WO2018108034A1 - Organic light-emitting device having double main-body structure - Google Patents

Abstract

An efficient double main-body organic light-emitting device, comprising: a hole transmission area (4), an electron transmission area (7) and a light-emitting layer (6), wherein the light-emitting layer (6) includes a first main body material represented by general formula (1) and a second main body material represented by general formula (2). The organic light-emitting device has the characteristics of high efficiency, long service life, low roll-off of efficiency and long high-temperature driving life.

Description

Organic light-emitting device with double body structure Technical field

The present invention relates to the field of semiconductor technology, and in particular to an organic electroluminescent device comprising a dual host structure.

Background technique

Organic Light Emission Diodes (OLED) device technology can be used to manufacture new display products, as well as to create new lighting products. It is expected to replace existing liquid crystal displays and fluorescent lighting, and has a wide application prospect. The OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device. As a current device, when a voltage is applied to the electrodes of both ends of the OLED light-emitting device, and the positive and negative charges in the film layer of the organic layer functional material are applied by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, OLED electroluminescence is generated.

At present, OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as television, but the luminous efficiency and service life of OLED devices are compared with actual product application requirements. Further improvement is needed.

The doping of host and guest in the light-emitting layer can effectively improve the efficiency of the OLED device, because the radiation transition of the triplet excitons of most organic molecules is forbidden, and the contribution to electroluminescence is small, by doping platinum. The organometallic complexes such as ruthenium and osmium can transfer the triplet excitons of the organic molecules to the triplet state of the metal complex, which greatly improves the efficiency of the organic light-emitting device. However, triplet excitons generate triplet-triplet annihilation (TTA) during the transfer process, resulting in energy loss, resulting in an efficiency drop in the organic light-emitting device. By using the double body, the triplet excitons can be dispersed on the two bodies, thereby reducing the TTA, thereby improving the efficiency of the organic light-emitting device and effectively reducing the efficiency roll-off.

Summary of the invention

In view of the problems existing in the conventional host-guest doping technology, the present invention provides a dual-body structure organic light-emitting device, which can effectively improve the efficiency and lifetime of the organic light-emitting device. The technical solution of the present invention is as follows:

The Applicant provides an organic light-emitting device comprising a hole transporting region, an electron transporting region and a light-emitting layer, characterized in that the light-emitting layer comprises a first host material represented by the general formula (1) and a general formula (2) ) the second host material indicated:

In the formula (1), R ₁ , R ₂ and R ₃ are each independently represented by a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a phenanolyl group, a benzimidazolyl group, a benzoxazolyl, pyridoindoleyl, quinoxalinyl or naphthyridyl group;

Ar _{1 is} represented by one of a phenyl group, a biphenyl group, a naphthyl group or a pyridyl group;

Expressed as a nitrogen-containing six-membered heterocyclic ring, n=1, 2 or 3;

In the formula (2), A ₁ , A ₂ , A ₃ and A ₄ are each independently represented by a phenyl group, a naphthyl group, a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group or a 2,6-naphthyridine group. 1,1,8-naphthyridinyl, 1,5-naphthyridinyl, 1,6-naphthyridinyl, 1,7-naphthyridinyl, 2,7-naphthyridinyl, quinoxalinyl, pyridazinyl Or one of a quinoxalinyl group or a porphyrin group;

X ₁ represents an oxygen atom, a sulfur atom, C(R ₉ )(R ₁₀ ), Si(R ₉ )(R ₁₀ ), P(R ₉ ), B(R ₉ ), P(=O)(R ₉ ) Or N-[(L ₃ )a ₃ -(R ₁₁ )b ₁₁ ];

a ₁ , a ₂ and a ₃ are independently represented as ₁ , ₂ , ₃ , 4 or 5; b ₄ , b ₅ , b ₆ , b ₇ , b ₈ and b ₁₁ are independently represented as 1, 2, 3 Or 4;

L ₁ , L ₂ and L ₃ are each independently represented by a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C6 group. -C60 aryl, substituted or unsubstituted C1-C60 heteroaryl, substituted or unsubstituted divalent non-aromatic fused polycyclic, substituted or unsubstituted divalent non-aromatic fused Any of a heteropolycyclic group;

