A spirofluorene silicon compound and its electroluminescent application

Abstract

The present invention provides a spirofluorene silicon compound having a structure shown in Formula I. The spirofluorene silicon compound can be used as an electron transport layer in an organic photoelectric device to increase the electron transport rate, balance the electron and hole injection, and increase the efficiency and life of an OLED device.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescent materials, in particular to a spirofluorene silicon compound and its electroluminescent application. Background Art

[0002] The electron transport material used in traditional electroluminescent devices is Alq3, but the electron mobility of Alq3 is relatively low (about 10 -6 cm 2 / Vs), which makes the carrier transmission of the device unbalanced. With the commercialization of electroluminescent devices, people hope to obtain ETL materials with higher electron mobility and better performance. In this field, researchers have done a lot of exploratory work.

[0003] Designing and developing stable and efficient electron transport materials and / or electron injection materials that have both high electron mobility and high glass transition temperature and are effectively doped with metal Yb or Liq can reduce threshold voltage, improve device efficiency, and extend device life, which has very important practical application value. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a spirofluorene silicon compound and its electroluminescent application, which can effectively improve the luminous efficiency and life of the device.

[0005] The present invention provides a spirofluorene silicon compound having a structure shown in Formula I:

[0006]

[0007] Wherein, A and B are independently selected from substituted or unsubstituted aryl or heteroaryl;

[0008] L1 and L2 are independently selected from a single bond, a substituted or unsubstituted aryl or heteroaryl group;

[0009] Ar1, Ar2, Ar3, Ar4 are independently selected from H, D, cyano, nitro, amino, hydroxyl, halogen, substituted or unsubstituted alkyl, aryl or heteroaryl.

[0010] The present invention provides an organic light-emitting device, which comprises an anode, a cathode, and an organic thin film layer located between the anode and the cathode, wherein the organic thin film layer comprises an electron transport layer, and the electron transport layer contains at least one of the above-mentioned spirofluorene silicon compounds.

[0011] The present invention provides a display panel, comprising the above organic light-emitting device.

[0012] Compared with the prior art, the present invention provides a spirofluorene silicon compound having a structure shown in Formula I. The spirofluorene silicon compound can be used as an electron transport layer in an organic photoelectric device to increase the electron transport rate, balance the electron and hole injection, and increase the efficiency and life of the OLED device. DETAILED DESCRIPTION

[0013] The present invention provides a spirofluorene silicon compound having a structure shown in Formula I:

[0014]

[0015] Wherein, A and B are independently selected from substituted or unsubstituted aryl or heteroaryl;

[0016] L1 and L2 are independently selected from a single bond, a substituted or unsubstituted aryl or heteroaryl group;

[0017] Ar1, Ar2, Ar3, Ar4 are independently selected from H, D, cyano, nitro, amino, hydroxyl, halogen, substituted or unsubstituted alkyl, aryl or heteroaryl.

[0018] Optionally, A and B are independently selected from substituted or unsubstituted C6-C20 aryl or C3-C20 heteroaryl;

[0019] The heteroatom of the heteroaryl group is selected from one or more of N, O, S and Si.

[0020] Optionally, A and B are independently selected from any of the following:

[0021] 1) Substituted or unsubstituted monocyclic aromatic group;

[0022] 2) substituted or unsubstituted monocyclic heteroaryl;

[0023] 3) A condensed-ring aromatic group formed by condensing 2 to 3 substituted or unsubstituted monocyclic aromatic groups;

[0024] 4) a fused heteroaryl group formed by condensing 2 to 3 substituted or unsubstituted monocyclic aromatic groups and monocyclic heteroaryl groups;

[0025] 5) A fused heteroaryl group formed by condensing 2 to 3 substituted or unsubstituted monocyclic heteroaryl groups.

[0026] Optionally, the monocyclic aromatic group is a phenyl group;

[0027] The monocyclic heteroaryl group is a five-membered, six-membered or seven-membered monocyclic heteroaryl group;

[0028] The heteroatom of the heteroaryl group is selected from one or more of N, O and S.

[0029] Optionally, the monocyclic heteroaryl group is selected from one or more of pyrrolyl, furanyl, thienyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, oxazolyl, thiazolyl, thiadiazolyl, triazole, tetrazole, pyridyl, pyranyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl.

