WO2022206389A1 - Nitrogen-containing compound and electronic element comprising same, and electronic device - Google Patents

Abstract

The present application relates to the field of organic materials, and provides a nitrogen-containing compound and an electronic element comprising same, and an electronic device. The structure of the nitrogen-containing compound is as shown in formula 1, wherein L, L₁, and L₂ are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6-25 carbon atoms, etc.; Ar₁, Ar₂, and Ar₃ are selected from a substituted or unsubstituted aryl group having 6-30 carbon atoms, etc. The nitrogen-containing compound can improve the performance of an electronic element.

Description

Nitrogen-containing compounds and electronic components and electronic devices containing the same

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority of the Chinese patent application with the application number CN202110352190.3 filed on March 31, 2021, the disclosure of which is incorporated into this application by reference in its entirety.

technical field

The present application relates to the field of organic materials, and in particular, to a nitrogen-containing compound and electronic components and electronic devices containing the same.

Background technique

Organic light-emitting diodes have the advantages of DC voltage driving, active light emission, small size, wide viewing angle, fast response speed, bright colors and simple production process, and have broad application prospects in the future display field.

In the structure of the organic light-emitting device, the electron blocking layer is used to block the electrons transmitted from the organic light-emitting layer, thereby ensuring that the electrons and holes can be efficiently recombined in the organic light-emitting layer; at the same time, the electron blocking layer can also prevent the organic light-emitting layer from diffusing. The excitons can reduce the triplet quenching of the excitons, thereby ensuring the luminous efficiency of the organic electroluminescent device. The compound of the electron blocking layer has a relatively high LUMO value, which can effectively block the transport and diffusion of electrons and excitons from the organic light-emitting layer to the anode direction.

Organic hole transport materials mainly include compounds such as carbazoles, triarylamines, styrenes and butadiene. Among them, triarylamines have the characteristics of high hole mobility and good electrochemical performance, and have been used as OLED holes. Transmission materials and luminescent materials are widely studied and applied. Triarylamines are centered on nitrogen atoms and have a propeller structure. Their large steric hindrance and hyperconjugation effect promote the high stability of nitrogen atom radicals. This unique free radical property makes triphenylamines more stable. Compounds have high hole mobility.

However, the lifespan and efficiency of organic light-emitting materials have always restricted the industrialization of OLEDs. Scholars at home and abroad have conducted extensive research on new organic light-emitting materials with excellent performance to shorten the process of OLED industrialization. Therefore, it is still necessary to develop new organic light-emitting materials.

SUMMARY OF THE INVENTION

In view of the above deficiencies in the prior art, the present application provides a nitrogen-containing compound and an electronic component and electronic device including the same, wherein the nitrogen-containing compound can improve the performance of the electronic component.

According to a first aspect of the present application, a nitrogen-containing compound is provided, and the structure of the nitrogen-containing compound is shown in formula 1:

Wherein, L, L ₁ and L ₂ are the same or different, and are independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted arylene group having 3 to 25 carbon atoms. substituted heteroarylene;

Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms. ;

The substituents in L, L ₁ , L ₂ , Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are independently selected from deuterium, halogen, cyano, heteroaryl with 3 to 18 carbon atoms, carbon An aryl group having 6 to 18 atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a carbon number of 3-10 cycloalkyl groups; optionally, two adjacent substituents form a ring.

According to a second aspect of the present application, there is provided an electronic component comprising an anode, a cathode, and a functional layer between the anode and the cathode, the functional layer comprising the nitrogen-containing compound described in the first aspect of the present application.

According to a third aspect of the present application, there is provided an electronic device including the electronic component described in the second aspect of the present application.

The nitrogen-containing compounds provided by the present application have triarylamine and biscarbazole structures, and the triarylamine compounds have good electricity donating properties and can form ammonium cations under the action of an electric field. The compounds have lower ionization potential and higher good hole mobility and good photostability. Further, carbazole is an electron-rich nitrogen-containing heterocyclic structure, with one of the carbazolyl groups (referred to as "carbazolyl A") as the center, and its N atom is connected to the 1st position of the other carbazolyl group.

At the same time, the benzene ring of carbazolyl A is connected to the triarylamine structure, so that the entire molecular structure is easily functionally modified in part of the active site of carbazolyl A due to its special rigid structure. A natural hole transport material. In addition, the introduction of the biscarbazole group with a specific linking position on the triarylamine structure can more effectively realize the effective matching between the transport material and the charge generating material, and at the same time improve the solubility of the compound and improve its thermal stability. Applying the nitrogen-containing compound of the present application to an organic electroluminescent device (OLED) can effectively improve the luminous efficiency and service life of the device under the condition that the device has a lower driving voltage.

It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not limiting of the present application.

Description of drawings

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

FIG. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present application.

FIG. 2 is a schematic structural diagram of a first electronic device according to an embodiment of the present application.

FIG. 3 is a schematic structural diagram of a photoelectric conversion device according to an embodiment of the present application.

FIG. 4 is a schematic structural diagram of a second electronic device according to an embodiment of the present application.