R ₄ and R ₁₁ are each independently represented by a substituted or unsubstituted C3-C10 cycloalkyl, a substituted or unsubstituted C1-C10 heterocycloalkyl, a substituted or unsubstituted C6-C60. Aromatic, substituted or unsubstituted C1-C60 heteroaryl, substituted or unsubstituted divalent non-aromatic fused polycyclic, substituted or unsubstituted valent non-aromatic fused heteropolycyclic Any one of -N(Q ₁ )(Q ₂ ), -Si(Q ₃ )(Q ₄ )(Q ₅ ) or -B(Q ₆ )(Q ₇ );

Wherein Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ and Q ₇ are each independently represented by a hydrogen atom, a C1-C60 alkyl group, a C1-C60 alkoxy group, or a C6-C60 aryl group. a C1-C60 heteroaryl group, a monovalent non-aromatic fused polycyclic group or a monovalent non-aromatic fused heterocyclic group;

R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently represented by a hydrogen atom, a halogen atom, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amino group, Mercapto, fluorenyl, fluorenyl, carboxy or carboxylate, sulfonate or sulfonate, phosphate or phosphate, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2- Alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted Substituted C1-C10 heterocycloalkyl, substituted or unsubstituted C3-C60 cycloalkenyl, substituted or unsubstituted C1-C60 heterocycloalkenyl, substituted or unsubstituted C6-C60 aromatic a substituted, unsubstituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted one Any one of a non-aromatically fused polycyclic group, a substituted or unsubstituted monovalent non-aromatic fused heterocyclic group.

Preferably, in the formula (1)

The structure represented by the general formula (3), the general formula (4), the general formula (5), the general formula (6) or the general formula (7):

Wherein R ₁₂ and R ₁₃ are each independently represented by phenyl, biphenyl, naphthyl, pyridyl, quinolyl, isoquinolinyl, phenanolyl, benzimidazolyl, benzoxazolyl, pyridine. One of a mercapto group, a quinoxalinyl group or a naphthyridinyl group.

Preferably, in the compound represented by the formula (1)

Expressed as:

Any of them.

Preferably, the second host material is represented by the general formula (8):

Wherein A ₁ to A ₄ , X ₁ , L ₁ , a ₁ , R ₄ and b ₄ in the formula (8) are as defined in the formula (2).

Preferably, the second host material is represented by the general formula (9):

Among them, A ₁ , A ₄ , X ₁ , L ₁ , a ₁ , R ₄ and b _{4 in the} formula (9) are as defined in the formula (2).

Preferably, the specific structural formula of the compound represented by the general formula (1) is:

Any of them.

Preferably, the specific structural formula of the compound represented by the general formula (2) is:

Any of them.

Preferably, the luminescent layer further comprises a guest dopant. Preferably, the guest dopant is represented by the general formula (10):

Wherein M is one of metal platinum, that is, Pt, yttrium, Ir, yttrium, or copper, or Cu; and X ₂ , X ₃ , X ₄ and X ₅ are independently represented by oxygen, carbon, or nitrogen atoms. One; A ₅ and A ₆ are each independently represented as an aromatic group, A ₇ is an organic ligand; n ₁ = 0, 1, 2 or 3; n ₂ = 1, 2 or 3.

Preferably, the specific structural formula of the compound represented by the general formula (10) is:

Any of them.

Preferably, the hole transporting region includes one or more of a hole injection layer, a hole transport layer, a buffer layer, and an electron blocking layer. Preferably, the hole injection layer material is one of structural formulas (11), (12) or (13):

Wherein, in the formula (11), Er ₁ -Er ₃ are independently represented as one of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C1-C60 heteroaryl group; Er ₁ -Er ₃ can be the same or different;

In the general formula (12) and the general formula (13), Fr ₁ -Fr ₆ are each independently represented by a hydrogen atom, a nitrile group, a halogen, an amide group, an alkoxy group, an ester group, a nitro group, and a C1-C60 straight. One of a chain or branched alkyl substituted carbon atom, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C1-C60 heteroaryl group.

