Phosphine oxide compound and organic electroluminescent device containing same

Abstract

The invention belongs to the technical field of organic electroluminescence, and particularly relates to a phosphine oxide compound and an organic electroluminescence device containing the same. The invention relates to a phosphine oxide compound, which has a structure shown in a formula (1): # imgabs0 #, in which X is selected from CR or N, and R is selected from hydrogen, substituted or unsubstituted aryl of C6-C60, and substituted or unsubstituted heteroaryl of C3-C60. The organic electroluminescent compound disclosed by the invention has a phosphine oxide structure, so that the electron injection and transmission capability is improved; the organic electroluminescent element prepared by using the compound can realize improved luminous efficiency, reduced driving voltage and durable service life.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and particularly relates to a phosphine oxide compound and an organic electroluminescent device containing the compound. Background Art

[0002] An organic light emitting diode (OLED) is a self-luminous display device based on organic electroluminescent materials. Unlike existing liquid crystal display devices, it has the characteristics of not requiring a backlight source and being thin, and is a technology suitable for flexible device devices (flexible light-emitting display devices). An organic light-emitting device has an anode and a cathode, and a structure in which an organic thin film is placed between the two electrodes. It includes a simple device with a single light-emitting unit or a series device with multiple light-emitting units. A simple device generally includes a hole transport layer, a light-emitting layer, and an electron transport layer. Since the electron mobility of the electron transport layer material is much lower than the hole mobility of the hole transport layer material, an imbalance of holes and electrons enter the light-emitting layer, which affects the luminous efficiency and life of the device. A series device generally provides a charge generation layer between the light-emitting units to ensure that the charge is effectively distributed to the light-emitting stack while improving the current efficiency in each light-emitting layer. Generally, the charge generation layer has a PN junction, in which an N-type charge generation layer and a P-type charge generation layer are stacked in sequence.

[0003] The injection barrier of electrons from the charge generation layer from the N-type charge generation layer to the adjacent electron transport layer is relatively large. Therefore, electrons accumulate at the interface between the N-type charge generation layer and the adjacent electron transport layer, which can easily cause degradation of the interface and shorten the life of the device. The energy level difference between the electron transport layer and the N-type charge generation layer will cause the driving voltage to increase.

[0004] Therefore, it is urgent to develop new materials to improve the luminous efficiency and life of the device. Summary of the invention

[0005] The present invention is directed to a phosphine oxide compound, the organic electroluminescent device prepared using the compound can achieve improved luminous efficiency, reduced driving voltage and durable service life.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] A phosphine oxide compound having a structure shown in formula (1):

[0008]

[0009] Wherein, X is selected from CR or N,

[0010] R is selected from hydrogen, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, L1 -L 2 are each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group,

[0011] R 1 -R 4 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

[0012] -L 1 R 1 , -L 2 R 2 Same or different,

[0013] When substituted or unsubstituted, the substituent is selected from one or a combination of deuterium, halogen, cyano, C1-C10 alkyl, C6-C30 aryl, C3-C30 heteroaryl;

[0014] The heteroatom of the heteroaryl group is selected from one or more of oxygen, sulfur and nitrogen.

[0015] Preferably, X is selected from CH or N; when -L 1 R 1 When it is hydrogen, -L 2 R 2 Not hydrogen or deuterium; when -L 1 R 1 When it is deuterium, -L 2 R 2 Not hydrogen or deuterium.

[0016] Preferably, X is selected from CH.

[0017] Preferably, X is selected from N.

[0018] Preferably, the R 3 Selected from phenyl.

[0019] Preferably, the R 4 Selected from phenyl.

[0020] As a preference, L 1 , L 2 , R 1 , R 2 At least one of them is selected from substituted or unsubstituted heteroaryl containing 1 to 3 N atoms.

[0021] As a preference, L 1is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from substituted or unsubstituted pyridylene, substituted or unsubstituted bipyridylene, substituted or unsubstituted terpyridylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted quinolylene, substituted or unsubstituted isoquinolylene, substituted or unsubstituted quinoxalylene, substituted or unsubstituted quinazolinylene, substituted or unsubstituted phenanthrolinylene, substituted or unsubstituted triazinylene, substituted or unsubstituted phenazinylene, substituted or unsubstituted pyrazinylene;

[0022] As a preference, L 2 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from substituted or unsubstituted pyridylene, substituted or unsubstituted bipyridylene, substituted or unsubstituted terpyridylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted quinolylene, substituted or unsubstituted isoquinolylene, substituted or unsubstituted quinoxalylene, substituted or unsubstituted quinazolinylene, substituted or unsubstituted phenanthrolinylene, substituted or unsubstituted triazinylene, substituted or unsubstituted phenazinylene, substituted or unsubstituted pyrazinylene;

[0023] As a preference, R 1 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted triazinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted pyrazinyl;

[0024] As a preference, R 2 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted triazinyl, substituted or unsubstituted phenazinyl, and substituted or unsubstituted pyrazinyl.

