Nitrogen-containing compounds and electronic components and electronic devices

Abstract

The present application belongs to the field of organic light-emitting materials, and specifically relates to a nitrogen-containing compound, an electronic component and an electronic device. The structure of the nitrogen-containing compound is shown in Formula 1, and the nitrogen-containing compound can improve the performance of the electronic component.

Description

Technical Field

[0001] The present application relates to the field of organic light-emitting materials, and specifically provides a nitrogen-containing compound, an electronic component, and an electronic device. Background Art

[0002] Organic electroluminescent (OLED: Organic Light Emission Diodes) device technology can be used to manufacture new display products and new lighting products, and is expected to replace existing liquid crystal displays and fluorescent lighting, with a wide range of applications. The OLED optoelectronic functional material film layer that constitutes the OLED device includes at least two layers of structure. The OLED device structure used in the industry includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other film layers. In other words, the optoelectronic functional materials used in OLED devices at least include hole injection materials, hole transport materials, light-emitting materials, electron transport materials, etc. The material types and matching forms are rich and diverse.

[0003] Currently, OLED display technology has been applied in smart phones, tablet computers and other fields, and will further expand to large-size application fields such as TVs. However, compared with the actual product application requirements, the luminous efficiency and service life of OLED devices need to be further improved. Research on improving the performance of OLED light-emitting devices includes: reducing the operating voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device. In order to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and manufacturing process of OLED devices, but also to continuously research and innovate OLED optoelectronic functional materials to create functional materials with higher performance OLEDs.

[0004] When organic OLED devices are used in display devices, they are required to have long life and high efficiency, especially blue light devices in the blue pixel area (compared with red and green light-emitting devices), which have high operating voltage and short life. In order to increase the life of blue pixels and reduce the operating voltage, the hole mobility and glass transition temperature of hole transport materials are increased, thereby increasing the life of blue light devices and reducing device voltage. Summary of the invention

[0005] In view of the above problems existing in the prior art, the purpose of the present application is to provide a nitrogen-containing compound, an electronic component and an electronic device. The nitrogen-containing compound of the present application can effectively improve the performance of the electronic component.

[0006] In a first aspect, the present application provides a nitrogen-containing compound, the structure of which is shown in Formula 1:

[0007]

[0008] Wherein, the structure of the group Ar1 is as shown in formula a or formula b:

[0009]

[0010] X is selected from O, S or N(Ar),

[0011] Ar is selected from a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms;

[0012] L, L1, and L2 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms;

[0013] Ar2 is selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 5 to 30 carbon atoms;

[0014] The substituents in Ar, L, L1, L2 and Ar2, and R1 and R2 are the same or different and are independently selected from deuterium, a halogen group, a cyano group, an alkyl group having 1 to 10 carbon atoms, a deuterated alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 5 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkylthio group having 1 to 10 carbon atoms;

[0015] n1 represents the number of R1 and is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n2 represents the number of R2 and is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0016] In a second aspect, the present invention provides an electronic component, comprising an anode, a cathode, and a functional layer disposed between the anode and the cathode, wherein the functional layer comprises the nitrogen-containing compound described in the first aspect of the present application.

[0017] In a third aspect, the present application provides an electronic device, comprising the electronic component described in the second aspect of the present application.

[0018] The compounds of the present application are triarylamine derivatives of fluorene, wherein two trideuterated methyl groups are introduced into the 9th position of fluorene, and the deuterated fluorene formed can effectively adjust the HOMO and LUMO energy levels of the compound, and combined with a specific heteroaryl condensed ring (group Ar1) and an aromatic group, the formed compounds of the present application are applied to the hole transport layer (including C-HT, Prime) of an OLED device, and can be better matched with the adjacent functional layer to better transport holes, effectively block electrons, and improve the effective recombination of excitons in the light-emitting layer; in addition, the heteroaryl condensed ring structure (Ar1) is conjugated, which improves the thermal stability of the entire molecule and is beneficial to the improvement of the device life performance; the material obtained by bonding the deuterated derivative to the heteroaryl condensed ring structure is applied to an organic electroluminescent device, which can simultaneously improve the luminous efficiency and significantly improve the device life while making the device have a lower operating voltage.

[0019] Other features and advantages of the present application will be described in detail in the subsequent detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings are used to provide further understanding of the present application and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present application, but do not constitute a limitation to the present application.

[0021] Figure 1 It is a schematic diagram of the structure of an organic electroluminescent device according to one embodiment of the present application.