Preferably, the specific structural formula of the compound represented by the general formulae (11), (12) and (13) is:

Any of them.

Preferably, the hole transport layer material is a compound of a triarylamine group, and the structural formula is as shown in the formula (14):

Wherein, in the general formula (14), Ar ₂ , Ar ₃ and Ar ₄ are each independently represented by a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C1-C60 heteroaryl group; . Preferably, the specific structural formula of the compound represented by the general formula (14) is:

Any of them.

Preferably, the electron transporting region includes one or more of an electron injecting layer, an electron transporting layer, and a hole blocking layer. Preferably, the material of the electron injecting layer is one of lithium, a lithium salt or a phosphonium salt. More preferably, the lithium salt is lithium quinolate, lithium fluoride, lithium carbonate or lithium azide; the cerium salt is cerium fluoride, cerium carbonate, cerium chloride or cerium azide.

Preferably, the material of the electron transport layer is any one of the compounds represented by the following formula (15), (16), (17, (18) or (19):

General formula (15) Formula (16) Formula (17)

Wherein, Dr ₁ -Dr _{10 in the} general formulae (15), (16), (17), (18) and (19) are independently represented by a hydrogen atom, a substituted or unsubstituted C6-C60 aryl group, and a substitution. Or any of the unsubstituted C1-C60 heteroaryl groups.

Preferably, the specific structural formula of the compound represented by the general formulae (15), (16), (17), (18) and (19) is:

Any of them.

Preferably, the organic light emitting device includes a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, and a light emitting layer, and the light emitting layer includes a first body, a second body, and an object. Dopant.

Preferably, the mass ratio of the first body and the second body is between (1:99) and (99:1); the ratio of the mass of the guest dopant to the total mass of the first and second bodies is (0.5~) 20): between 100. More preferably, the mass ratio of the first body and the second body is 1:5 to 5:1; the ratio of the mass of the guest dopant to the total mass of the first and second bodies is 0.1 to 1:1.

The beneficial effects of the invention are:

The invention provides an organic light-emitting device with double body structure, which effectively solves the problems existing in the conventional host-guest doping technology. Conventional techniques can transfer triplet excitons of organic molecules to the triplet state of metal complexes by doping organometallic complexes such as platinum, rhodium, ruthenium, etc., greatly improving the efficiency of organic light-emitting devices, but triplet excitons Transferred The triplet-triplet annihilation (TTA) is generated in the process to cause energy loss, which causes the organic light-emitting device to produce an efficiency roll-off. By using the dual-body structure of the present invention, triplet excitons can be dispersed on two bodies, thereby reducing TTA, thereby improving the efficiency of the organic light-emitting device and effectively reducing the efficiency roll-off.

The first host material in the host material of the organic light-emitting device of the present invention adopts a molecule having a skeleton of ruthenium and a nitrogen-containing six-membered heterocyclic ring having a high glass transition temperature and molecular thermal stability, and suitable HOMO and LUMO energy. The higher Eg can effectively improve the photoelectric performance and lifetime of the organic light-emitting device. The dual-body organic light-emitting device of the invention has good application effects and has good industrialization prospects.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of a device of one embodiment of the present invention. It should be noted that the structure of FIG. 1 is only for the convenience of understanding the embodiments, and does not represent the entire structure of the present invention.

Wherein, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking/electron transport layer, 8 is The electron injection layer, 9 is a cathode reflective electrode layer.

detailed description

1 is a schematic structural view of an organic light emitting device according to an embodiment of the present invention. Referring to FIG. 1, the transparent substrate layer 1 may be a glass substrate or a plastic substrate having good mechanical strength, thermal stability, transparency, surface flatness, handling convenience, and water resistance.

