一层或多层，制作有机电致发光器件；实施例5采用化合物5作为功能层3中的一层或多层，制作有机电致发光器件；实施例6采用化合物6作为功能层3中的一层或多层，制作有机电致发光器件；实施例7采用化合物7作为功能层3中的一层或多层，制作有机电致发光器件；实施例8采用化合物8作为功能层3中的一层或多层，制作有机电致发光器件；且各器件性能参数详见表1。
比较例1-比较例4
在比较例1～比较例4中，可分别使用化合物A～化合物D作为电子阻挡层32(EBL)替代化合物之外，采用与实施例1相同的方法制造有机电致发光器件。其中，化合物A～化合物D的结构分别如下所示：
Figure PCTCN2020096880-appb-000056
即：比较例1采用化合物A制造有机电致发光器件；比较例2采用化合物B制造有机电致发光器件；比较例3采用化合物C制造有机电致发光器件；比较例4采用化合物D制造有机电致发光器件；制备出的各器件的性能详见表1。其中，IVL(电流、电压、亮度)数据对比的是在10mA/cm 2下的测试结果，T95寿命是20mA/cm 2电流密度下的测试结果。
表1 实施例1～8和比较例1～4的器件性能
Figure PCTCN2020096880-appb-000057
根据上述表1的结果可知，采用化合物1～化合物8作为电子阻挡层32(EBL)的实施例1、实施例2、实施例3、实施例4、实施例5、实施例6、实施例7及实施例8与使用化合物A～化合物D的比较例1、比较例2、比较例3及比较例4相比，发光效率和器件寿命均有很高提升。本申请中实施例5使用的化合物5作为电子阻挡层32(EBL)制备的有机电致发光器件相对于比较例1，发光效率(Cd/A)提高了54.7％，外量子效率至少提高56.5％，寿命延长了42小时，提高了75.4％。因而可见，本申请实施方式的有机电致发光器件的在发光效率和寿命性能有显著提高。
如表1所示，相比化合物A、化合物C以及化合物D，本申请化合物1～化合物8均在效率和寿命两方面均有明显提高；具体而言，可通过将咔唑的氮原子和三芳基胺的氮原子通过亚苯基相连，可缩短氮原子之间的距离，进而可缩小三芳胺和咔唑平面的夹角，从而可将材料的HOMO能级通过共轭作用同时分布在三芳胺以及咔唑基团上，从而提高材料的空穴迁移率，进而提高器件的光电转化效率；同时，非对称的三芳基胺支链长度，外加空间位阻的萘/菲基团，使得化合物的结晶性大幅降低且成膜均一性明显提高，以上结果中尤以化合物1和化合物5为最佳。
相比于化合物B，本申请化合物1～化合物8，均在效率和寿命两方面均有明显提高；本申请化合物1～化合物8可通过在三芳基胺的另两个分支引入大平面稠环基团，可有效分散对三芳基胺的电子云密度，避免C-N键的裂解，同时，可通过垂直构型的稠环连接方式，增大分子空间体积，降低分子间堆叠带来的结晶效应，进而可降低器件的工作电压，延长器件寿命。
图4和图5为本申请化合物1和化合物A的计算HOMO能级图。从图中可以看出，本申请化合物1的HOMO能级通过共轭作用同时分布在三芳胺以及咔唑基团上，咔唑的氮原子和三芳基胺的氮原子通过亚苯基相连，缩短氮原子之间的距离提高材料的空穴迁移率，进而提高器件的光电转化效率。本申请还提供一种电子装置，该电子装置可以包括上述任一实施方式的光电转化器件，其有益效果及具体细节可参考上述光电转化器件，在此不在赘述。举例而言，该电子装置可以是显示器、阵列基板、光伏组件等，当然，还可以是其他装置，在此不再一一列举。
本领域技术人员在考虑说明书及实践这里公开的发明后，将容易想到本申请的其它实施方案。本申请旨在涵盖本申请的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本申请的一般性原理并包括本申请未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的，本申请的真正范围和精神由所附的权利要求指出。

Claims (13)

  1. 一种含氮化合物，其中，所述含氮化合物的结构通式如式I所示：
    Figure PCTCN2020096880-appb-100001