[0025] Preferably, the L 1 , L 2Each is independently selected from a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted substituted or unsubstituted fluoranthene, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxaline substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted indenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted fluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl.

[0026] Preferably, the L 1 , L 2 Each is independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted pyrenylene, and substituted or unsubstituted fluoranthenylene.

[0027] Preferably, the R 1 , R 2 and each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted substituted or unsubstituted fluoranthene, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted indenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzopyrenyl, substituted or unsubstituted substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzimidazolyl, or substituted or unsubstituted carbolyl.

[0028] Preferably, the substituents in “substituted or unsubstituted” are each independently selected from deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclyl, substituted or unsubstituted C3-C60 heterocyclyl.

[0029] Preferably, the substituents in "substituted or unsubstituted" are each independently selected from deuterium, halogen, cyano, methyl, ethyl, tert-butyl, cyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrene, fluoranthenyl, triphenylene, A combination of one or more of phenyl, pyridyl, pyrimidinyl, triazine, phenazine, quinolyl and isoquinolyl.

[0030] An organic electroluminescent element comprises a first electrode, a second electrode and an organic layer between the first electrode and the second electrode. The organic layer has one or more layers, and at least one organic layer comprises the phosphine oxide compound of the present invention.

[0031] Preferably, the organic layer includes at least two light-emitting units, and the light-emitting unit includes at least one layer of a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer; a charge generation layer is included between the two light-emitting units, and the charge generation layer includes an N-type charge generation layer and a P-type charge generation layer; the N-type charge generation layer includes the phosphine oxide compound described in the present invention.

[0032] Preferably, the organic layer comprises at least one of a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer; and the electron transport layer comprises the phosphine oxide compound of the present invention.

[0033] Preferably, the electron transport layer comprises the electron transport layer of each light-emitting unit, and at least one of the N-type charge generation layer and the electron transport layer comprises the phosphine oxide compound of the present invention, which means that one N-type charge generation layer comprises the phosphine oxide compound of the present invention; or multiple N-type charge generation layers comprise the phosphine oxide compound of the present invention; or one electron transport layer in one light-emitting unit comprises the phosphine oxide compound of the present invention; or one N-type charge generation layer and one electron transport layer in one light-emitting unit comprise the phosphine oxide compound of the present invention; or one N-type charge generation layer and each electron transport layer in multiple light-emitting units comprise the phosphine oxide compound of the present invention; or multiple N-type charge generation layers and each electron transport layer in multiple light-emitting units comprise the phosphine oxide compound of the present invention, etc. When more than 2 layers comprise the phosphine oxide compound of the present invention, the phosphine oxide compounds are the same or different.

[0034] An electronic device comprises: one or more of a display, a monitor and a lighting device, including the organic electroluminescent element of the present invention; and a control unit for driving the display device.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The organic electroluminescent compound of the present invention has a phosphine oxide structure, which improves the electron injection and transmission capabilities; the organic electroluminescent element prepared using the compound can achieve improved luminous efficiency, reduced driving voltage and durable service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 1, wherein the first electrode layer 1, the hole injection layer 2, the hole transport layer 3, the light-emitting layer 4, the electron transport layer 5, the N-type charge generation layer 6, the P-type charge generation layer 7, the hole transport layer 8, the light-emitting layer 9, the electron transport layer 10, the electron injection layer 11 and the second electrode layer 12, wherein 100 is the first light-emitting unit and 200 is the second light-emitting unit.

[0038] Figure 2 1 is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 2, wherein the first electrode layer 110 , the hole injection layer 120 , the hole transport layer 130 , the light-emitting layer 140 , the electron transport layer 150 , the electron injection layer 160 and the second electrode layer 170 . DETAILED DESCRIPTION

[0039] In order to more fully describe the present invention to those skilled in the art, embodiments of the present invention are provided. The scope of the present invention is not limited to the following embodiments. These embodiments can make the present invention more thorough and complete, and fully convey the viewpoints of the present invention to those skilled in the art.

[0040] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.

[0041] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0042] As used in the present invention, the term "C1-C10 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 10 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0043] As used in the present invention, the term "C3-C10 cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornyl, adamantane, and the like.

[0044] As used in the present invention, the term "C2-C10 heterocycloalkyl" is a monovalent substituent having a monocyclic or polycyclic ring of 2 to 10 carbon atoms, and the ring contains at least one heteroatom selected from O, S, N, P, and Si.

[0045] As used in the present invention, the term "alkoxy" refers to a straight chain, a branched chain or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited herein, but the alkoxy group preferably has 1 to 10 carbon atoms. Specific examples thereof include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentyloxy, n-hexyloxy, and benzyloxy.

[0046] As used in the present invention, the term "C6-C60 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a monocyclic ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such an aryl may have a form in which two or more rings are simply lateral or fused to each other. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0047] As used in the present invention, the term "arylene group" refers to a divalent aromatic group derived from an "aryl group" by removing a hydrogen atom. For example, a phenyl group is phenylene when a hydrogen atom is removed, and a naphthyl group is naphthylene when a hydrogen atom is removed.