The anode layer 2 can be made of a conductor having a high work function (specifically, 4.0 eV or more) to aid in hole injection. The anode may be a metal, a metal oxide and/or a conductive polymer such as nickel, platinum, vanadium, chromium, copper, zinc, gold or an alloy, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide. (IZO), poly(3-methylthiophene), poly(3,4-(extended ethyl-1,2-dioxy)thiophene), polypyrrole, and polyaniline, but are not limited thereto.

The cathode reflective electrode layer 9 can be made of a conductor having a low work function (specifically, 3.8 eV or less) to aid electron injection. The cathode may be a metal, a metal oxide and/or a conductive polymer such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver or the like; a multilayer structure such as LiF/Al, LiF/Ca LiO ₂ /Al, BaF ₂ /Ca, but is not limited thereto.

The hole transporting region may include a hole injection layer 3 (HIL), a hole transport layer 4 (HTL), a buffer layer (not shown in the drawings, but the organic light emitting device provided by the present application may include this layer) and electrons One or more of barrier layers 5 (EBL); the electron transport region includes one or more of a hole blocking layer (HBL) / an electron transport layer (ETL) 7 and an electron injection layer 8 (EIL). The hole transporting region may have a single layer structure formed of a single material, a single layer structure formed of a plurality of different materials, or a multilayer structure formed of a plurality of different materials. For example, the hole transporting region may be a single layer structure formed of a different material, or may have a structure of a hole injection layer/hole transport layer, a structure of a hole injection layer/hole transport layer/buffer layer, and hole injection. Structure of layer/buffer layer, structure of hole transport layer/buffer layer, structure of hole injection layer/hole transport layer/electron barrier layer or structure of hole transport layer/electron barrier layer, but hole transport region is not Limited to this.

The electron transport region may include one or more of a hole blocking layer (HBL) / an electron transport layer 7 (ETL) and an electron injection layer 8 (EIL). For example, the electron transporting region may have a structure of an electron transport layer/electron injection layer, a structure of a hole blocking layer/electron transport layer/electron injection layer, but is not limited thereto. The luminescent layer can comprise a host material and a guest dopant. The host material contains a first host represented by the general formula (1) and a second host represented by the general formula (2). The compound of the formula (1) can be synthesized according to the method shown below:

Wherein R ₁ , R ₂ and R ₃ are each a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a phenanolyl group, a benzimidazolyl group, a benzoxazolyl group, a pyridine group. One of a mercapto group, a quinoxaline group or a naphthyridinyl group;

The preparation method uses Br-Ar-Br as a raw material, obtains a Grignard reagent by Grignard reaction, and then reacts with 9-fluorenone to form a tertiary alcohol; then the tertiary alcohol and HR ₁ are subjected to a Friedel-Craft reaction to obtain a Brominated compounds, then

The compound was prepared by CC coupling. The above preparation method specifically includes the following steps:

1) Br-Ar-Br and magnesium powder as raw materials, the molar ratio of Br-Ar-Br and magnesium powder is 1:1, adding tetrahydrofuran, heating to 70 ° C under nitrogen atmosphere, refluxing reaction for 3-5 hours, no Magnesium powder remaining, the reaction is complete, forming a format reagent; the above tetrahydrofuran is preferably used in an amount of 1 g of Br-Ar-Br added to 3-6 mL of tetrahydrofuran;

2) Weighing 9-fluorenone in tetrahydrofuran, the 9-fluorenone and the Br-Ar-Br molar ratio is 1:1, and then adding the format reagent prepared in the step 1), after the dropwise addition, Heating to 60-70 ° C, refluxing reaction for 10-25 hours, a large amount of white salt precipitate formed, the reaction is completed, then the saturated NHCl ₄ solution is added dropwise, the format salt is converted into a tertiary alcohol; and then extracted with diethyl ether to obtain an extract The extract is dried over anhydrous sodium sulfate, and then de-hydrogenated to a fraction without distillation to obtain a crude product of a tertiary alcohol. The crude product of the obtained tertiary alcohol is purified by using a petroleum ether: dichloromethane mixed solvent over a neutral silica gel column. The alcohol purification product; preferably the above petroleum ether: dichloromethane volume ratio of 3:2; the tetrahydrofuran in the step 2) is preferably used in an amount of 4-8 mL of tetrahydrofuran per 1 g of 9-fluorenone; Add 1 g of tertiary alcohol to 5-10 mL of diethyl ether;