[0022] Figure 2 It is a schematic structural diagram of a first electronic device according to an embodiment of the present application.

[0023] Figure 3 It is a schematic structural diagram of a photoelectric conversion device according to one embodiment of the present application.

[0024] Figure 4 It is a schematic structural diagram of a second electronic device according to an embodiment of the present application.

[0025] Description of Reference Numerals

[0026] 100, 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, first electronic device; 500, second electronic device. DETAILED DESCRIPTION

[0027] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0028] In a first aspect, the present application provides a nitrogen-containing compound, the structure of which is shown in Formula 1:

[0029]

[0030] Wherein, the structure of the group Ar1 is as shown in formula a or formula b:

[0031]

[0032] X is selected from O, S or N(Ar),

[0033] Ar is selected from a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms;

[0034] L, L1, and L2 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 5 to 20 carbon atoms;

[0035] Ar2 is selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 5 to 30 carbon atoms;

[0036] The substituents in Ar, L, L1, L2 and Ar2, and R1 and R2 are the same or different and are independently selected from deuterium, a halogen group, a cyano group, an alkyl group having 1 to 10 carbon atoms, a deuterated alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 5 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkylthio group having 1 to 10 carbon atoms;

[0037] n1 represents the number of R1 and is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n2 represents the number of R2 and is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0038] In this application, the descriptions "each... is independently selected from" and "... is independently selected from" are interchangeable and should be understood in a broad sense, which can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or in the same group, the specific options expressed by the same symbols do not affect each other. For example, " Wherein, each q is independently selected from 0, 1, 2 or 3, and each R" is independently selected from hydrogen, deuterium, fluorine, and chlorine, which means: Formula Q-1 indicates 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 indicates that there are q substituents R" on each benzene ring of biphenyl, the number q of R" substituents on the two benzene rings can be the same or different, each R" can be the same or different, and the options of each R" do not affect each other.

[0039] In the present application, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have a substituent (hereinafter, for the convenience of description, the substituent is collectively referred to as R c ). For example, "substituted or unsubstituted aryl" refers to an aryl group having a substituent Rc or an unsubstituted aryl group. c , for example, it may be deuterium, a halogen group, a cyano group, a heteroaryl group, an aryl group, a trialkylsilyl group, an alkyl group, a deuterated alkyl group, a halogenated alkyl group, a cycloalkyl group, etc. In addition, the number of carbon atoms of a substituted or unsubstituted functional group refers to the number of all carbon atoms.

[0040] In the present application, aryl refers to a group formed by aromatic carbocyclic rings. Aryl can be a monocyclic aryl (e.g., phenyl) or a polycyclic aryl. In other words, aryl can be a monocyclic aryl, a condensed ring aryl, two or more monocyclic aryl groups (e.g., biphenyl, terphenyl) connected by carbon-carbon bond conjugation, a monocyclic aryl and a condensed ring aryl (e.g., phenyl-naphthyl) connected by carbon-carbon bond conjugation, and two or more condensed ring aryl groups connected by carbon-carbon bond conjugation. That is, unless otherwise specified, two or more aromatic groups connected by carbon-carbon bond conjugation can also be regarded as aryl of the present application. Among them, condensed ring aryl can include, for example, a bicyclic condensed aryl (e.g., naphthyl), a tricyclic condensed aryl (e.g., phenanthrenyl, fluorenyl, anthracenyl), etc. Aryl does not contain heteroatoms such as B, N, O, S, P, Se, and Si. It should be noted that biphenyl and terphenyl are both regarded as aryl in the present application. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, benzo[9,10]phenanthrenyl, pyrenyl, benzofluoranthenyl, In the present application, the arylene group refers to a divalent group formed by further losing a hydrogen atom from an aryl group.

[0041] In the present application, the substituted aryl group may be one or more hydrogen atoms in the aryl group replaced by groups such as deuterium, fluorine, cyano, aryl, heteroaryl, alkyl, cycloalkyl, deuterated alkyl, alkoxy, alkylthio, trialkylsilyl, etc. Specific examples of heteroaryl substituted aryl groups include, but are not limited to, dibenzofuranyl substituted phenyl, dibenzothiophenyl substituted phenyl, etc. It should be understood that the number of carbon atoms in the substituted aryl group refers to the total number of carbon atoms in the aryl group and the substituents on the aryl group, for example, a substituted aryl group with 18 carbon atoms means that the total number of carbon atoms in the aryl group and the substituents is 18.