[0048] As used in the present invention, the term "C3-C60 heteroaryl group" refers to a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S, P, B or Si. In addition, this heteroaryl group may have a form in which two or more rings are simply lateral to each other or fused to each other or fused to an aromatic group. Examples of such heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthroline, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl and the like, but the present invention is not limited thereto.

[0049] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl group derived from a "heteroaryl" by removing a hydrogen atom. For example, a pyridyl group is derived from a pyridylene group by removing a hydrogen atom.

[0050] As used in the present invention, "L 1 R 1 "Hydrogen" means L 1 Selected from single bonds, R 1 Selected from hydrogen; "L 2 R 2 "Hydrogen" means L 2 Selected from single bonds, R 2 Selected from hydrogen.

[0051] As used in the present invention, the "carbon number is AA-BB" in the expression "Z group having carbon atoms AA-BB" or "Z group having C(AA-BB)" means the carbon number of the Z group when it is unsubstituted, and does not include the carbon number of the substituent when it is substituted. For example, a C6-C30 aryl group means that when it is unsubstituted, the number of carbon atoms in the aryl group is any integer between 6 and 30, that is, the number of carbon atoms when it is unsubstituted can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20...30.

[0052] As used herein, the term "single bond" refers to a direct connection of groups, e.g. Medium 1 is a single bond, which means

[0053] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where the substitution occurs can be the position where the hydrogen atom is replaced. That is, the position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. For example, carbazolyl includes any of the following groups, but is not limited thereto, as long as it is not otherwise described in this specification,

[0054]

[0055] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0056] As used herein, the term "phenylene naphthyl" refers to

[0057] As used herein, the term "phenylnaphthyl" includes

[0058] Refers to the replacement position.

[0059] As used in the present invention, the term "1-3 N heteroaryl" includes any of the following groups, but is not limited thereto,

[0060] Indicates the connection location.

[0061] When two or more substituents are present, the two or more substituents may be the same or different.

[0062] As used in the present invention, hydrogen atoms include protium, deuterium and tritium. The compounds of the present invention may contain deuterium atoms of natural origin, or may introduce deuterium atoms by deuterating a portion or all of the raw material compounds. If deuterium atoms are introduced from the raw materials, the deuteration rate may be 100%, or may be less than 100%, or less than 95%, or less than 90%, or less than 80%, and the deuteration rate may also be more than 1%, or more than 5%, or more than 10%. If the deuteration rate is not 100%, it means a mixture of deuterated compounds and undeuterated compounds, or a mixture of completely deuterated compounds and incompletely deuterated compounds, or a mixture of completely deuterated compounds and undeuterated compounds and incompletely deuterated compounds.

[0063] As used in the present invention, terms such as first, second, A, B, etc. are used. The above terms are only used to distinguish components, and do not limit the nature or order of the components to which the terms correspond.

[0064] Organic electroluminescent element

[0065] The structure of the organic electroluminescent element of the present invention is a disclosed structure, comprising an anode, a cathode and an organic layer located between the anode and the cathode, wherein the organic layer comprises a light-emitting layer, and at least one layer of the organic layer comprises the compound of the present invention.

[0066] The organic layer may further include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0067] The light-emitting element of the present invention may emit fluorescence or phosphorescence or a combination thereof. The light-emitting element may emit light alone or in series with multiple light-emitting units.

[0068] As simple light emitting elements, the following may be cited, but are not limited thereto:

[0069] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0070] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0071] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0072] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0073] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0074] (6) hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer;

[0075] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0076] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0077] (9) hole transport layer / electron blocking layer / phosphorescent emitting layer / hole blocking layer / electron transport layer;

[0078] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0079] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0080] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0081] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0082] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0083] As a tandem type organic electroluminescent element, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer can also be generally called a charge generation layer, an electron extraction layer, a connecting layer, etc. For example, when stacking a fluorescent light-emitting layer and a phosphorescent light-emitting layer, an intermediate layer is placed between the fluorescent light-emitting layer and the phosphorescent light-emitting layer in order to prevent the excitons generated by the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer or to adjust the balance of carriers.

[0084] When the organic light emitting element includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

[0085] The organic electroluminescent element of the present specification can be manufactured by materials and methods known in the art, except that one or more of the organic material layers is prepared by using a compound comprising the formula (1).

[0086] As the anode material, a material having a relatively large work function may be used, and a transparent conductive oxide, a metal, a conductive polymer, or the like may be used.

[0087] As the cathode material, a material having a low work function is generally used to facilitate electron injection into the organic material layer, and metals, metal oxides, conductive polymers, etc. can be used.

[0088] The hole injection layer is a layer that injects holes from the electrodes and has the ability to transport holes. In order to reduce the energy level difference between the electrodes, the hole injection layer is mainly prepared based on aromatic amine compounds, and other materials with hole transport ability can also be used.