3) Weigh the solid tertiary alcohol purified product and R ₁ -H in a ratio of 1:2 equivalent, dissolved in dichloromethane, and the amount of the dichloromethane is 1 g of the solid tertiary alcohol purified product dissolved in 5-8 mL of dichloromethane. Further, a boron trifluoride·ethyl ether complex is further added dropwise at room temperature, and the molar ratio of the purified product of the solid tertiary alcohol to the boron trifluoride·diethyl ether complex is 1:1.5, the reaction is carried out for 30-60 minutes, and then ethanol is added. The mixture is quenched with water, then extracted with dichloromethane, dried over anhydrous sodium sulfate, and then evaporated to dryness to a fraction, petroleum ether over a neutral silica gel column, and recrystallized from a solvent mixture of ethanol and dichloromethane to obtain a monobromo compound; Preferably, the ethanol: dichloromethane mixed solvent has a volume ratio of ethanol to dichloromethane of 1:1;

4) with a brominated compound and a boric acid compound

As a raw material, toluene is dissolved, and the amount of the toluene is 1 g of a monobromo compound, and 30-50 mL of toluene is used, wherein the monobromo compound and the boric acid compound are used.

The molar ratio is 1: (1.2 ~ 1.5);

5) adding Pd(PPh ₃ ) ₄ and sodium carbonate to the final reaction system of step 4);

Wherein, preferably, the molar ratio of the Pd(PPh ₃ ) ₄ to the monobromo compound is (0.005 to 0.02): 1, and the molar ratio of the sodium carbonate to the monobromo compound is (1.5 to 3.0): ;

6) Under nitrogen protection, the mixed solution obtained in the step 5) is reacted at 95 to 110 ° C for 10 to 24 hours, naturally cooled to room temperature, and the reaction solution is filtered, and the filtrate is rotary-screwed to a solvent-free, neutral silica gel column. The target product was obtained.

In the present invention, the mass ratio of the first body and the second body of the light-emitting layer is between (1:99) and (99:1), preferably between (1:10) and (10:1); guest dopant The ratio of mass to total mass of the host is between (0.5 and 20): 100, preferably between (0.1 and 1): 10.

As the method of forming each layer of the organic light-emitting device of the present embodiment, vacuum evaporation, spin coating, drop casting, inkjet printing, laser printing, or LB film method can be employed.

When the film is formed by vacuum evaporation, it may be at a deposition temperature of about 100 ° C to about 500 ° C.

to

The range can be deposited at a rate for vacuum deposition. When the film is formed by spin coating, spin coating may be performed at a spin coating rate in the range of about 2000 rpm to about 5000 rpm and a temperature in the range of 20 ° C to 200 ° C.

In the organic light-emitting device of the present embodiment, the thickness of each of the layers of the film is not limited. Generally, if the film is too thin, defects such as pinholes are likely to occur, and if it is too thick, a high applied voltage is required and the efficiency is deteriorated. Therefore, a range of from 0.1 nm to 1000 nm is usually preferred.

The present invention will be further described in detail below with reference to the embodiments.

Example 1 Synthesis of Starting Material A1:

The synthetic route is as follows:

A 250 mL four-necked flask was charged with 15.6 g of 3,4'-dibromo-1,1'-biphenyl (0.05 mol) and 1.33 g of Mg powder (0.055 mol) in 60 mL of tetrahydrofuran under a nitrogen atmosphere. 70 ° C, reflux reaction for 4 hours, no magnesium powder remaining, the reaction is complete, the formation of reagents;

9.01 g of 9-fluorenone (0.05 mol) was dissolved in 50 ml of tetrahydrofuran, and the reagent of the above format was added dropwise, and reacted at 60 ° C for 24 hours to form a large amount of white precipitate. Finally, saturated NHCl _{4 was} added to convert the format salt into alcohol; after completion of the reaction, diethyl ether Extraction, drying and rotary evaporation, petroleum ether: dichloromethane mixed solvent (3:2) silica gel column purification to obtain a slightly yellow solid tertiary alcohol (yield: 91%); using DEI-MS to identify the compound, formula C ₂₅ H ₁₇ BrO, found [M+1] ⁺ = 413.02, calculated value 412.05;