[0042] In the present application, heteroaryl refers to a monovalent aromatic ring or a derivative thereof containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatoms may be at least one of B, O, N, P, Si, Se and S. The heteroaryl may be a monocyclic heteroaryl or a polycyclic heteroaryl, in other words, the heteroaryl may be a single aromatic ring system or a plurality of aromatic ring systems conjugated by carbon-carbon bonds, and any aromatic ring system may be an aromatic monocyclic ring or an aromatic condensed ring. For example, heteroaryl groups include thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazine, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothiphenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl, as well as N-phenylcarbazolyl, N-pyridylcarbazolyl, N-methylcarbazolyl, and the like, without being limited thereto. Among them, thienyl, furanyl, phenanthroline, etc. are heteroaryl groups of single aromatic ring system type, N-phenylcarbazolyl, N-pyridyl are heteroaryl groups of polycyclic system type connected by carbon-carbon bond conjugation. In this application, the heteroaryl group involved refers to a divalent group formed by further losing a hydrogen atom of the heteroaryl group.

[0043] In the present application, the substituted heteroaryl group may be a heteroaryl group in which one or more hydrogen atoms are substituted by groups such as deuterium, fluorine, cyano, aryl, heteroaryl, alkyl, cycloalkyl, deuterated alkyl, alkoxy, alkylthio, trialkylsilyl, etc. Specific examples of aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, phenyl-substituted pyridyl, etc. It should be understood that the number of carbon atoms in the substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituents on the heteroaryl group.

[0044] In this application, an unpositioned connecting bond refers to a single bond extending from the ring system. It means that one end of the connecting bond can be connected to any position in the ring system that the bond passes through, and the other end is connected to the rest of the compound molecule. For example, as shown in the following formula (f), the naphthyl represented by formula (f) is connected to other positions of the molecule through two non-positional connecting bonds that pass through the bicyclic ring, and the meaning represented by it includes any possible connection mode shown in formula (f-1) to formula (f-10).

[0045]

[0046] For another example, as shown in the following formula (X'), the dibenzofuranyl represented by formula (X') is connected to other positions of the molecule through a non-positional connecting bond extending from the middle of one side of the benzene ring, and the meaning represented by it includes any possible connection mode shown in formula (X'-1) to formula (X'-4):

[0047]

[0048] The non-positioning substituent in the present application refers to a substituent connected by a single bond extending from the center of the ring system, which means that the substituent can be connected to any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R' represented by formula (Y) is connected to the quinoline ring through a non-positioning connection bond, and the meaning represented includes any possible connection mode shown in formula (Y-1) to formula (Y-7).

[0049]

[0050] In the present application, the halogen group includes bromine, fluorine, chlorine, iodine, etc., preferably fluorine.

[0051] In the present application, the alkyl group with 1-10 carbon atoms includes a linear alkyl group with 1-10 carbon atoms and a branched alkyl group with 3-10 carbon atoms, and the carbon atoms may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. Specific examples of the alkyl group with 1-10 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, and the like.

[0052] In the present application, the carbon number of the aryl group as a substituent may be 6-12, for example, 6, 10, 12, etc. Specific examples of the aryl group as a substituent include, but are not limited to, phenyl, naphthyl, biphenyl.

[0053] In the present application, the number of carbon atoms of the heteroaryl group as a substituent can be 5-12, for example, the number of carbon atoms is 5, 8, 9, 10, 12, etc. Specific examples of the heteroaryl group as a substituent include, but are not limited to, pyridyl, quinolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, etc.

[0054] In the present application, the carbon number of the cycloalkyl group as a substituent may be 3 to 10, preferably 5 to 8. Specific examples of the cycloalkyl group include, but are not limited to, cyclopentyl, cyclohexyl, and the like.

[0055] In the present application, the carbon number of the trialkylsilyl group as a substituent may be 3 to 12, preferably 5 to 7. Specific examples of the trialkylsilyl group include, but are not limited to, trimethylsilyl.

[0056] In the present application, the carbon number of the deuterated alkyl group as a substituent may be 1 to 10, preferably 1 to 4. Specific examples of the deuterated alkyl group include, but are not limited to, trideuterated methyl group.

[0057] In the present application, the carbon number of the halogenated alkyl group as a substituent may be 1 to 10, preferably 1 to 4. Specific examples of deuterated alkyl groups include, but are not limited to, trideuterated methyl groups.

[0058] In the present application, among Ar, L, L1, L2 and Ar2, each substituent does not form a ring.

[0059] Specifically, the structure of the nitrogen-containing compound of the present application is selected from at least one of the structures shown in the following formulas 1-1 to 1-4:

[0060]

[0061]

[0062] In a preferred embodiment, the structure of the nitrogen-containing compound is as shown in Formula 1-1.