Description of reference numerals

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 electro- 340, electron transport layer; 350, electron injection layer; 360, photoelectric conversion layer; 400, first electronic device; 500, second electronic device.

Detailed ways

The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, but not to limit the present application.

In this application, the description methods "each independently selected from" and "...respectively independently are" and "...independently selected from" can be interchanged, and should be understood in a broad sense, which can either be It means that in different groups, the specific options expressed between the same symbols do not affect each other, and it can also mean that in the same group, the specific options expressed between 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, chlorine", and its meaning is: 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 indicates that each benzene ring of biphenyl has q substituents R", and the two benzene rings have q substituents R". 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.

In this application, the terms "optional" and "optionally" mean that the subsequently described event or circumstance can, but need not, occur, and that the description includes instances where the event or circumstance does or does not occur. For example, "optionally, two adjacent substituents form a ring" means that the two substituents may form a ring but need not form a ring, including: the situation where two adjacent substituents form a ring and the adjacent A scenario where the two substituents do not form a ring.

In this 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 substituents are collectively referred to as R _c ), if there is a substitution In the case of a group, the number of substituents may be one or plural. For example, "substituted or unsubstituted aryl" refers to an aryl group having one or more substituents _Rc or an unsubstituted aryl group. The above-mentioned substituent, ie R _c , can be, for example, deuterium, halogen group, cyano group, heteroaryl group, aryl group, trialkylsilyl group, alkyl group, haloalkyl group, cycloalkyl group and the like. When two substituent groups R _c are attached to the same atom, the two substituent groups R _c may exist independently or be connected to each other to form a ring with the atom; when there are two adjacent substituent groups R _c on the functional group When , the adjacent substituents R _c can exist independently or be condensed with the functional group to which they are connected to form a ring.

In this application, the number of carbon atoms of a substituted or unsubstituted functional group refers to the number of all carbon atoms. For example, if Ar ₁ is a substituted aryl group having 12 carbon atoms, then all carbon atoms of the aryl group and the substituents thereon are 12.

In this application, aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. Aryl groups can be monocyclic aryl groups (eg, phenyl) or polycyclic aryl groups, in other words, aryl groups can be monocyclic aryl groups, fused-ring aryl groups, two or more monocyclic aryl groups conjugated through carbon-carbon bonds. Cyclic aryl groups, monocyclic aryl groups and fused-ring aryl groups linked by carbon-carbon bond conjugation, two or more fused-ring aryl groups linked by carbon-carbon bond conjugation. That is, unless otherwise specified, two or more aromatic groups linked by carbon-carbon bond conjugation may also be considered aryl groups in the present application. Among them, the fused ring aryl group may include, for example, a bicyclic fused aryl group (eg, naphthyl), a tricyclic fused aryl group (eg, phenanthrenyl, fluorenyl, anthracenyl), and the like. The aryl group does not contain heteroatoms such as B, N, O, S, P, Se and Si. It should be noted that both biphenyl and fluorenyl are regarded as aryl groups in this application. Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, benzo[9,10]phenanthryl, pyrenyl, benzofluoranthene base,

Base et al.

In the present application, a substituted aryl group may be one or more than two hydrogen atoms in the aryl group replaced by a group such as deuterium, halogen group, cyano, aryl, heteroaryl, trialkylsilyl, haloalkyl, Alkyl, cycloalkyl and other groups are substituted. It should be understood that the number of carbon atoms in a 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 a carbon number of 18 refers to the aryl group and its substituents. The total number of carbon atoms of the substituents is 18. In addition, in the present application, the fluorenyl group may be substituted, and when there are two substituent groups, the two substituent groups may combine with each other to form a spiro structure. Specific examples of substituted fluorenyl groups include, but are not limited to,

In this 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 can be B, O, N, P At least one of , Si, Se, and S. A heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, a heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems linked by carbon-carbon bonds, and any aromatic The ring system is an aromatic monocyclic ring or an aromatic fused ring. Illustratively, heteroaryl groups can include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl Azinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thiophene thienyl, benzofuranyl, phenanthroline, isoxazolyl, thiadiazolyl, phenothiazinyl, silafluorenyl, dibenzofuranyl and N-phenylcarbazolyl, N-pyridine carbazolyl, N-methylcarbazolyl, etc., but not limited thereto. Among them, thienyl, furanyl, phenanthroline and the like are heteroaryl groups of a single aromatic ring system type, and N-phenylcarbazolyl is a heteroaryl group of a polycyclic system type connected by carbon-carbon bond conjugation. In the present application, the heteroarylene group referred to refers to a divalent or higher valent group formed by the further loss of one or more hydrogen atoms from the heteroaryl group.

In the present application, a substituted heteroaryl group may be a heteroaryl group where one or more than two hydrogen atoms are replaced by groups such as deuterium, halogen, cyano, aryl, heteroaryl, trialkylsilyl, alkane substituted by groups such as radicals, cycloalkyls, etc. It should be understood that the number of carbon atoms in a substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituents on the heteroaryl group.