16.5 g of the above tertiary alcohol (0.04 mol) and 6.24 g of benzene (0.08 mol) were dissolved in 100 mL of dichloromethane in an amount of 1:2 equivalent, and 8 mL of boron trifluoride·ethyl ether complex was added dropwise at room temperature, and the reaction was carried out. After a minute, the reaction was quenched by the addition of 20 mL of ethanol and 20 mL of water, extracted with dichloromethane (20 mL*3), and then evaporated to dryness, purified from petroleum ether silica gel column, recrystallized from ethanol: methylene chloride, yield 72%; using DEI - MS to identify the compound, m.p. C ₃₁ H ₂₁ Br, </ ^RTI ><RTIgt;

Example 2 Synthesis of Starting Material A2:

The starting material A2 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 1,4-dibromobenzene was used instead of 3,4'-dibromo-1,1'-biphenyl, and the third step was used in the reaction. Benzene instead of benzene;

The compound was identified using DEI-MS, mp. C ₃₁ H ₂₁ Br, </ ^RTI ><RTIgt;

Example 3 Synthesis of Starting Material A3:

Starting material A3 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 1,4-dibromobenzene was used in place of 3,4'-dibromo-1,1'-biphenyl; DEI-MS was used to identify the Compound: C ₂₅ H ₁₇ Br, calc. [M+1] ⁺ = 397.11.

Example 4 Synthesis of Starting Material A4:

Raw material A4 was prepared according to the synthesis method of starting material A1 in Example 1, except that biphenyl was used instead of benzene in the third step reaction; DEI-MS was used to identify the compound, molecular formula C ₃₇ H ₂₅ Br, detection value [M+ 1] ⁺ = 549.08, calculated 548.11.

Example 5 Synthesis of Starting Material A5:

The starting material A5 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 4,4'-dibromo-1,1'-biphenyl was used instead of 3,4'-dibromo-1,1'-biphenyl. ; DEI-MS using the identified compound, the molecular formula C ₃₁ H ₂₁ Br, detected value ^{[M + 1] + = 473.15} , 472.08 calc.

Example 6 Synthesis of Starting Material A6:

The starting material A2 was prepared according to the synthesis method of the starting material A1 in Example 1, except that 1,4-dibromobenzene was used instead of 3,4'-dibromo-1,1'-biphenyl, and the pyridine was used in the third step. Instead of benzene; DEI-MS using the identified compound, the molecular formula C ₂₄ H ₁₆ BrN, the detected value ^{[M + 1] + = 397.98} , 397.05 calc.

Synthesis of Compound 3 of Example 7:

A 250 mL four-necked flask was charged with 0.01 mol of raw material A3, 0.012 mol of raw material B1, 0.02 mol of sodium carbonate, 1 × 10 ^-4 mol of Pd(PPh ₃ ) ₄ , 150 mL of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was completed; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain a target product with a purity of 99.4% and a yield of 77.5%.

Elemental analysis structure (Molecular formula C ₄₀ H ₂₇ N ₃ ): Theory C, 87.40; H, 4.95; N, 7.64; Tests: C, 87.41; H, 4.95; N, 7.63. HPLC-MS: The material had a molecular weight of 549.22 and a molecular weight of 549.45.

Synthesis of Compound 5 of Example 8:

A 250 mL four-necked flask was charged with 0.01 mol of raw material A1, 0.012 mol of raw material B3, 0.02 mol of sodium carbonate, 1 × 10 ^-4 mol of Pd(PPh ₃ ) ₄ , 150 mL of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was complete; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain the desired product, purity 99.3%, yield 78.1%.