[0063] In the present application, Ar can be selected from: substituted or unsubstituted aryl groups having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms, and substituted or unsubstituted heteroaryl groups having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms.

[0064] Optionally, Ar is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.

[0065] In one embodiment, Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl.

[0066] Optionally, the substituents in Ar are selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl or phenyl.

[0067] Optionally, R1 and R2 are the same or different and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl or naphthyl.

[0068] In one embodiment, the group Ar1 in Formula 1 is selected from the group consisting of the following groups:

[0069]

[0070] In the application, L, L1, and L2 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, and a substituted or unsubstituted heteroarylene group having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.

[0071] Optionally, L, L1, and L2 are the same or different, and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms.

[0072] In some embodiments, L, L1, and L2 are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, or a group formed by a phenylene group and a naphthylene group connected by a single bond.

[0073] Optionally, the substituents in L, L1 and L2 are each independently selected from deuterium, fluorine, cyano, an alkyl group having 1 to 4 carbon atoms, a deuterated alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

[0074] Optionally, the substituents in L, L1 and L2 are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trideuterated methyl, phenyl, naphthyl, biphenyl.

[0075] In one embodiment, L, L1, and L2 are each independently selected from a single bond, a substituted or unsubstituted group W, wherein the unsubstituted group W is selected from the group consisting of the following groups:

[0076]

[0077] The substituted group W has one or more substituents, each of which is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trideuterated methyl or phenyl.

[0078] Optionally, L, L1 and L2 are each independently selected from a single bond or the group consisting of the following groups:

[0079]

[0080] In a specific embodiment, L is selected from the group consisting of a single bond or the following groups:

[0081]

[0082] In a specific embodiment, L1 and L2 are each independently selected from a single bond or the group consisting of the following groups:

[0083]

[0084] In the present application, Ar2 is selected from substituted or unsubstituted aryl having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms, and substituted or unsubstituted heteroaryl having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms.

[0085] Optionally, Ar2 is selected from a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 25 carbon atoms.

[0086] Further optionally, Ar2 is selected from a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, and a substituted or unsubstituted heteroaryl group having 12 to 25 carbon atoms.

[0087] In some embodiments, Ar2 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl.

[0088] Optionally, the substituents in Ar2 are each independently selected from deuterium, fluorine, cyano, an alkyl group having 1-4 carbon atoms, a deuterated alkyl group having 1-4 carbon atoms, a haloalkyl group having 1-4 carbon atoms, a trialkylsilyl group having 3-7 carbon atoms, an aryl group having 6-12 carbon atoms, a heteroaryl group having 5-12 carbon atoms or a cycloalkyl group having 5-8 carbon atoms.

[0089] Optionally, the substituents in Ar2 are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, trideuterated methyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, dibenzothienyl or carbazolyl.

[0090] In a specific embodiment, Ar2 is selected from the group consisting of the following groups:

[0091]

[0092] Optionally, Ar2 is selected from the group consisting of:

[0093]

[0094]

[0095] Optionally, the nitrogen-containing compound is selected from the group consisting of the following compounds:

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] The present application does not particularly limit the synthesis method of the nitrogen-containing compounds provided. Those skilled in the art can determine a suitable synthesis method based on the nitrogen-containing compounds of the present application in combination with the preparation methods provided in the synthesis examples. In other words, the synthesis examples of the present invention provide exemplary preparation methods of nitrogen-containing compounds, and the raw materials used can be obtained commercially or by methods well known in the art. Those skilled in the art can obtain all nitrogen-containing compounds provided in the present application according to these exemplary preparation methods, and all specific preparation methods for preparing the nitrogen-containing compounds will not be described in detail here, and those skilled in the art should not be understood as limiting the present application.

[0114] A second aspect of the present application provides an electronic component, comprising an anode, a cathode, and a functional layer disposed between the anode and the cathode, wherein the functional layer comprises the nitrogen-containing compound described in the first aspect of the present application.

[0115] Optionally, the functional layer includes a hole transport layer, and the hole transport layer includes the nitrogen-containing compound of the present application.

[0116] In the present application, the electronic component may be an organic electroluminescent device or a photoelectric conversion device.

[0117] According to a specific embodiment, the electronic component is an organic electroluminescent device. Figure 1 As shown, the organic electroluminescent device includes an anode 100, a hole transport layer 320, an organic light-emitting layer 330, an electron transport layer 340 and a cathode 200 which are stacked in sequence.