[0030] Optionally, A and B are independently selected from substituted or unsubstituted phenyl, pyrrolyl, furanyl, thienyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, oxazolyl, thiazolyl, triazole, tetrazole, pyridyl, pyranyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazine, naphthyl, quinolyl, quinoxalinyl, isoquinolyl, quinazolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, imidazopyrimidinyl, 4-azabenzimidazolyl, 5-azabenzimidazolyl, 4,7-azabenzimidazolyl, benzothiadiazolyl, benzotriazolyl, anthracenyl, phenanthryl, acridinyl, carbazolyl, fluorenyl, dibenzofuranyl or dibenzothienyl.

[0031] Optionally, the spirofluorene silicon compound has a structure shown in Formula II or Formula III:

[0032]

[0033] Wherein, M1 and M2 are independently selected from C or N.

[0034] Optionally, A is substituted or unsubstituted phenyl, pyrrolyl, furanyl, thienyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, oxazolyl, thiazolyl, triazole, tetrazole, pyridyl, pyranyl, pyrimidinyl, pyridazinyl, pyrazinyl or triazinyl.

[0035] Optionally, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C20 aryl group or a C3-C20 heteroaryl group;

[0036] The heteroatom of the heteroaryl group is selected from one or more of N, O, S and Si.

[0037] Optionally, L1 and L2 are independently selected from a single bond, or any of the following:

[0038] 1) Substituted or unsubstituted monocyclic aromatic group;

[0039] 2) substituted or unsubstituted monocyclic heteroaryl;

[0040] 3) A condensed-ring aromatic group formed by condensing 2 to 3 substituted or unsubstituted monocyclic aromatic groups;

[0041] 4) a fused heteroaryl group formed by condensing 2 to 3 substituted or unsubstituted monocyclic aromatic groups and monocyclic heteroaryl groups;

[0042] 5) A fused heteroaryl group formed by condensing 2 to 3 substituted or unsubstituted monocyclic heteroaryl groups.

[0043] Optionally, the monocyclic aromatic group is a phenyl group;

[0044] The monocyclic heteroaryl group is selected from one or more of pyrrolyl, furanyl, thienyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, oxazolyl, thiazolyl, thiadiazolyl, triazole, tetrazole, pyridyl, pyranyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl.

[0045] Optionally, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted phenyl, a pyrrolyl, a furyl, a thienyl, an imidazolyl, a pyrazolyl, an isothiazolyl, an isoxazolyl, an oxazolyl, a thiazolyl, a triazole, a tetrazole, a pyridyl, a pyranyl, a pyrimidinyl, a pyridazinyl, a pyrazinyl, a triazine, a naphthyl, a quinolyl, a quinoxalinyl, an isoquinolyl, a quinazolinyl, a benzimidazolyl, a benzothiazolyl, a benzoxazolyl, an imidazopyrimidinyl, a 4-azabenzimidazolyl, a 5-azabenzimidazolyl, a 4,7-azabenzimidazolyl, a benzothiadiazolyl, a benzotriazolyl, anthracenyl, a phenanthrenyl, a 1-azaphenanthrenyl, a 1,10-diazaphenanthrenyl, an acridinyl, a carbazolyl, a fluorenyl, a dibenzofuranyl or a dibenzothienyl.

[0046] Optionally, Ar1, Ar2, Ar3, and Ar4 are independently selected from H, D, cyano, nitro, amino, hydroxyl, halogen, substituted or unsubstituted C1-C10 alkyl, C6-C20 aryl, or C3-C20 heteroaryl;

[0047] The heteroatom of the heteroaryl group is selected from one or more of N, O, S and Si.

[0048] Optionally, Ar1, Ar2, Ar3, Ar4 are independently selected from H, D, cyano, nitro, amino, hydroxyl, halogen, substituted or unsubstituted C1-C6 alkyl, or any of the following:

[0049] 1) Substituted or unsubstituted monocyclic aromatic group;

[0050] 2) substituted or unsubstituted monocyclic heteroaryl;

[0051] 3) A condensed-ring aromatic group formed by condensing 2 to 3 substituted or unsubstituted monocyclic aromatic groups;

[0052] 4) a fused heteroaryl group formed by condensing 2 to 3 substituted or unsubstituted monocyclic aromatic groups and monocyclic heteroaryl groups;

[0053] 5) A fused heteroaryl group formed by condensing 2 to 3 substituted or unsubstituted monocyclic heteroaryl groups.