[0089] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and the hole transport material is suitably a material having high hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

[0090] The luminescent material is a material that receives holes and electrons from the hole transport layer and the electron transport layer, respectively, and combines the holes and electrons to emit light in the visible light region. The luminescent layer material includes a host material and a doping material. Red, green or blue luminescent materials can be used, and two or more luminescent materials can be mixed as needed. As the luminescent material, a fluorescent material can be used, and a phosphorescent material can also be used. As the luminescent material, a single component material can be used, and a multi-component material can also be used.

[0091] The electron transport layer receives electrons from the electron injection layer and transports the electrons to the light-emitting layer, and the electron transport material can receive electrons from the cathode and transfer the electrons to the light-emitting layer. The metal complexes of triazine derivatives, oxadiazole derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, 8-hydroxyquinoline and its derivatives, etc. can be used, and polymer materials and small molecule materials can also be used.

[0092] The electron injection layer is a layer that injects electrons from the electrode.

[0093] The hole blocking layer is a layer that blocks holes from reaching the cathode.

[0094] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0095] The organic light-emitting element of the present specification may be a top-emitting element, a bottom-emitting element, or a dual-emission element depending on the materials used.

[0096] The charge generation layer is an intermediate layer between the anode and cathode in a tandem structure element, and is a layer that generates holes and electrons by charge separation. The charge generation layer is usually formed by a P-type layer on the cathode side and an N-type layer on the anode side, and can effectively separate charges and effectively transport carriers.

[0097] In one specific embodiment of the present invention, in formula (1), X is selected from CH;

[0098] L 1 , L 2each 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 naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted benzopyrenylene group, a substituted or unsubstituted ... substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted pyridinylene;

[0099] R 1 , R 2 and each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted substituted or unsubstituted fluoranthene, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted indenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzopyrenyl, substituted or unsubstituted substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted carbolinyl;

[0100] R 3 , R 4 are selected from phenyl.

[0101] Preferably, L 1 , L 2 , R 1, R 2 At least one of them is selected from a heteroaryl group containing 1 to 3 N atoms.

[0102] As a preference, L 1 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from a substituted or unsubstituted pyridylene, a substituted or unsubstituted bipyridylene, a substituted or unsubstituted terpyridylene, a substituted or unsubstituted pyrimidylene, a substituted or unsubstituted pyridazinylene, a substituted or unsubstituted quinolylene, a substituted or unsubstituted isoquinolylene, a substituted or unsubstituted quinoxalylene, a substituted or unsubstituted quinazolinylene, a substituted or unsubstituted phenanthrolinylene, a substituted or unsubstituted triazinylene, a substituted or unsubstituted phenazinylene, and a substituted or unsubstituted pyrazinylene.

[0103] As a preference, L 2 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from a substituted or unsubstituted pyridylene, a substituted or unsubstituted bipyridylene, a substituted or unsubstituted terpyridylene, a substituted or unsubstituted pyrimidylene, a substituted or unsubstituted pyridazinylene, a substituted or unsubstituted quinolylene, a substituted or unsubstituted isoquinolylene, a substituted or unsubstituted quinoxalylene, a substituted or unsubstituted quinazolinylene, a substituted or unsubstituted phenanthrolinylene, a substituted or unsubstituted triazinylene, a substituted or unsubstituted phenazinylene, and a substituted or unsubstituted pyrazinylene.

[0104] As a preference, R 1 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted triazinyl, substituted or unsubstituted phenazinyl, and substituted or unsubstituted pyrazinyl.

[0105] As a preference, R 2 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1is selected from substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted triazinyl, substituted or unsubstituted phenazinyl, and substituted or unsubstituted pyrazinyl.

[0106] In one specific embodiment of the present invention, in formula (1), X is selected from N;

[0107] L 1 , L 2 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 naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted benzopyrenylene group, a substituted or unsubstituted ... substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted pyridinylene;

[0108] R 1 , R 2 and each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted substituted or unsubstituted fluoranthene, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted indenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzopyrenyl, substituted or unsubstituted substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted carbolinyl;

[0109] R 3 , R 4 are selected from phenyl.

[0110] Preferably, L 1 , L 2 , R 1 , R 2 At least one of them is selected from a heteroaryl group containing 1 to 3 N atoms.

[0111] As a preference, L 1 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from a substituted or unsubstituted pyridylene, a substituted or unsubstituted bipyridylene, a substituted or unsubstituted terpyridylene, a substituted or unsubstituted pyrimidylene, a substituted or unsubstituted pyridazinylene, a substituted or unsubstituted quinolylene, a substituted or unsubstituted isoquinolylene, a substituted or unsubstituted quinoxalylene, a substituted or unsubstituted quinazolinylene, a substituted or unsubstituted phenanthrolinylene, a substituted or unsubstituted triazinylene, a substituted or unsubstituted phenazinylene, and a substituted or unsubstituted pyrazinylene.