[0118] Optionally, the hole transport layer 320 includes the nitrogen-containing compound of the present application.

[0119] Optionally, the hole transport layer 320 includes a first hole transport layer 321 (C-HT) and a second hole transport layer 322 (Prime, also known as "light-emitting auxiliary layer" or "electron blocking layer") stacked, and the first hole transport layer 321 is closer to the anode than the second hole transport layer 322. The first hole transport layer 321 and / or the second hole transport layer 322 contain the nitrogen-containing compound of the present application.

[0120] In the present application, the anode 100 includes the following anode materials, which are preferably materials with a large work function that facilitates hole injection into the functional layer. Specific examples of anode materials include: 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 SnO2:Sb; or conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, but are not limited thereto. Preferably, a transparent electrode comprising indium tin oxide (indium tin oxide, indiumtin oxide) (ITO) as an anode is included.

[0121] Optionally, the second hole transport layer 322 includes the nitrogen-containing compound of the present application.

[0122] Optionally, the material of the first hole transport layer 321 can be selected from carbazole polymers, carbazole-linked aromatic amine compounds, dibenzofuran-linked aromatic amine compounds, substituted fluorene-linked triarylamine compounds or other types of compounds, which are not specifically limited in the present application. For example, the material of the first hole transport layer 321 is selected from at least one of the following compounds:

[0123]

[0124] In a specific embodiment, the material of the first hole transport layer 321 is HT-1 (ie, NPB).

[0125] The organic light-emitting layer 330 may be composed of a single light-emitting material, or may include a host material and a guest material (also called a "dopant"). Optionally, the organic light-emitting layer 330 is composed of a host material and a guest material, and holes injected into the organic light-emitting layer 330 and electrons injected into the organic light-emitting layer 330 may be recombined in the organic light-emitting layer 330 to form excitons, and the excitons transfer energy to the host material, and the host material transfers energy to the guest material, thereby enabling the guest material to emit light.

[0126] The main material of the organic light-emitting layer 330 may be a metal chelate compound, a bisphenylethylene derivative, an aromatic amine derivative, a dibenzofuran derivative, an anthracene derivative or other types of materials, and the present application does not impose any special restrictions thereon. For example, the main material is selected from one or more of the following compounds:

[0127]

[0128] In a specific implementation, the main material of the organic light-emitting layer 330 is RH-1.

[0129] The guest material of the organic light-emitting layer 330 may be a compound having a condensed aromatic ring or a derivative thereof, a compound having a heteroaromatic ring or a derivative thereof, a biarylamine derivative having a fused aromatic subunit, or other materials, and the present application does not impose any particular limitation thereto. For example, the guest material is selected from at least one of the following compounds:

[0130]

[0131]

[0132] In a specific embodiment, the guest material of the organic light emitting layer 330 is composed of Ir(piq)2(acac).

[0133] The electron transport layer 340 may be a single-layer structure or a multi-layer structure, and may include one or more electron transport materials. The electron transport material may generally include a metal complex and / or a nitrogen-containing heterocyclic derivative, wherein the metal complex material may be selected from, for example, LiQ, Alq3, Bepq2, etc.; the nitrogen-containing heterocyclic derivative may be an aromatic ring having a nitrogen-containing six-membered ring or five-membered ring skeleton, a condensed aromatic ring compound having a nitrogen-containing six-membered ring or five-membered ring skeleton, etc. Specific examples include, but are not limited to, 1,10-phenanthroline compounds such as BCP, Bphen, NBphen, DBimiBphen, BimiBphen, or at least one of the following compounds:

[0134]

[0135] In a specific embodiment, the electron transport layer 340 is composed of ET-5 and LiQ.

[0136] In the present application, cathode 200 includes a cathode material, which is a material with a small work function that facilitates electron injection into the functional layer. Specific examples of 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 alloys thereof; or multilayer materials such as LiF / Al, Liq / Al, LiO2 / Al, LiF / Ca, LiF / Al and BaF2 / Ca. It is preferred to include a metal electrode containing magnesium and silver as the cathode.

[0137] Alternatively, if Figure 1 As shown, a hole injection layer 310 is further provided between the anode 100 and the hole transport layer 320 to enhance the ability of injecting holes into the hole transport layer 320. The hole injection layer 310 may be made of benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives or other materials, and the present application does not impose any special restrictions on this. For example, the hole injection layer 310 is selected from the group consisting of the following compounds:

[0138]

[0139] In a specific embodiment, the hole injection layer 310 is composed of HAT-CN.