[0054] Optionally, Ar1, Ar2, Ar3, Ar4 are independently selected from H, D, cyano, nitro, amino, hydroxyl, F, Cl, Br, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, phenyl, pyrrolyl, furanyl, thienyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, oxazolyl, thiazolyl, triazole, tetrazole, pyridyl, pyranyl, pyrimidine 1-azaphenanthrenyl, 1,10-diazaphenanthrenyl, 1-oxaphenanthrenyl, 1,2-diazaphenanthrenyl, 1,3-dinitrophenyl, 1,4-dinitrophenyl, 1,6-dinitrophenyl, 1,8 ...

[0055] Optionally, the substituents of A, B, L1, L2, Ar1, Ar2, Ar3, and Ar4 are independently selected from D, cyano, nitro, amino, hydroxyl, halogen, substituted or unsubstituted alkyl, aryl, or heteroaryl.

[0056] Optionally, the substituents of A, B, L1, L2, Ar1, Ar2, Ar3, and Ar4 are independently selected from D, cyano, nitro, amino, hydroxyl, halogen, substituted or unsubstituted C1-C10 alkyl, C6-C20 aryl, or C3-C20 heteroaryl.

[0057] Optionally, the substituents of A, B, L1, L2, Ar1, Ar2, Ar3, and Ar4 are independently selected from D, cyano, nitro, amino, hydroxyl, F, Cl, Br, phenyl, biphenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazine, furanyl, thienyl, pyrrolyl, pyranyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, naphthyl, anthracenyl, phenanthrenyl, carbazolyl, fluorenyl, dibenzofuranyl, dibenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, or quinazolinyl.

[0058] The hydrogen atoms in the above substituents may be further substituted with a phenyl group.

[0059] Optionally, the spirofluorene silicon compound has any of the following structures:

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] The spirofluorene silicon compound provided by the present invention has a lower LUMO value, easier electron injection, wider LUMO distribution, easier electron transmission, and can increase the material Tg temperature, reduce the injection barrier, reduce the device operating voltage, increase the electron transmission rate, balance the electron and hole injection, and improve the device luminous efficiency and life.

[0070] The present invention provides an organic light-emitting device, which comprises an anode, a cathode, and an organic thin film layer located between the anode and the cathode, wherein the organic thin film layer comprises an electron transport layer, and the electron transport layer contains at least one of the above-mentioned spirofluorene silicon compounds.

[0071] The present invention provides a display panel, comprising the above organic light-emitting device.

[0072] The organic light-emitting device provided by the present invention can be an organic light-emitting device familiar to those skilled in the art. Optionally, the organic light-emitting device includes a substrate, an ITO anode, a first hole transport layer, a second hole transport layer, an electron blocking layer, a light-emitting layer, a first electron transport layer, a second electron transport layer, a cathode (magnesium-silver electrode, with a magnesium-silver mass ratio of 1:9) and a capping layer (CPL).

[0073] Optionally, the anode material of the organic light-emitting device can be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc. and their alloys; such as metal oxides such as indium oxide, zinc oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; such as conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), etc., in addition to the above materials that facilitate hole injection and their combinations, also include known materials suitable for being anodes.

[0074] Optionally, the cathode material of the organic light-emitting device can be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, etc. and their alloys; such as multilayer metal materials such as LiF / Al, LiO2 / Al, BaF2 / Al, etc.; in addition to the above materials and combinations thereof that facilitate electron injection, it also includes known materials suitable for the cathode.

[0075] Optionally, the organic photoelectric device, such as the organic thin film layer in the organic light-emitting device, has at least one light-emitting layer (EML) and may also include other functional layers, including a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a hole blocking layer (HBL), an electron transport layer (ETL), and an electron injection layer (EIL).

[0076] Optionally, the organic light-emitting device is prepared according to the following method:

[0077] An anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer.

[0078] Optionally, the organic thin layer may be formed by a known film-forming method such as evaporation, sputtering, spin coating, dipping, ion plating, etc.

[0079] The present invention provides a display device, comprising the above-mentioned display panel.

[0080] In the present invention, an organic light-emitting device (OLED device) can be used in a display device, wherein the organic light-emitting display device can be a mobile phone display, a computer display, a TV display, a smart watch display, a smart car display panel, a VR or AR helmet display, a display of various smart devices, etc.

[0081] The following will be described clearly and completely in conjunction with the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0082] Example 1 Preparation of substrate

[0083] Preparation of A2

[0084]

[0085] Under nitrogen flow, 1,2-dibromobenzene (23.4 g, 100 mmol), magnesium (2.4 g, 100 mmol) and 200 ml tetrahydrofuran were added and stirred for 1 hour. After the reaction solution was cooled to 0°C, a tetrahydrofuran solution (100 ml) containing trichlorophenylsilane (22.0 g, 104 mmol) was slowly added dropwise. The reaction solution was returned to room temperature and stirred for 3 hours. Solids were filtered off under nitrogen and the filtrate was concentrated under reduced pressure. The residue was separated by column chromatography to obtain 17.8 g M1-1 (55% yield).