In the present application, a non-positioned connecting bond refers to a single bond extending from the ring system

It means that one end of the linking bond can be connected to any position in the ring system through which the bond runs, and the other end is connected to the rest of the compound molecule. For example, as shown in the following formula (f), the naphthyl group represented by the formula (f) is connected to other positions of the molecule through two non-positioned linkages running through the bicyclic ring. -1) to any possible connection method shown in formula (f-10).

For another example, as shown in the following formula (X'), the phenanthrene represented by the formula (X') is connected to other positions of the molecule through a non-positioned link extending from the middle of one side of the benzene ring, which represents The meaning of , includes any possible connection modes shown by formula (X'-1) to formula (X'-4).

A non-positioned substituent in the present application refers to a substituent attached through a single bond extending from the center of the ring system, which means that the substituent may be attached at any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R' represented by the formula (Y) is connected to the quinoline ring through a non-positioning link, and the meanings represented by the formula (Y-1) to Any possible connection mode shown by formula (Y-7).

In the present application, the number of carbon atoms in the alkyl group may be 1-10, specifically 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and the alkyl group may include straight-chain alkyl groups and branched-chain alkyl groups. Alkyl. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl , heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, etc.

In the present application, halogen groups may include fluorine, iodine, bromine, chlorine, and the like.

In this application, the number of carbon atoms of the aryl group as a substituent may be 6-18, and the number of carbon atoms is specifically 6, 10, 12, 13, 14, 15, etc. Specific examples of the aryl group include, but are not limited to, Phenyl, naphthyl, biphenyl, phenanthryl, anthracenyl, etc.

In the present application, the number of carbon atoms of the heteroaryl group as a substituent may be 3 to 18, and the number of carbon atoms is, for example, 3, 4, 5, 8, 9, 10, 12, 13, 14, 15, etc. Specific examples of aryl groups include, but are not limited to, pyridyl, quinolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and the like.

In the present application, the number of carbon atoms of the trialkylsilyl group as a substituent may be 3 to 12, such as 3, 6, 7, 8, 9, etc. Specific examples thereof include, but are not limited to, trimethylsilyl , ethyldimethylsilyl, triethylsilyl, etc.

In the present application, the number of carbon atoms of the cycloalkyl group as a substituent may be 3-10, for example, 5-10 or 5-8, and specific examples include, but are not limited to, cyclopentyl, cyclohexyl, adamantyl, etc. .

In the present application, specific examples of haloalkyl include, but are not limited to, trifluoromethyl.

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

Wherein, L, L ₁ and L ₂ are the same or different, and are independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted arylene group having 3 to 25 carbon atoms. substituted heteroarylene;

Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms. ;

The substituents in L, L ₁ , L ₂ , Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are independently selected from deuterium, halogen, cyano, heteroaryl with 3 to 18 carbon atoms, carbon An aryl group having 6 to 18 atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a carbon number of 3-10 cycloalkyl groups; optionally, two adjacent substituents form a ring.

Specifically, the nitrogen-containing compound has the structure shown below:

Optionally, the substituents in L, L ₁ , L ₂ , Ar ₁ , Ar ₂ and Ar ₃ are independently selected from deuterium, fluorine, cyano, heteroaryl with 5 to 12 carbon atoms, carbon atoms Aryl with 6 to 15 carbon atoms, trialkylsilyl group with 3 to 7 carbon atoms, alkyl group with 1 to 5 carbon atoms, haloalkyl group with 1 to 5 carbon atoms or 5 carbon atoms ~10 cycloalkyl; optionally, two adjacent substituents form a 5-13 membered saturated or unsaturated ring.

Optionally, L, L ₁ and L ₂ are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, and a substituted or unsubstituted arylene group having 5 to 15 carbon atoms. Heteroaryl. For example, L, L ₁ , L ₂ are each independently selected from a single bond, or selected from substituted or unsubstituted carbon atoms having 6, 7, 8, 9, 10, 12, 14, 15, 16, 17, and 18 carbon atoms. An arylene group, or a substituted or unsubstituted heteroarylene group selected from the group consisting of 5, 6, 7, 8, 9, 10, 12, 14, and 15 carbon atoms.

Optionally, the substituents in L, L ₁ and L ₂ are selected from deuterium, fluorine, cyano, alkyl with 1 to 4 carbon atoms, trialkylsilyl with 3 to 7 carbon atoms, carbon A haloalkyl group having 1 to 4 atoms, an aryl group having 6 to 12 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. For example, the substituents in L, L ₁ , L ₂ are selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl, cyclopentyl, Cyclohexyl, trifluoromethyl or trimethylsilyl.

Optionally, L, L and _L are independently selected from _single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted Substituted dibenzofuranylene group, substituted or unsubstituted dibenzothienylene group, substituted or unsubstituted fluorenylene group, or a divalent group selected from the group consisting of at least two of the above-mentioned groups connected to each other through a single bond group.

According to one embodiment, L is selected from a single bond, or from a substituted or unsubstituted group V, and the unsubstituted group V is selected from the group consisting of:

Wherein, the substituted group V has one or more substituents, each of which is independently selected from deuterium, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthalene group, cyclopentyl, cyclohexyl, trimethylsilyl or trifluoromethyl; when the number of substituents is greater than 1, the substituents are the same or different.