[0140] Alternatively, if Figure 1 As shown, an electron injection layer 350 is 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 a complex of an alkali metal and an organic substance. For example, the electron injection layer 350 includes LiQ or Yb.

[0141] In the present application, the organic electroluminescent device may be a blue light device, a red light device or a green light device, preferably a red light device.

[0142] According to another embodiment, the electronic component is a photoelectric conversion device. Figure 3 As shown, 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 stacked in sequence. The hole transport layer 320 includes the nitrogen-containing compound of the present application.

[0143] Optionally, the photoelectric conversion device is a solar cell, such as an organic thin film solar cell.

[0144] A third aspect of the present application provides an electronic device, comprising the electronic component described in the second aspect of the present application.

[0145] According to one embodiment, Figure 2As shown, the electronic device is a first electronic device 400, and the first electronic device 400 includes the above-mentioned organic electroluminescent device. The first electronic device 400 is, for example, a display device, a lighting device, an optical communication device, or other types of electronic devices, such as, but not limited to, a computer screen, a mobile phone screen, a television, an electronic paper, an emergency lighting lamp, an optical module, etc.

[0146] According to another embodiment, Figure 4 As shown, the electronic device is a second electronic device 500, and the second electronic device 500 includes the above-mentioned photoelectric conversion device. The second electronic device 500 is, for example, a solar power generation device, a light detector, a fingerprint recognition device, an optical module, a CCD camera or other types of electronic devices.

[0147] Hereinafter, the present application will be described in further detail by way of examples. However, the following examples are merely illustrative of the present application and are not intended to limit the present application.

[0148] The compounds whose synthesis methods are not mentioned in this application are all raw materials obtained through commercial channels.

[0149] Synthesis Example 1: Synthesis of Compound 1

[0150]

[0151] (1) Under nitrogen protection, 2-bromofluorene (122.6 g, 0.5 mol), potassium tert-butoxide (140 g, 1.25 mol) and THF (800 mL) were placed in a 2000 mL three-necked round-bottom flask, stirred at 0°C for 10 min, and then iodomethane-d3 (72.5 g, 0.5 mol) was added dropwise. After the addition, the reaction temperature rose to room temperature and the reaction was continued for 24 h. After the reaction was completed, the mixture was extracted with dichloromethane and deionized water, and the organic phase was washed with water until neutral, and the organic phase was dried with anhydrous magnesium sulfate and concentrated. The crude product was separated by column chromatography using dichloromethane: n-heptane = 1:4 (v / v) as the eluent, and then recrystallized with a mixed solvent of ethyl acetate: petroleum ether = 1:3 (v / v) to obtain a white product, namely, intermediate IM-A (128 g, yield 92.0%).

[0152]

[0153] (2) Under nitrogen protection, IM-A (6.6 g, 23.7 mmol), raw material sub 2 (4 g, 23.7 mmol) and toluene (80 mL) were placed in a reaction flask, heated to reflux for 30 min, cooled to 80°C, sodium tert-butoxide (3.43 g, 35.7 mmol), x-Phos (0.23 g, 0.4 mmol) and Pd2(dba)3 (0.18 g, 0.24 mmol) were added, and the reflux reaction was continued for 2 h. The reaction was stopped, and the reaction solution was cooled to room temperature, extracted with water and toluene, and the organic phase was washed with water until neutral, anhydrous magnesium sulfate was added to dry, filtered and concentrated, and passed through a silica gel funnel column with toluene as the eluent. The liquid after the column was concentrated and recrystallized with a mixed solvent of dichloromethane: n-heptane = 1:4 (v / v) to obtain a white solid P1-1 (7.5 g, yield 86.5%).

[0154]

[0155] (3) Under nitrogen protection, P1-1 (7.5 g, 20.5 mmol) and the raw material sub 3 (5.1 g, 20.5 mmol) and toluene (80 mL) were placed in a reaction bottle, heated to reflux for 30 min, cooled to 80 ° C, added with sodium tert-butoxide (2.9 g, 30.7 mmol), S-Phos (0.17 g, 0.4 mmol) and Pd2(dba)3 (0.18 g, 0.2 mmol), continued to reflux for 5 h, stopped the reaction, and the reaction solution was cooled to room temperature, extracted with water and toluene, washed with water until the organic phase was neutral, added with anhydrous magnesium sulfate to dry, filtered and concentrated, passed through a silica gel funnel column with toluene as the eluent, concentrated the liquid after the column, and recrystallized with a mixed solvent of dichloromethane: n-heptane (v / v) = 1:4 to obtain a white solid, namely compound 1 (8.6 g, yield 78.6%); mass spectrum (m / z) = 534.26 [M+H] + .