[0086]

[0087] The preparation method of M1-2 is consistent with that of M1-1. According to the preparation method of M1-1, using the same molar ratio, 1,2-dibromobenzene is replaced by 1,3-dibromobenzene, and trichlorophenylsilane is replaced by M1-1.

[0088]

[0089] Under argon atmosphere, 1-(diethoxymethyl)-1H-imidazole (44.0 g, 200 mmol) and 500 ml THF were added to the container. At -40 ° C, n-butyl lithium (132 ml, 3.3 mmol, 2.5 M hexane) was added dropwise. The reaction mixture was stirred at -40 ° C for 20 minutes, and then a 500 ml THF solution of phenyldiisopropylsilyl chloride (73.5 g, 300 mmol) was added dropwise. The resulting mixture was warmed to room temperature, quenched (saturated NH4Cl), extracted with ethyl acetate, dried and concentrated. The residue was separated by column chromatography to obtain 69.2 g M1-3 (65% yield).

[0090]

[0091] K2CO3 (57.2 g, 210 mmol), CuI (38 mg, 20 mmol), all-6-amino-β-cyclodextrin (10 g, 8 mmol) and DMSO (100 ml) were added to the reactor. Then a solution of M1-3 (53.2 g, 100 mmol) in DMSO (100 ml) was added. Stir at 110° C. for 24 hours under a nitrogen atmosphere. After the reaction was completed, water (500 ml) was added to the reaction mixture. Then the mixture was extracted and dried and concentrated. The residue was purified by silica gel column chromatography to obtain 38.4 g M1-4 (85%).

[0092]

[0093] Under nitrogen atmosphere, compound 2,4-bis([1,1'-biphenyl]-3-yl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,5-triazine (3.6 g, 10 mmol) and M1-4 (4.5 g, 10 mmol) were completely dissolved in 100 ml of tetrahydrofuran, and PdP(Ph)3 (320 mg, 0.268 mmol) was added thereto to react for half an hour, followed by addition of K2CO3 (3.7 g, 53.7 mmol) dissolved in 20 ml of water, followed by heating and stirring for 7 hours. The reaction temperature was lowered to room temperature to complete the reaction, and then the K2CO3 solution was filtered to remove the K2CO3 solution and the filter residue was washed twice with tetrahydrofuran and ethyl acetate to obtain A2 (4.84 g, 80%).

[0094] Preparation of A21

[0095]

[0096] The preparation method of A21 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine is replaced with 2,4-bis([1,1′-biphenyl]-3-yl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine.

[0097] Preparation of A29

[0098]

[0099] The preparation method of A29 is consistent with that of A2. According to the preparation method of A2, 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine is replaced with 4′-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-2,2′:6′,2′-tripyridine in the same molar ratio.

[0100] Preparation of A76

[0101]

[0102] A solution of 6-bromo-1H-benzimidazole (19.6 g, 100 mmol) and benzenesulfonic acid (0.5 g, 3.2 mmol) in triethyl orthoformate (100 ml) was heated to reflux for 10 hours and then slowly distilled for 2 hours.

[0103] The product M2-1 (19.4 g, 65%) was isolated by fractional distillation.

[0104]

[0105] The preparation method of M2-2 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M2-1.

[0106]

[0107] The preparation method of M2-3 is consistent with that of M1-3. According to the preparation method of M1-3, using the same molar ratio, 1-(diethoxymethyl)-1H-imidazole is replaced by M2-2, and M1-2 is replaced by 1-bromo-2-(chlorodiphenylsilyl)benzene.

[0108]

[0109] The preparation method of A76 is consistent with that of M1-4. According to the preparation method of M1-4, the same molar ratio is used and M1-3 is replaced by M2-3.

[0110] Preparation of A80

[0111]

[0112] The preparation method of A80 is the same as that of A76.

[0113] Preparation of A81

[0114]

[0115] The preparation method of M3-1 is consistent with that of M1-1. According to the preparation method of M1-1, the same molar ratio is used, and 1,2-dibromobenzene is replaced by 1,2,3-tribromobenzene, and trichlorophenylsilane is replaced by dichlorodiphenylsilane.