[0112] As a preference, L 2 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1is selected from a substituted or unsubstituted pyridylene, a substituted or unsubstituted bipyridylene, a substituted or unsubstituted terpyridylene, a substituted or unsubstituted pyrimidylene, a substituted or unsubstituted pyridazinylene, a substituted or unsubstituted quinolylene, a substituted or unsubstituted isoquinolylene, a substituted or unsubstituted quinoxalylene, a substituted or unsubstituted quinazolinylene, a substituted or unsubstituted phenanthrolinylene, a substituted or unsubstituted triazinylene, a substituted or unsubstituted phenazinylene, and a substituted or unsubstituted pyrazinylene.

[0113] As a preference, R 1 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted triazinyl, substituted or unsubstituted phenazinyl, and substituted or unsubstituted pyrazinyl.

[0114] As a preference, R 2 is selected from substituted or unsubstituted heteroarylene containing 1-3 N; more preferably, L 1 is selected from substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted triazinyl, substituted or unsubstituted phenazinyl, and substituted or unsubstituted pyrazinyl.

[0115] In a specific embodiment of the present invention, the phosphine oxide compound is selected from any one of the following compounds No. 1-192:

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129] Synthesis formula: The following general formula is only one method for synthesizing the compounds of the present invention. The compounds of the present invention can also be synthesized by other methods.

[0130]

[0131] Among them, X, L 1 , L 2 , R 1 -R 4 With X, L in formula (1) 1 , L 2 , R 1 -R 4 The meaning expressed is the same.

[0132] Compound Preparation Examples

[0133] The present invention is specifically described by way of compound examples 1-3.

[0134] Compound Example 1 Synthesis of Compound 32

[0135]

[0136] Under nitrogen atmosphere, 2-chloropyrimidine (10 g, 87.7 mmol), hexamethyltin (15 mL, 96.4 mmol), tetrakistriphenylphosphine palladium (1 g, 1.7 mmol) and xylene 100 mL were added to a four-necked flask in sequence. After heating and reflux for 2 h, 100 mL of xylene was added again to dissolve, and intermediate 48-2 (30 g, 61.23 mmol) was added, and the temperature was refluxed for 2 h. The temperature was lowered, the filtrate was filtered, and after concentrating under reduced pressure, the compound 32 (15 g, 28 mmol) was obtained by slurrying with ethanol.

[0137] LC-MS: [M+H] + =533.17

[0138] 1HNMR(400MHz,MethyleneChloride-d2)δ8.81(d,3H),8.75–8.62(m,3H),7.96–7.82(m,4H),7.75– 7.66(m,4H),7.64–7.60(m,1H),7.58(dd,1H),7.57–7.51(m,2H),7.49–7.41(m,5H),7.25(t,1H).

[0139] Compound Example 2

[0140] 1. Synthesis of intermediate 48-1

[0141]

[0142] Under nitrogen atmosphere, 2,6-dichloro-4-iodopyridine (3.8 g, 14 mmol), diphenylphosphine oxide (2.26 g, 11 mmol), tetrakis(triphenylphosphine)palladium (0.8 g, 0.7 mmol) and potassium carbonate (3.87 g, 28 mmol) were added to a four-necked reaction flask, 150 mL of DMF was added, and refluxed for 1 hour. The reaction solution was cooled to room temperature, water was added to precipitate the solid, filtered, and the filter cake was washed with ethanol and hexane, and dried to obtain a yellow solid. The solid was purified by chromatography (developing solvent was n-hexane: ethyl acetate volume ratio = 1:5). Thus, a white solid (3.0 g, yield 60%) of intermediate 48-1 was obtained.

[0143] LC-MS(APCI):348.15(M+H) + .

[0144] 2. Synthesis of Intermediate 48-2

[0145]

[0146] Under nitrogen atmosphere, intermediate 48-1 (2.56 g, 7.3 mmol), 9-phenanthrene boronic acid (1.36 g, 6 mmol), tetrakis(triphenylphosphine)palladium (0.21 g, 0.18 mmol) and potassium carbonate (4.55 g, 12.2 mmol) were added to a four-necked reaction flask, 50 mL of tetrahydrofuran and 15 mL of water were added, and refluxed for 2 hours. The reaction solution was cooled to room temperature, extracted with ethyl acetate, and the organic phase was concentrated and passed through a chromatography column (developing solvent was n-hexane: ethyl acetate volume ratio = 1:3). Thus, a white solid of intermediate 48-2 (2.0 g, yield 67%) was obtained.

[0147] LC-MS(APCI):490.31(M+H) + .