[0156] Synthesis example 2-50

[0157] The compounds listed in Table 1 were synthesized by referring to the method of compound 1, except that raw material 1 was used instead of 2-bromofluorene, raw material 2 was used instead of sub 2, and raw material 3 was used instead of sub 3. The main raw materials used, the synthesized compounds and their yields (yields of the last step) and mass spectra are shown in Table 1.

[0158] Table 1

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167] Synthesis Example 51: Synthesis of Compound 203

[0168]

[0169] (1) Under nitrogen protection, IM-A (55 g, 0.2 mol), p-chlorophenylboric acid (31 g, 0.2 mol), potassium carbonate (55.2 g, 0.4 mol), TBAB (1.288 g, 0.004 mol) and tetrakistriphenylphosphine palladium (1.155 g, 0.001 mol) were placed in a 1000 mL three-necked flask, and toluene (300 mL), anhydrous ethanol (150 mL) and water (50 mL) were added, heated to 80° C. and refluxed for 24 h to terminate the reaction. After the reaction solution was cooled to room temperature, it was extracted with toluene and water, the organic phase was washed with water until neutral, anhydrous magnesium sulfate was added for drying, filtered and concentrated, and passed through a silica gel funnel column with toluene as the eluent, and then recrystallized with a mixed solvent of toluene: n-heptane = 1:3 (v / v) to obtain a white solid product, namely, intermediate IM-Aa (55.9 g, yield 90%).

[0170]

[0171] (2) Under nitrogen protection, IM-Aa (9.3 g, 30 mmol), 4-aminobiphenyl (5 g, 30 mmol) and toluene (80 mL) were placed in a reaction bottle, heated to reflux for 30 min, cooled to 80°C, sodium tert-butoxide (4.32 g, 45 mmol), x-Phos (0.29 g, 0.6 mmol) and Pd2(dba)3 (0.27 g, 0.3 mmol) were added, and the reflux reaction was continued for 2 h. The reaction was stopped, and the reaction solution was cooled to room temperature, extracted with water and toluene, and the organic phase was washed with water until neutral, dried with anhydrous magnesium sulfate, filtered and concentrated, and passed through a silica gel funnel column with toluene as the eluent, and the liquid after the column was concentrated. Recrystallization was carried out with a mixed solvent of toluene: n-heptane = 1:3 (v / v) to obtain a white solid P203-1 (11.9 g, yield 89.6%).

[0172]

[0173] (3) Under nitrogen protection, P203-1 (9.08 g, 20.5 mmol), 2-bromodibenzofuran (5.1 g, 20.5 mmol) and toluene (80 mL) were placed in a reaction flask, heated to reflux for 30 min, cooled to 80 °C, and sodium tert-butoxide (2.9 g, 30.7 mmol), S-Phos (0.17 g, 0.4 mmol) and Pd2(dba)3 (0.18 g, 0.2 mmole) were added. ol), continue to reflux for 5 hours, stop the reaction, wait for the reaction solution to cool to room temperature, extract with water and toluene, wash the organic phase with water until neutral, add anhydrous magnesium sulfate to dry, filter and concentrate, pass through a silica gel funnel column with toluene as eluent, concentrate the liquid after the column, and recrystallize with a mixed solvent of dichloromethane: n-heptane = 1:4 (v / v) to obtain a white solid compound 203 (8.65 g, yield 69.3%); mass spectrum (m / z) = 610.29 [M+H] + .

[0174] Synthesis Example 52-55

[0175] The compounds listed in Table 2 were synthesized by referring to the method of compound 203, except that raw material 4 was used instead of p-chlorophenylboronic acid, raw material 5 was used instead of 4-aminobiphenyl, and raw material 6 was used instead of 2-bromodibenzofuran. The main raw materials used, the synthesized compounds and their yields (yields of the last step) and mass spectra are shown in Table 2.

[0176] Table 2

[0177]

[0178] The NMR data of some compounds are shown in Table 3.

[0179] Table 3

[0180]

[0181] Example of fabrication and evaluation of organic electroluminescent devices

[0182] Example 1: Red organic electroluminescent device

[0183] The anode was prepared by the following process: An ITO / Ag / ITO substrate (manufactured by Corning) was cut into a size of 40 mm × 40 mm × 0.5 mm and prepared into an experimental substrate with cathode, anode and insulating layer patterns using a photolithography process. The surface was treated with UV ozone and O2:N2 plasma to increase the work function of the anode (experimental substrate) and remove scum.