Further optionally, L is selected from single bond or the group that the following groups are formed:

Optionally, L ₁ and L ₂ are each independently selected from a single bond, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

Optionally, L ₁ and L ₂ are each independently selected from single bond, substituted or unsubstituted phenylene.

Optionally, the substituents in L ₁ and L ₂ are each independently selected from deuterium, fluorine, cyano, alkyl with 1 to 4 carbon atoms or phenyl.

Further optionally, L ₁ and L ₂ are each independently selected from the group consisting of a single bond or the following groups:

Optionally, Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from substituted or unsubstituted aryl groups with 6-25 carbon atoms, or substituted or unsubstituted heteroaryl groups with 5-25 carbon atoms . For example, Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from the group consisting of 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23 carbon atoms , 24 or 25 substituted or unsubstituted aryl groups, or selected from the group consisting of 5, 6, 7, 8, 9, 10, 12, 13, 14, 15, 16, 17, 18, 20, 21, Substituted or unsubstituted heteroaryl of 22, 23, 24 or 25.

Alternatively, Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted Substituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted phenanthrene base.

Optionally, the substituents in Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from deuterium, fluorine, cyano, aryl with 6-12 carbon atoms, and heteroaryl with 5-12 carbon atoms , an alkyl group with 1 to 5 carbon atoms, a trialkylsilyl group with 3 to 7 carbon atoms, a haloalkyl group with 1 to 4 carbon atoms or a cycloalkyl group with 5 to 10 carbon atoms; any Optionally, two adjacent substituents form a 5-13 membered saturated or unsaturated ring.

For example, the substituents in Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from deuterium, cyano, fluorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl , naphthyl, cyclopentyl, cyclohexyl, carbazolyl, dibenzofuranyl, dibenzothienyl, pyridyl, quinolyl, trimethylsilyl or trifluoromethyl; optionally, phase The adjacent two substituents form a 5- to 13-membered saturated or unsaturated ring (for example, a cyclopentane, cyclohexane or fluorene ring).

Optionally, Ar ₁ and Ar ₂ are independently selected from substituted or unsubstituted groups W ₁ , and the unsubstituted group W ₁ is selected from the group consisting of:

Wherein, the substituted group W ₁ has one or more than two substituents, each of which is independently selected from: deuterium, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl , naphthyl, cyclopentyl, cyclohexyl, trimethylsilyl or trifluoromethyl; when the number of substituents is greater than 1, each substituent is the same or different; optionally, two adjacent substituents form A 5- to 13-membered saturated or unsaturated ring (eg forming a cyclopentane, cyclohexane or fluorene ring).

Optionally, Ar ₁ and Ar ₂ are independently selected from the group consisting of the following groups:

In one embodiment, Ar ₁ and Ar ₂ are each independently selected from a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 18 carbon atoms.

Optionally, Ar ₃ is selected from substituted or unsubstituted group W ₂ , and unsubstituted group W ₂ is selected from the group consisting of the following groups:

Wherein, the substituted group W ₂ has one or more substituents, each of which is independently selected from: deuterium, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl , naphthyl, cyclopentyl or cyclohexyl; when the number of substituents is greater than 1, each substituent is the same or different.

Further optionally, Ar ₃ is selected from the group that the following groups are formed:

Optionally, the nitrogen-containing compound is selected from the group formed by:

The present application does not specifically limit the synthesis method of the nitrogen-containing compound provided, and those skilled in the art can determine a suitable synthesis method according to the preparation method provided in the synthesis example section of the present application for the nitrogen-containing compound. In other words, the synthesis examples section of the present invention exemplarily provides a method for preparing 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 interpret it as a limit.

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 includes the nitrogen-containing compound described in the first aspect of the present application .

The nitrogen-containing compound provided in the present application can be used to form at least one organic film layer in the functional layer, so as to improve characteristics such as the lifespan of electronic components.

Optionally, the functional layer includes a hole transport layer comprising the nitrogen-containing compound of the present application. Wherein, the hole transport layer may be composed of the nitrogen-containing compound provided by the present application, or may be composed of the nitrogen-containing compound provided by the present application and other materials. The structure of the hole transport layer may be one layer or two or more layers.

Optionally, the electronic element is an organic electroluminescence device or a photoelectric conversion device.

According to one embodiment, the electronic component is an organic electroluminescent device, the hole transport layer includes a first hole transport layer and a second hole transport layer (also referred to as an "electron blocking layer"), the hole transport layer The first hole transport layer is closer to the anode than the second hole transport layer, wherein the second hole transport layer includes the nitrogen-containing compound, ie, the electron blocking layer includes the nitrogen-containing compound.

According to a specific embodiment, the electronic component is an organic electroluminescent device. As shown in FIG. 1 , the organic electroluminescent device may include an anode 100 , a first hole transport layer 321 , a second hole transport layer 322 , an organic light emitting layer 330 serving as an energy conversion layer, and an electron transport layer 340 , which are stacked in sequence. and cathode 200.