[0148] 3. Synthesis of Compound 48

[0149]

[0150] Under nitrogen atmosphere, intermediate 48-2 (4.6 g, 94 mmol), 2-pyridine boronic acid (1.2 g, 9.9 mmol), [1,1'bis(diphenylphosphino)ferrocene]dichloropalladium (0.20 g, 0.28 mmol) and potassium carbonate (2.59 g, 18 mmol) were added to a four-necked reaction flask, 1,4-dioxane 60 mL was added, and refluxed for 2 hours. The reaction solution was cooled to room temperature, extracted with dichloromethane, and the organic phase was concentrated and passed through a chromatography column (n-hexane: ethyl acetate volume ratio = 1: 2). Thus, a white solid of compound 48 (3.4 g, yield 68%) was obtained.

[0151] LC-MS(APCI):533.38(M+H) + .

[0152] 1 HNMR(400MHz,MethyleneChloride-d2)δ8.81(dd,1H),8.79–8.70(m,2H),8.67(ddd,1 H),8.49(dt,1H),8.17(dd,1H),8.02–7.93(m,3H),7.86–7.50(m,15H),7.34(ddd,1H).

[0153] Compound Example 3

[0154] 1. Synthesis of Intermediate 84-1

[0155]

[0156] In a 1L four-necked bottle, 1-bromo-3-chloro-5-iodobenzene (50.00 g, 157.55 mmol), 9-phenanthreneboric acid (35.00 g, 157.55 mmol), potassium carbonate (43.55 g, 315.10 mmol), tetrakis(triphenylphosphine)palladium (1.82 g, 1.57 mmol), 400 mL of tetrahydrofuran, and 100 mL of water were added in sequence, and after nitrogen replacement, reflux reaction was carried out for 2 hours. After the reaction was completed, the liquid was extracted with DCM and water, and the intermediate 84-1 (52 g, yield 90%) was obtained by column chromatography (eluted with n-hexane).

[0157] LC-MS(APCI):[M+H] + =367.12.

[0158] 2. Synthesis of Intermediate 84-2

[0159]

[0160] In a 1L four-necked flask, intermediate 84-1 (52 g, 141.43 mmol) and tetrahydrofuran 500 mL were added. After nitrogen replacement, n-butyl lithium in n-hexane solution (155.57 mmol) was injected into the system at ultra-low temperature (-78 ° C). After the reaction was kept warm for 2 hours, 200 mL of 2-bromopyrimidine in tetrahydrofuran solution (24.74 g in 200 mL THF, 155.57 mmol) was injected into the system. After the reaction was kept warm for 2 hours, 200 mL of water was quenched, and after dichloromethane extraction, column chromatography (n-hexane: dichloromethane volume ratio = 10: 1) was used to obtain intermediate 84-2 (45 g, yield 87%).

[0161] LC-MS(APCI):[M+H] + =367.35.

[0162] 3. Synthesis of Compound 84

[0163]

[0164] Into a 1L four-necked bottle, add intermediate 84-2 (45g, 122.66mmol), diphenylphosphine oxide (37.20g, 183.99mmol), potassium carbonate (33.90g, 245.32mmol), bis(triphenylphosphine) nickel dichloride (4.00g, 6.133mmol), tetrahydrofuran 500mL, nitrogen replacement, reflux reaction for 3 hours. After the reaction is completed, filter, concentrate the filtrate and column chromatography (eluted with dichloromethane) to obtain compound 84 (59g, yield 90%)

[0165] LC-MS(APCI):[M+H] + =533.42.

[0166] 1 H NMR(400MHz,MethyleneChloride-d2)δ8.93–8.84(m,2H),8.83–8.71(m,4H),7.98–7.89(m,2H),7.87–7.75(m,6H),7.74–7.48(m,10H),7.25(td,1H).

[0167] Device Preparation Example

[0168] Application Example 1 illustrates the application effect of the compound of the present invention as an N-type charge generation layer in a device.

[0169] Application Example 1

[0170] Device Comparison Example 1

[0171] This embodiment provides an organic electroluminescent element, such as Figure 1 As shown, it includes a stacked first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a light-emitting layer 4, an electron transport layer 5, an N-type charge generation layer 6, a P-type charge generation layer 7, a hole transport layer 8, a light-emitting layer 9, an electron transport layer 10, an electron injection layer 11 and a second electrode layer 12, wherein the hole injection layer 2, the hole transport layer 3, the light-emitting layer 4 and the electron transport layer 5 are the first light-emitting unit 100, and the hole transport layer 8, the light-emitting layer 9, the electron transport layer 10 and the electron injection layer 11 are the second light-emitting unit 200.

[0172] The specific component structure is:

[0173] ITO(100nm) / NPD:F4-TCNQ(10%)(10nm) / NPD(120nm) / BH:BD(3%)(20nm) / TmPyPB(10nm) / Bphen:Li(2%)( 10nm) / NPD:F4-TCNQ(10%)(20nm) / NPD(20nm) / BH:BD(3%)(20nm) / Alq3(10nm) / LiF(0.5nm) / Al(200nm).