[0184] Vacuum evaporation on the experimental substrate anode HAT-CN is used as a hole injection layer (HIL), and then evaporated on the hole injection layer NPB is used to form a first hole transport layer.

[0185] Compound 1 is vacuum evaporated on the first hole transport layer to form The second hole transport layer is formed by a plurality of holes.

[0186] On the second hole transport layer, RH-1 and Ir(piq)2(acac) were co-evaporated at a film thickness ratio of 95%:5% to form The red organic light emitting layer (R-EML)

[0187] Next, ET-5 and LiQ were co-evaporated on the organic light-emitting layer in a weight ratio of 1:1 to form The electron transport layer (ETL) is formed by evaporating Yb on the electron transport layer to form a layer with a thickness of Then, magnesium (Mg) and silver (Ag) were mixed at a deposition rate of 1:10 and vacuum-deposited on the electron injection layer to form a layer with a thickness of cathode.

[0188] Finally, CP-1 is evaporated on the cathode to form a layer with a thickness of An organic cover layer (CPL) is formed on the organic light-emitting device to complete the manufacturing process.

[0189] Example 2-55

[0190] An organic electroluminescent device was prepared by the same method as in Example 1, except that the other compounds shown in Table 4 below were used instead of Compound 1 when forming the second hole transport layer.

[0191] Comparative Examples 1-4

[0192] An organic electroluminescent device was prepared in the same manner as in Example 1, except that compound A, compound B, compound C and compound D were used instead of compound 1 when forming the second hole transport layer.

[0193] The main material structures used in the above embodiments and comparative examples are as follows:

[0194]

[0195]

[0196] At 10mA / cm 2 The IVL (current efficiency, voltage, and color coordinates) of the organic electroluminescent devices prepared in the embodiments and comparative examples were tested under the following conditions: 2The T95 life of each device was tested under the following conditions, and the results are shown in Table 4.

[0197] Table 4

[0198]

[0199]

[0200]

[0201] According to the results in Table 4, the performance of the organic electroluminescent device of Example 1-55 is improved compared with that of the organic electroluminescent device of Comparative Example 1-4; specifically, the operating voltage of the organic electroluminescent device of Example 1-55 is close to that of the comparative example, but the efficiency is at least increased by 16.4%, and the life is at least increased by 15.3%. Therefore, the use of the present compound as the second hole transport layer of the organic electroluminescent device has the characteristics of maintaining a low operating voltage while improving efficiency and life.

[0202] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0203] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further explain various possible combinations.

[0204] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A nitrogen-containing compound, characterized in that The structure of the nitrogen-containing compound is shown in Formula 1: Wherein, the structure of the group Ar1 is as shown in formula a or formula b: X is selected from O, S or N(Ar); Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl or substituted or unsubstituted phenanthrenyl; The substituent in Ar is selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl or phenyl; L, L1, L2 are the same or different and are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, or a substituted or unsubstituted biphenylene group; The substituents in L, L1 and L2 are the same or different and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl or phenyl; Ar2 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl; The substituents in Ar2 are the same or different and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl or naphthyl; R1 and R2 are the same or different and are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl or phenyl; n1 represents the number of R1 and is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n2 represents the number of R2 and is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

2. The nitrogen-containing compound according to claim 1, wherein The group Ar1 is selected from the group consisting of:

3. The nitrogen-containing compound according to claim 1, wherein L, L1, L2 are each independently selected from a single bond, a substituted or unsubstituted group W, and the unsubstituted group W is selected from the group consisting of the following groups: The substituted group W has one or more substituents, each of which is independently selected from deuterium, fluorine, cyano, methyl, ethyl, isopropyl, tert-butyl or phenyl.

4. The nitrogen-containing compound according to claim 1, wherein Ar2 is selected from the group consisting of:

5. The nitrogen-containing compound according to claim 1, wherein The nitrogen-containing compound is selected from the group consisting of the following compounds:

6. An electronic component comprising an anode, a cathode, and a functional layer disposed between the anode and the cathode, characterized in that: The functional layer comprises the nitrogen-containing compound according to any one of claims 1 to 5.

7. The electronic component according to claim 6, wherein: The functional layer includes a hole transport layer, and the hole transport layer contains the nitrogen-containing compound.

8. The electronic component according to claim 7, wherein: The electronic component is an organic electroluminescent device or a photoelectric conversion device.

9. An electronic device comprising the electronic component according to any one of claims 6 to 8.

Images