[0116]

[0117] The preparation method of M3-2 is consistent with that of M1-3. According to the preparation method of M1-3, use the same molar ratio and replace M1-2 with M3-1.

[0118]

[0119] The preparation method of M3-3 is consistent with that of M1-4. According to the preparation method of M1-4, use the same molar ratio and replace M1-3 with M3-2.

[0120]

[0121] The preparation method of A81 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M3-3, and 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine is replaced by 4′-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-2,2′:6′,2′-tripyridine.

[0122] Preparation of B2

[0123]

[0124] The preparation method of M4-1 is the same as that of M1-2.

[0125]

[0126] Indole (11.8 g, 100 mmol), M4-1 (62.4 g, 150 mmol), Ru3(CO) 12 (0.95 g, 1.5 mmol) and anhydrous toluene (1 L) and the mixture was reacted at 120°C for 12 hours under Ar atmosphere. Then it was diluted with CH2Cl2, silica was added to the flask and the solvent was evaporated. M4-2 (34.6 g, 65%) was obtained by column chromatography.

[0127]

[0128] M4-2 (53.2 g, 100 mmol), K2CO3 (20.7 g, 150 mmol) and The copper complex (0.45 g, 1 mmol) was dissolved in 300 ml of toluene and reacted at room temperature for 6 hours. After the reaction, the reaction solution was concentrated and directly separated by silica gel column chromatography to obtain M4-3 (42.9 g, 95%).

[0129]

[0130] The preparation method of B2 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M4-3.

[0131] Preparation of B21

[0132]

[0133] The preparation method of B21 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M4-3, and 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine is replaced by 2,4-bis([1,1′-biphenyl]-3-yl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine.

[0134] Preparation of B29

[0135]

[0136] The preparation method of B29 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M4-3, and 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine is replaced by 4′-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-2,2′:6′,2′-tripyridine.

[0137] Preparation of B76

[0138]

[0139] The preparation method of M5-1 is consistent with that of M1-1. According to the preparation method of M1-1, the same molar ratio is used and trichlorophenylsilane is replaced by chlorodiphenylsilane.

[0140]

[0141] The preparation method of M5-2 is consistent with that of M4-2. According to the preparation method of M4-2, using the same molar ratio, M4-1 is replaced by M5-1, and indole is replaced by 5-chloroindole.

[0142]

[0143] The preparation method of M5-3 is consistent with that of M4-3. According to the preparation method of M4-3, use the same molar ratio and replace M4-2 with M5-2.

[0144]

[0145] The preparation method of B76 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M5-3.

[0146] Preparation of B80

[0147]

[0148] The preparation method of B80 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M5-3, and 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine is replaced by 4′-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-2,2′:6′,2′-tripyridine.

[0149] Preparation of B81

[0150]

[0151] The preparation method of M5-1 is consistent with that of M1-1. According to the preparation method of M1-1, the same molar ratio is used, and 1,2-dibromobenzene is replaced with 1,2-dibromo-4-chlorobenzene, and trichlorophenylsilane is replaced with chlorodiphenylsilane.

[0152]

[0153] The preparation method of M6-2 is consistent with that of M4-2. According to the preparation method of M4-2, the same molar ratio is used and M4-1 is replaced by M6-1.

[0154]

[0155] The preparation method of M6-3 is consistent with that of M4-3. According to the preparation method of M4-3, the same molar ratio is used and M4-2 is replaced by M6-2.

[0156]

[0157] The preparation method of B81 is consistent with that of A2. According to the preparation method of A2, using the same molar ratio, M1-4 is replaced by M6-3, and 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-1,3,5-triazine is replaced by 4′-(4,4,5,5-tetramethyl-1,3,2-dioxybenzofuran-2-yl)-2,2′:6′,2′-tripyridine.

[0158] The compounds in the above examples were identified by matrix-assisted laser desorption ionization time-of-flight mass spectrometry and elemental analysis, and the results are shown in Table 1 below.

[0159] Table 1

[0160]

[0161]

[0162] Using density functional theory (DFT), for the organic compounds provided by the present invention, the distribution of molecular frontier orbitals HOMO and LUMO was optimized and calculated at the B3LYP / 6-31G(d) calculation level by using Gaussian09 program package (Gaussian Inc.), and the singlet energy level E of the compound molecule was simulated and calculated based on time-dependent density functional theory (TDDFT). S and triplet energy level E T , the results are shown in Table 2.