Optionally, the anode 100 includes an anode material, which is preferably a material 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 alloys thereof; 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 conducting polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene ](PEDT), polypyrrole and polyaniline, but not limited thereto. It is preferable to include a transparent electrode comprising indium tin oxide (ITO) as an anode.

Optionally, the first hole transport layer 321 may include one or more hole transport materials, and the hole transport materials may be selected from carbazole polymers, carbazole-linked triarylamine compounds or other types of compounds. There are no special restrictions on the application. For example, the first hole transport layer 321 is composed of the compound NPB.

Optionally, 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. Optionally, the organic light-emitting layer 330 is composed of a host material and a guest material. The holes injected into the organic light-emitting layer 330 and the electrons injected into the organic light-emitting layer 330 can recombine in the organic light-emitting layer 330 to form excitons, and the excitons transfer energy to the organic light-emitting layer 330. Host material, the host material transfers energy to the guest material, thereby enabling the guest material to emit light.

The host material of the organic light-emitting layer 330 may be metal chelate compounds, bis-styryl derivatives, aromatic amine derivatives, dibenzofuran derivatives or other types of materials, which are not specifically limited in this application.

The guest material of the organic light-emitting layer 330 may be a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative or other materials, which are not specially made in this application. limit.

The electron transport layer 340 may be a single-layer structure or a multi-layer structure, which may include one or more electron transport materials, and the electron transport materials may be selected from, but not limited to, benzimidazole derivatives, oxadiazole derivatives , quinoxaline derivatives or other electron transport materials. In one embodiment of the present application, the electron transport layer 340 is composed of ET-1 (structure shown below) and LiQ.

In the present application, the cathode 200 may include 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 multi-layer materials such as LiF/Al , Liq/Al, LiO ₂ /Al, LiF/Ca, LiF/Al and BaF ₂ /Ca. A metal electrode comprising magnesium and silver is preferably included as the cathode.

Optionally, as shown in FIG. 1 , a hole injection layer 310 may be further disposed between the anode 100 and the first hole transport layer 321 to enhance the capability of injecting holes into the first hole transport layer 321 . The hole injection layer 310 can be selected from benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives or other materials, which are not specifically limited in this application. For example, the hole injection layer 310 is composed of F4-TCNQ.

Optionally, as shown in FIG. 1 , an electron injection layer 350 may also be disposed between the cathode 200 and the electron transport layer 340 to enhance the capability of injecting electrons into the electron transport layer 340 . The electron injection layer 350 may include inorganic materials such as alkali metal sulfide and alkali metal halide, or may include a complex compound of alkali metal and organic matter. For example, the electron injection layer 350 contains LiQ or Yb.

According to a specific embodiment, the organic electroluminescent device is a blue light device.

According to another embodiment, the electronic component is a photoelectric conversion device. As shown in FIG. 3 , the photoelectric conversion device may include an anode 100 and a cathode 200 disposed opposite to each other, and a functional layer 300 disposed between the anode 100 and the cathode 200 ; the functional layer 300 includes the nitrogen-containing compound provided in the present application.

According to an exemplary embodiment, as shown in FIG. 3 , the functional layer 300 includes a hole transport layer 320 , and the hole transport layer 320 includes the nitrogen-containing compound of the present application. Wherein, the hole transport layer 320 may be composed of the nitrogen-containing compound provided in the present application, or may be composed of the nitrogen-containing compound provided by the present application and other materials.

Optionally, the hole transport layer 320 may further include an inorganic dopant material to improve the hole transport performance of the hole transport layer 320 .

According to a specific embodiment, as shown in FIG. 3 , the photoelectric conversion device may include an anode 100 , a hole transport layer 320 , a photoelectric conversion layer 360 , an electron transport layer 340 and a cathode 200 which are stacked in sequence.

Alternatively, the photoelectric conversion device may be a solar cell, especially an organic thin film solar cell. For example, in one embodiment of the present application, a solar cell may include an anode, a hole transport layer, a photoelectric conversion layer, an electron transport layer and a cathode that are stacked in sequence, wherein the hole transport layer includes the Nitrogenous compounds.

A third aspect of the present application provides an electronic device including the electronic component described in the first aspect of the present application.

According to an embodiment, as shown in FIG. 2 , the electronic device is a first electronic device 400 , and the first electronic device 400 includes the above-mentioned organic electroluminescence device. The first electronic device 400 may be, for example, a display device, a lighting device, an optical communication device, or other types of electronic devices, such as but not limited to computer screens, mobile phone screens, televisions, electronic paper, emergency lighting, light modules, and the like.

According to another embodiment, as shown in FIG. 4 , 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 may be, for example, a solar power generation device, a light detector, a fingerprint identification device, an optical module, a CCD camera, or other types of electronic devices.

The present invention is further illustrated by the following examples, but the present invention is not limited thereby.

Synthesis Examples are used to illustrate the synthesis of nitrogen-containing compounds of the present application.