[0174] Component preparation process:

[0175] The bottom-emitting glass substrate used in this embodiment was purchased from Guangdong Xinli Display Technology Co., Ltd., and 100 nm ITO was used as the first electrode layer 1. First, the bottom-emitting glass substrate was cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol in sequence, and then the bottom-emitting glass substrate was baked at 180 degrees Celsius for 30 minutes to dry it.

[0176] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10 -8Each organic layer is deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second under the condition of 1000 Å / s. Among them, F4-TCNQ (mass content 10%) is doped into NPD to form a thickness of 10nm as a hole injection layer. NPD is formed to a thickness of 120nm as a hole transport layer, and the anthracene main body ADN (9,10-di(naphtha-2-yl-) anthracene) is doped with a 3% mass content of pyrene dopant 1,6-bis(diphenylamino)pyrene to form a blue light-emitting layer with a thickness of 20nm. TmPyPB is formed to a thickness of 10nm as the first electron transport layer, and the comparison compound Ref1 is doped with 2% mass content of Li to form an N-type charge generation layer 6 with a thickness of 10nm. F4-TCNQ with a mass content of 10% is doped on NPD to form a P-type charge generation layer with a thickness of 20nm. The layers are formed, NPD is formed to a thickness of 20nm as a hole transport layer, 1,6-bis(diphenylamino)pyrene, a pyrene dopant with a mass content of 3%, is doped on the anthracene main body ADN (9,10-di(naphtha-2-yl-)anthracene) to form a blue light-emitting layer with a thickness of 20nm, Alq3(Tris-(8-hydroxyquinolinato)aluminum) is formed to a thickness of 10nm as a second electron transport layer, LiF is formed to a thickness of 0.5nm as an electron injection layer, and Al is formed to a thickness of 200nm as a cathode.

[0177] Finally, the component was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the component, which was recorded as organic electronic component 1.

[0178]

[0179]

[0180] Synthesis of comparative compounds

[0181]

[0182] Under nitrogen atmosphere, 2,3,4,5-tetraphenyl-pyrrole (30.0 g, 80.8 mmol) was put into a four-necked bottle, and about 300 mL of THF was added to dissolve. The temperature in the system was lowered to below -78°C with liquid nitrogen, and then n-butyl lithium was slowly dripped in, and stirred at low temperature for 1 hour after the dripping was completed. Diphenylphosphine chloride was then slowly dripped in, and stirred at low temperature for 1 hour after the dripping was completed, and then the cold bath was removed and stirred at room temperature for 2 hours. Extracted with DCM and H2O, the organic phases were combined and spin-dried. The crude product obtained above was purified by silica gel column chromatography (developing solvent was n-hexane: dichloromethane = 1:3), and then recrystallized from chlorobenzene to obtain a white comparison compound Ref1 (12.7 g, yield 28%).

[0183] 1 HNMR (400MHz, CD2CL2) δ7.42–7.32(m,4H),7.13–7.08(m,2H),7.07–7.00(m,8H),6.99–6.89(m,10H),6.86–6.77(m,6H).

[0184] LC-MS (APCI): 572.46 (M+H + ).

[0185] Device Example 1

[0186] Charge Generation Layer The N-type charge generation layer 6 was prepared by using the compound prepared in Example 1 of the present invention instead of the comparative compound material, and the organic electronic element 2 was prepared by the same method.

[0187] Device Example 2

[0188] Charge Generation Layer The N-type charge generation layer 6 was prepared by using the compound prepared in Example 2 of the present invention instead of the comparative compound material, and the organic electronic element 3 was prepared by the same method.

[0189] Device Example 3

[0190] Charge Generation Layer The N-type charge generation layer 6 was prepared by using the compound prepared in Example 3 of the present invention instead of the comparative compound material, and the organic electronic element 4 was prepared by the same method.

[0191] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30mA / cm 2 The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hour)) was measured.

[0192] The driving voltage and current efficiency are both at a current density of 15mA / cm 2 The following test results are shown in Table 1.

[0193] Table 1

[0194] Drive voltage, V Current efficiency, cd / A LT95,h Organic electronic components1 15.46 12.34 65 Organic Electronic Components2 7.06 17.44 71 Organic Electronic Components3 6.96 17.55 94 Organic Electronic Components4 7.20 17.69 97

[0195] In summary, the organic electroluminescent element prepared from the compound of the present invention has significantly lower driving voltage and improved current efficiency and service life than the comparative compound Ref1, and is therefore suitable as a material for an organic electroluminescent element.

[0196] Application Example 2 illustrates the application effect of the compound of the present invention as an electron transport layer in a device.

[0197] Application Example 2

[0198] Device Comparison Example 2

[0199] This embodiment provides an organic electroluminescent device, such as Figure 2 As shown, it includes a first electrode layer 110 , a hole injection layer 120 , a hole transport layer 130 , a light emitting layer 140 , an electron transport layer 150 , an electron injection layer 160 and a second electrode layer 170 .

[0200] The specific device structure is:

[0201] ITO(100nm) / NPD:F4-TCNQ(10%)(10nm) / NPD(120nm) / BH:BD(3%)(20nm) / Alq3:Liq(50%)(10nm) / LiF(0.5nm) / Al(200nm).