[0163] Table 2

[0164]

[0165] Comparative Example 1

[0166] ITO (indium tin oxide) is used The glass substrate coated with a film of thickness of 1000 nm was placed in distilled water dissolved with detergent and washed with ultrasound. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes. After the distilled water washing was completed, ultrasonic washing was performed with a solvent of isopropanol, acetone, and methanol, and after drying, it was transported to a plasma cleaning machine. In addition, the above substrate was cleaned for 5 minutes using oxygen plasma, and then the substrate was transported to a vacuum evaporation machine.

[0167] On the ITO transparent electrode prepared above, the following compounds HI are deposited in sequence by thermal vacuum deposition: and HAT On the hole injection layer, the following chemical formula HT Then vacuum evaporation of EB As an electron blocking layer.

[0168] Next, on the electron blocking layer, the following compounds [BH] and [BD] were coated at a weight ratio of 96:4 and a film thickness of The light emitting layer is formed by vacuum deposition.

[0169] On the above-mentioned light-emitting layer, HB as a hole blocking layer was vacuum deposited Then, ET and Liq were vacuum-deposited at a weight ratio of 1:1. The Liq compound was then vacuum deposited onto On the electron injection layer, magnesium and silver are sequentially deposited in a weight ratio of 10:1 to a thickness of The thickness of aluminum is A cathode is formed, thereby manufacturing an organic light emitting diode.

[0170]

[0171] Examples 1-1 to 1-12 were prepared by the same method as Comparative Example 1, except that the compounds shown in Table 3 were used as electron transport layer materials, and corresponding light-emitting devices were manufactured.

[0172] For the above organic light emitting device, at 10mA / cm 2 The driving voltage and luminous efficiency were measured at a current density of 20 mA / cm 2 The time required for the luminance to reach 95% of the initial luminance (LT95) was measured at a current density of . The results are shown in Table 3 below.

[0173] Table 3

[0174] name Electron transport layer Voltage (V) Current efficiency (cd / A) LT95(h) Comparative Example HB 5.14 4.12 94 Experimental Example 1-1 A2 4.92 5.18 125 Experimental Example 1-2 A21 5.08 4.95 121 Experimental Examples 1-3 A29 5.11 5.06 119 Experimental Examples 1-4 A76 5.09 4.55 116 Experimental Examples 1-5 A80 5.10 4.67 112 Experimental Examples 1-6 A81 4.99 4.72 114 Experimental Examples 1-7 B2 4.88 5.30 118 Experimental Examples 1-8 B21 5.04 5.07 115 Experimental Example 1-9 B29 5.07 5.18 112 Experimental Example 1-10 B76 5.05 4.67 109 Experimental Example 1-11 B80 5.06 4.79 105 Experimental Example 1-12 B81 4.95 4.84 107

[0175] Examples 2-1 to 2-12 were prepared in the same manner as in Comparative Example 1, except that the compounds shown in Table 4 were used as hole blocking layer materials. 2 The driving voltage and luminous efficiency were measured at a current density of 20 mA / cm 2 The time required for the luminance to reach 95% of the initial luminance (LT95) was measured at a current density of . The results are shown in Table 4 below.

[0176] Table 4

[0177]

[0178]

[0179] As shown in Tables 3 and 4, the organic light-emitting devices of the examples partially using the compounds of the present disclosure as hole blocking layer and electron transport layer materials exhibited excellent device characteristics compared to the organic light-emitting devices of the comparative examples using the compounds not included in Chemical Formula 1.

[0180] Generally, considering that the luminous efficiency and lifespan characteristics of an organic light-emitting device have a trade-off relationship with each other, it can be seen that compared with the device of the comparative example, it can be confirmed that when the type of substituent or atom in Chemical Formula 1 is changed, the electron transfer rate can be adjusted, and then the balance of the device carriers can be adjusted, showing a significant improvement.

[0181] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A spirofluorene silicon compound having a structure shown in Formula II or Formula III: in, M1 and M2 are independently selected from C or N; A is phenyl; L1 and L2 are both phenyl groups; Ar1, Ar2, Ar3, Ar4 are independently selected from substituted or unsubstituted pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl or triazinyl; The substituents of Ar1, Ar2, Ar3 and Ar4 are independently selected from phenyl, biphenyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl or triazinyl.

2. A spirofluorene silicon compound, characterized in that: Has any of the following structures:

3. An organic light-emitting device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode, wherein the organic thin film layer comprises an electron transport layer, and the electron transport layer contains at least one spirofluorene silicon compound as described in any one of claims 1-2.

4. A display panel comprising the organic light-emitting device according to claim 3.

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