1. Synthesis of intermediates

1. Synthesis of intermediate C-X

The synthesis of intermediate C-X is described below by taking intermediate C-1 as an example.

In the there-necked flask equipped with mechanical stirring, thermometer and spherical condenser, nitrogen (0.100L/min) was introduced for replacement for 15min, and reactant A-1 (5.0g, 17.05mmol), reactant B-1 (3.55g, 17.4mmol), cuprous iodide (0.65g, 3.4mmol), potassium carbonate (5.18g, 37.5mmol), 1,10-phenanthroline (0.62g, 1.7mmol), 18-crown-6-ether (1.23 g, 6.820 mmol) and N,N-dimethylformamide (50 mL) were added to the reaction flask, the temperature was raised to 150 ° C, and stirred for 12 h; cooled to room temperature, methylene chloride and water were added to the reaction solution, and the liquids were separated, The organic phase was washed with water, dried by adding anhydrous magnesium sulfate, filtered, the filtrate was passed through a short silica gel column, the solvent was removed under reduced pressure, and the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain intermediate C-1 (4.72 g, yield 75%).

The intermediates C-X listed in the following table 1 are synthesized with reference to the synthesis method of intermediate C-1, wherein each reactant B-X (X represents a variable) is used to replace the reactant B-1, and the intermediate C-X synthesized by the adopted reactant B-X Its yield is shown in Table 1.

Table 1

2. Synthesis of intermediate E-X

The synthesis of intermediate E-X is described below by taking intermediate E-1 as an example.

Into the there-necked flask equipped with mechanical stirring, thermometer and spherical condenser, nitrogen (0.100L/min) was introduced for replacement for 15min, and intermediate C-1 (5.0g, 13.5mmol), reactant D-1 (3.4g, 13.8mmol), cuprous iodide (0.52g, 2.7mmol), potassium carbonate (4.12g, 29.8mmol), 1,10-phenanthroline (0.5g, 1.35mmol), 18-crown-6-ether (0.98 g, 5.4 mmol) and N,N-dimethylformamide (50 mL) were added to the flask, the temperature was raised to 150 °C, and stirred for 12 h; cooled to room temperature, dichloromethane and water were added to the reaction solution, and the organic phase was separated. After washing with water, adding anhydrous magnesium sulfate, drying, filtering, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure. 75%).

The intermediates E-X listed in the following table 2 are synthesized with reference to the synthesis method of intermediate E-1, wherein, intermediate C-1 is replaced by each intermediate C-X, reactant D-1 is replaced by reactant D-X, and the main raw materials used are , the corresponding synthetic intermediates E-X and their yields are shown in Table 2.

Table 2

NMR data of intermediate E-2: ¹ H-NMR (400MHz, Cl ₂ D ₂ ): 8.34(d, 1H), 8.23(d, 1H), 7.79(d, 1H), 7.69(d, 1H), 7.51-7.45(m, 2H), 7.36-7.25(m, 3H), 7.14(t, 1H), 7.07(d, 1H), 6.99-6.93(m, 3H), 6.70-6.63(m, 2H), 6.54-6.48 (m, 2H), 6.37 (t, 1H).

3. Synthesis of intermediate G-X

The synthesis of intermediate G-X is described below by taking intermediate G-1 as an example.

Into the three-necked flask equipped with mechanical stirring, thermometer and spherical condenser, nitrogen (0.100L/min) was introduced for replacement for 15min, and intermediate E-1 (5.0g, 10.3mmol), reactant F-1 (1.60g, 10.2 mmol), potassium carbonate (4.25 g, 30.7 mmol), tetrakis(triphenylphosphine)palladium (0.60 g, 0.51 mmol), tetrabutylammonium bromide (0.12 g, 0.51 mmol), and toluene (40 mL) was added , a mixed solvent of ethanol (20 mL) and water (10 mL). Turn on stirring and heat to reflux for 12 h, and after the reaction is completed, cool to room temperature. Extract and separate the organic phase with toluene and water, wash with water until neutral, dry the organic phase with anhydrous magnesium sulfate, and filter the filtrate to remove the solvent under reduced pressure; use dichloromethane/n-heptane system to purify the crude product by silica gel column chromatography, Then use dichloromethane/ethyl acetate system for recrystallization and purification to obtain intermediate G-1 (4.04 g, yield 77%).

The intermediates G-X listed in the following table 3 are synthesized with reference to the synthesis method of intermediate G-1, wherein, intermediate E-1 is replaced by each intermediate E-X, reactant F-1 is replaced by reactant F-X, and the main raw materials used are , the corresponding synthetic intermediates G-X and their yields are shown in Table 3.

table 3

2. Synthesis of Compounds

Synthesis Example 1: Synthesis of Compound 4

Into the three-necked flask equipped with mechanical stirring, thermometer and spherical condenser, nitrogen (0.100L/min) was introduced for replacement for 15min, and intermediate E-1 (5.0g, 10.3mmol), reactant H-1 (1.74g) were added successively. , 10.3mmol), tris(dibenzylideneacetone)dipalladium (0.09g, 0.10mmol), 2-dicyclohexylphosphorus-2',4',6'-triisopropylbiphenyl (0.09g, 0.2 mmol), sodium tert-butoxide (2.96 g, 30.8 mmol) and toluene (40 mL). The stirring was started, the temperature was raised to 105-115° C. for 3 h, and after the reaction was completed, it was cooled to room temperature. The reaction solution was extracted with dichloromethane and water, and the organic phase was dried over anhydrous magnesium sulfate. After filtration, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to obtain compound 4. (2.07 g, 35% yield), mass spectrum: m/z=576.2 [M+H] ⁺ .