    其中，Ar 1和Ar 2分别独立的选自取代或未取代的碳原子数为6-30的芳基；
    所述Ar 1和所述Ar 2的取代基相同或不同，且分别独立地选自：氘、氚、卤素、氰基、氨基、羟基、硝基、碳原子数为1-20的烷基、碳原子数为3-20的环烷基、碳原子数为6-30的芳基。
  2. 根据权利要求1所述的含氮化合物，其特征在于，所述Ar 1和所述Ar 2分别独立地选自：取代或未取代的成环碳原子数为6-20的芳基。
  3. 根据权利要求1或2所述的含氮化合物，其中，所述Ar 1和所述Ar 2分别独立地选自如下结构所组成的组：
    Figure PCTCN2020096880-appb-100002
    其中，各A 1～A 19分别独立地选自氘、氚、氟、氯、溴、氰基、碳原子数为1～4的烷基、碳原子数为3～10的环烷基、碳原子数为6～15的芳基；
    b 1～b 19以b k表示，A 1～A 19以A k表示，k为变量，表示1～19的任意整数，b k表示取代基A k的个数，当b k大于1时，相应的取代基A k相同或不同；
    其中，当k选自1、3、6、14、15、17或19时，b k选自0、1、2、3、4或5；
    当k选自2、4、9、11、13或18时，b k选自0、1、2、3或4；
    当k选自5、12、16时，b k选自0、1、2或3；
    当k选自10时，b k选自0、1、2、3、4、5或6；
    当k选自7时，b k选自0、1、2、3、4、5、6或7；
    当k选自8时，b k选自0、1、2、3、4、5、6、7、8或9。
  4. 根据权利要求1～3中任意一项所述的含氮化合物，其中，所述Ar 1和所述Ar 2分别独立地选自以下基团：
    Figure PCTCN2020096880-appb-100003
  5. 根据权利要求1～4中任意一项所述的含氮化合物，其中，所述Ar 1和所述Ar 2相同或不同，且分别独立的选自如下基团：
    Figure PCTCN2020096880-appb-100004
    其中，*表示上述基团用于与式I中
    Figure PCTCN2020096880-appb-100005
    基团结合。
  6. 根据权利要求1～5中任意一项所述的含氮化合物，其中，所述Ar 1和所述Ar 2不同时为
    Figure PCTCN2020096880-appb-100006
    其中，*表示上述基团用于与式I中
    Figure PCTCN2020096880-appb-100007
    基团结合。
  7. 根据权利要求1～6中任意一项所述的含氮化合物，其中，所述含氮化合物选自如下化合物：
    Figure PCTCN2020096880-appb-100008
    Figure PCTCN2020096880-appb-100009
  8. 一种光电转化器件，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1～7任一项所述的含氮化合物。
  9. 根据权利要求8所述的光电转化器件，其特征在于，所述功能层包括电子阻挡层，所述电子阻挡层包含权利要求1～7任一项所述的含氮化合物。
  10. 根据权利要求8或9所述的光电转化器件，其特征在于，所述功能层还包括：
    发光层，设于所述电子阻挡层远离所述阳极的一侧；
    空穴传输层，设于所述电子阻挡层远离所述发光层的一侧；
    电子传输层，设于所述发光层与所述阴极之间。
  11. 根据权利要求8～10中任意一项所述的光电转化器件，其特征在于，所述光电转化器件为有机电致发光器件。
  12. 根据权利要求8～11中任意一项所述的光电转化器件，其特征在于，所述光电转化器件为太阳能电池。
  13. 一种电子装置，其特征在于，包括权利要求8～12中任意一项所述的光电转化器件。
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