[0202] Device preparation process:

[0203] The bottom-emitting glass substrate used in this embodiment was purchased from Guangdong Xinli Display Technology Co., Ltd., and 100 nm ITO was used as the first electrode layer 110. First, the bottom-emitting glass substrate was cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol in sequence, and then the bottom-emitting glass substrate was baked at 180 degrees Celsius for 30 minutes to dry it.

[0204] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10 -8Each organic layer was deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second under the condition of 1000 Å / s. Among them, F4-TCNQ (2,3,5,6-Tetrafluoro-tetracyanoquinodimethane) with a mass content of 10% was doped on NPD to form a thickness of 10nm as a hole injection layer, NPD was formed to a thickness of 120nm as a hole transport layer, 1,6-bis (diphenylamino) pyrene, a pyrene dopant with a mass content of 3%, was doped on the anthracene main body ADN (9,10-di (naphtha-2-yl-) anthracene) to form a blue light emitting layer with a thickness of 20nm, Alq3 (Tris- (8-hydroxyquinolinato) aluminum) was doped with a mass content of 50% Liq to form an electron transport layer with a thickness of 10nm, LiF (Lithium Fluoride) was formed to a thickness of 0.5nm as an electron injection layer, and Al was formed to a thickness of 200nm as a cathode.

[0205] Finally, the device was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device, which was recorded as organic electronic component 5.

[0206] Device Example 4

[0207] The electron transport layer was prepared by using the compound prepared in Example 2 of the present invention instead of Alq3, and the organic electronic component 6 was prepared by the same method.

[0208] Test Results

[0209] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30mA / cm 2 The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hour)) was measured.

[0210] The driving voltage and current efficiency are both at a current density of 15mA / cm 2 The test results are shown in Table 2.

[0211] Table 2

[0212] Drive voltage, V Current efficiency, cd / A Life LT95, hours Organic electronic components5 5.44 5.38 14 Organic electronic components6 5.52 5.47 375

[0213] Compared with element 5, the organic electronic element using the compound of the present invention in the electron transport layer has lower driving voltage, higher current efficiency and longer service life. Therefore, the compound of the present invention can also be used as an electron transport layer material for making an organic electroluminescent element.

[0214] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0215] The above is a detailed introduction to a phosphine oxide compound and an organic electroluminescent device containing the compound provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified in a number of ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A phosphine oxide compound, characterized in that The compound has the structure shown in formula (1): Wherein, X is selected from CR or N, R is selected from hydrogen, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, L 1 -L 2 are each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group, R 1 -R 4 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, -L 1 R 1 , -L 2 R 2 Same or different, When substituted or unsubstituted, the substituent is selected from one or a combination of deuterium, halogen, cyano, C1-C10 alkyl, C6-C30 aryl, C3-C30 heteroaryl; The heteroatom of the heteroaryl group is selected from one or more of oxygen, sulfur and nitrogen.

2. The phosphine oxide compound according to claim 1, characterized in that: The R 3 , R 4 Selected from phenyl.

3. The phosphine oxide compound according to claim 1, characterized in that: Said X is selected from CH or N; When -L 1 R 1 When it is hydrogen, -L 2 R 2 Not hydrogen or deuterium; when -L 1 R 1 When it is deuterium, -L 2 R 2 Not hydrogen or deuterium.

4. The phosphine oxide compound according to claim 1, characterized in that: The L 1 , L 2 Each is independently selected from a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted substituted or unsubstituted fluoranthene, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxaline substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted indenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted fluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl.

5. The phosphine oxide compound according to claim 1, characterized in that: The R 1 , R 2 and each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted substituted or unsubstituted fluoranthene, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazine, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted indenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthroline, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzopyrenyl, substituted or unsubstituted substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzimidazolyl, or substituted or unsubstituted carbolyl.

6. The phosphine oxide compound according to claim 1, characterized in that The compound is selected from any of the following compounds No. 1-192:

7. An organic electroluminescent element, comprising a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, characterized in that: The organic layer has one or more organic layers, and at least one organic layer comprises the phosphine oxide compound according to any one of claims 1 to 6.

8. The organic electroluminescent element according to claim 7, characterized in that: The organic layer includes at least two light-emitting units, and the light-emitting unit includes at least one layer of a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer; A charge generation layer is included between the two light-emitting units, and the charge generation layer includes an N-type charge generation layer and a P-type charge generation layer; the N-type charge generation layer includes the phosphine oxide compound according to any one of claims 1-6.

9. The organic electroluminescent element according to claim 7, characterized in that: The organic layer comprises at least one of a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer; The electron transport layer comprises the phosphine oxide compound according to any one of claims 1 to 6.

10. An electronic device, comprising: One or more of a display, a monitor, and a lighting device, comprising the organic electroluminescent element according to claim 8 or 9; and a control unit for driving the display device.

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