Synthesis Example 2-37

With reference to the synthesis method of compound 4, the compounds shown in the following table 4 are synthesized, wherein, intermediate E-X or intermediate G-X is used instead of intermediate E-1, reactant H-X is replaced by reactant H-1, the main raw materials used, the corresponding synthesis The compounds, their yields, and mass spectrometry characterization results are shown in Table 4.

Table 4

NMR data of compound 679: ¹ H-NMR (400 MHz, Cl ₂ D ₂ ): 5.61 (d, 1H), 5.50 (d, 1H), 5.07-5.16 (m, 2H), 4.53-4.88 (m, 20H) , 4.42-4.50(m, 5H), 4.28-4.36(m, 2H), 4.11-4.24(m, 3H), 3.79-4.10(m, 3H).

Fabrication and performance evaluation of organic electroluminescent devices

Example 1

Set the ITO thickness to

The substrate was cut into a size of 40mm × 40mm × 0.7mm, and a photolithography process was used to prepare it into an experimental substrate with a cathode overlapping area, an anode and an insulating layer pattern, and the surface was treated with ultraviolet ozone and O2:N2 plasma. Increase the work function of the anode (experimental substrate) and remove scum.

Compound F4-TCNQ was vacuum evaporated on the experimental substrate (anode) to form a thickness of

The hole injection layer (HIL); and the compound NPB is vacuum-evaporated on the hole injection layer to form a thickness of

The first hole transport layer (HTL1).

Compound 4 was vacuum evaporated on the first hole transport layer to form a thickness of

The second hole transport layer (HTL2).

On the second hole transport layer, BH-1 and BD-1 were co-evaporated at a film thickness ratio of 98%: 2% to form a thickness of

The blue light-emitting layer (EML).

ET-1 and LiQ were mixed in a weight ratio of 1:1 and evaporated to form

Thick electron transport layer (ETL), then Yb was evaporated on the electron transport layer to form a thickness of

the electron injection layer (EIL).

Magnesium (Mg) and silver (Ag) were vacuum-deposited on the electron injection layer at a film thickness ratio of 1:10 to form a thickness of

the cathode.

In addition, CP-1 was vapor-deposited on the above-mentioned cathode to form a thickness of

The cover layer (CPL) of the organic electroluminescent device is completed.

In this embodiment, the main material structures used to prepare the device are shown below.

Example 2-37

An organic electroluminescent device was fabricated by the same method as in Example 1, except that the remaining compounds shown in Table 6 were respectively used instead of Compound 4 when forming the second hole transport layer.

Comparative Examples 1 to 4

The organic electroluminescent device was fabricated by the same method as in Example 1, except that Compound A to Compound D were respectively used instead of Compound 4 when forming the second hole transport layer. The structures of compounds A to D are as follows:

For the organic electroluminescent device prepared as above, the IVL performance of the device was tested under the condition of 20 mA/cm ² , and the lifetime of the T95 device was also tested under the condition of 20 mA/cm ² . The results are shown in Table 6.

Table 6

According to the results in Table 6, compared with Comparative Examples 1-4, various properties of the organic electroluminescent devices prepared in Examples 1-37 were improved. Specifically, as the material of the second hole transport layer, the luminous efficiency (Cd/A) of Examples 1-37 using the nitrogen-containing compound of the present application was at least improved compared with Comparative Examples 1-4 using the existing compound 11.8%, the external quantum efficiency is increased by at least 11.8%, the device life of the embodiment is the least increased by 15.2%, and the embodiment 1-37 also has a lower driving voltage.

In summary, when the nitrogen-containing compound of the present application is used as the material of the second hole transport layer (that is, the material of the electron blocking layer), the luminous efficiency and service life of the organic electroluminescence device can be effectively improved, and the device can be kept relatively high. low drive voltage.

It should be understood that this application does not limit its application to the detailed structure and arrangement of components presented in this specification. The application is capable of other embodiments, of being implemented and of being carried out in various ways. The foregoing variations and modifications fall within the scope of the present application. It is to be understood that the application disclosed and defined in this specification extends to all alternative combinations of two or more of the individual features mentioned or evident in the text and/or drawings. All of these different combinations constitute various alternative aspects of the present application. The embodiments described in this specification illustrate the best mode known to carry out the application, and will enable those skilled in the art to utilize the application.

Claims (14)

1. A nitrogen-containing compound, characterized in that the structure of the nitrogen-containing compound is shown in formula 1:

   

   Wherein, L, L ₁ and L ₂ are the same or different, and are independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 25 carbon atoms, and a substituted or unsubstituted arylene group having 3 to 25 carbon atoms. substituted heteroarylene;

   Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are independently selected from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms. ;

   The substituents in L, L ₁ , L ₂ , Ar ₁ , Ar ₂ and Ar ₃ are the same or different, and are independently selected from deuterium, halogen, cyano, heteroaryl with 3 to 18 carbon atoms, carbon An aryl group having 6 to 18 atoms, a trialkylsilyl group having 3 to 12 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a carbon number of 3-10 cycloalkyl groups; optionally, two adjacent substituents form a ring.
2. The nitrogen-containing compound according to claim 1, wherein L, L ₁ and L ₂ are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, and a 5 carbon atom group. ~15 substituted or unsubstituted heteroarylene;

   Preferably, the substituents in L, L ₁ and L ₂ are selected from deuterium, fluorine, cyano, alkyl groups with 1 to 4 carbon atoms, trialkylsilyl groups with 3 to 7 carbon atoms, carbon atoms A halogenated alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
3. The nitrogen-containing compound of claim 1, wherein L, L ₁ and L ₂ are each independently selected from single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothienylene, substituted or unsubstituted fluorenylene, or at least two groups selected from the above through each other A divalent group formed by a single bond;

   Preferably, the substituents in L, L ₁ and L ₂ are each independently selected from deuterium, fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl, Cyclopentyl, cyclohexyl, trifluoromethyl or trimethylsilyl.
4. The nitrogen-containing compound of claim 1, wherein L is selected from a single bond, or from a substituted or unsubstituted group V, and the unsubstituted group V is selected from the group consisting of:

   

   Wherein, the substituted group V has one or more substituents, each of which is independently selected from deuterium, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthalene group, cyclopentyl, cyclohexyl, trimethylsilyl or trifluoromethyl; when the number of substituents is greater than 1, the substituents are the same or different.
5. The nitrogen-containing compound according to claim 1, wherein Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from substituted or unsubstituted aryl groups having 6 to 25 carbon atoms, or 5 to 25 carbon atoms. substituted or unsubstituted heteroaryl;

   Preferably, the substituents in Ar ₁ , Ar ₂ and Ar ₃ are independently selected from deuterium, fluorine, cyano, aryl with 6-12 carbon atoms, heteroaryl with 5-12 carbon atoms, An alkyl group with 1-5 carbon atoms, a trialkylsilyl group with 3-7 carbon atoms, a haloalkyl group with 1-4 carbon atoms or a cycloalkyl group with 5-10 carbon atoms; optional Typically, two adjacent substituents form a 5- to 13-membered saturated or unsaturated ring.
6. The nitrogen-containing compound of claim 1, wherein Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl , substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted phenanthryl;

   Preferably, the substituents in Ar ₁ , Ar ₂ and Ar ₃ are each independently selected from deuterium, cyano, fluorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, biphenyl radical, naphthyl, cyclopentyl, cyclohexyl, carbazolyl, dibenzofuranyl, dibenzothienyl, pyridyl, quinolyl, trimethylsilyl or trifluoromethyl; optionally, Two adjacent substituents form a 5-13-membered saturated or unsaturated ring.
7. The nitrogen-containing compound of claim 1, wherein Ar ₁ and Ar ₂ are independently selected from substituted or unsubstituted groups W ₁ , and the unsubstituted group W ₁ is selected from the group consisting of:

   

   Wherein, the substituted group W ₁ has one or more substituents, each of which is independently selected from: deuterium, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl , naphthyl, cyclopentyl, cyclohexyl, trimethylsilyl or trifluoromethyl; when the number of substituents is greater than 1, each substituent is the same or different; optionally, two adjacent substituents form 5-13-membered saturated or unsaturated ring.
8. The nitrogen-containing compound according to claim 1, wherein Ar ₃ is selected from substituted or unsubstituted group W ₂ , and unsubstituted group W ₂ is selected from the group consisting of:

   

   Wherein, the substituted group W ₂ has one or more substituents, each of which is independently selected from: deuterium, cyano, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl , naphthyl, cyclopentyl or cyclohexyl; when the number of substituents is greater than 1, each substituent is the same or different.
9. The nitrogen-containing compound of claim 1, wherein the nitrogen-containing compound is selected from the group consisting of:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
10. An electronic component, characterized in that the electronic component comprises an anode, a cathode, and a functional layer interposed between the anode and the cathode, the functional layer comprising the nitrogen-containing compound according to any one of claims 1-9.
11. 11. The electronic component according to claim 10, wherein the functional layer includes a hole transport layer including the nitrogen-containing compound.
12. The electronic component according to claim 11, wherein the electronic component is selected from an organic electroluminescence device or a photoelectric conversion device.
13. The electronic component of claim 11, wherein the electronic component is an organic electroluminescence device, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the first hole transport layer The transport layer is closer to the anode than a second hole transport layer, the second hole transport layer comprising the nitrogen-containing compound.
14. An electronic device, characterized by comprising the electronic component described in any one of claims 10-13.

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