Elemental Analysis Structure (Molecular Formula C ₄₈ H ₃₃ N): Theory C, 92.42; H, 5.33; N, 2.25; </ RTI> C, 92.40; H, 5.34; N, 2.26. HPLC-MS: The material had a molecular weight of 623.26 and a molecular weight of 623.51.

Synthesis of Compound 7 of Example 9:

A 250 mL four-necked flask was charged with 0.01 mol of raw material A2, 0.012 mol of raw material B3, 0.02 mol of sodium carbonate, 1 × 10 ^-4 mol of Pd(PPh ₃ ) ₄ , 150 mL of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was completed; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain a target product with a purity of 99.5% and a yield of 74.3%.

Elemental Analysis Structure (Molecular Formula C ₄₈ H ₃₃ N): Theory C, 92.42; H, 5.33; N, 2.25; Tests: C, 92.43; H, 5.32; N, 2.25. HPLC-MS: The material had a molecular weight of 623.26 and a molecular weight of 623.53.

Synthesis of Compound 28 of Example 10:

A 250 mL four-necked flask was charged with 0.01 mol of raw material A4, 0.012 mol of raw material C2, 0.02 mol of sodium carbonate, 1 × 10 ^-4 mol of Pd(PPh ₃ ) ₄ , 150 mL of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was completed; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain the desired product, purity 99.1%, yield 65.1%.

Elemental Analysis Structure (Molecular Formula C ₅₃ H ₃₆ N ₂ ): Theory C, 90.83; H, 5.18; N, 4.40; Tests: C, 90.81; H, 5.17; N, 4.02. HPLC-MS: The material had a molecular weight of 700.29 and a molecular weight of 700.55.

Synthesis of Compound 35 of Example 11:

250 mL four-necked flask, 0.01 mol of raw material A5, 0.012 mol of raw material C1, 0.02 mol of sodium carbonate, 1 × 10 ^-4 mol of Pd(PPh ₃ ) ₄ , 150 mL of toluene, heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was complete; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain a target product with a purity of 99.4% and a yield of 71.7%.

Elemental analysis structure (Molecular formula C ₄₅ H ₃₀ N ₄ ): Theory C, 86.24; H, 4.82; N, 8.94; Tests: C, 86.22; H, 4.83; N, 8.95. HPLC-MS: The material had a molecular weight of 626.25 and a molecular weight of 626.52.

Synthesis of Compound 42 of Example 12:

Prepared according to the synthesis method of compound 7 in Example 10, except that the raw material C3 is used instead of the raw material B3;

Elemental analysis structure (Molecular formula C ₄₇ H ₃₂ N ₂ ): Theory C, 90.35; H, 5.16; N, 4.48; Tests: C, 90.36; H, 5.17; N, 4.47. HPLC-MS: The material had a molecular weight of 624.26 and a molecular weight of 624.53.

Synthesis of Compound 53 of Example 13:

Prepared according to the synthesis method of compound 7 in Example 10, except that the raw material D1 is used instead of the raw material B3;

Elemental analysis structure (Formula C ₄₆ H ₃₁ N _3): Theory C, 88.29; H, 4.99; N, 6.72; test value: C, 88.27; H, 5.00 ; N, 6.73. HPLC-MS: The material had a molecular weight of 625.25 and a molecular weight of 625.59.

Synthesis of Compound 58 of Example 14:

A 250 mL four-necked flask was charged with 0.01 mol of raw material A6, 0.012 mol of raw material D1, 0.02 mol of sodium carbonate, 1 × 10 ^-4 mol of Pd(PPh ₃ ) ₄ , 150 mL of toluene, and heated to 105 ° C under a nitrogen atmosphere. After refluxing for 24 hours, the spot plate was sampled, indicating that there was no bromine residue remaining, and the reaction was complete; natural cooling, filtration, and the filtrate was rotary-steamed to a fraction without a fraction, and passed through a neutral silica gel column to obtain a target product with a purity of 99.4% and a yield of 71.7%.

Elemental analysis structure (Molecular formula C ₃₉ H ₂₆ N ₄ ): Theory C, 85.07; H, 4.76; N, 10.17; Tests: C, 85.07; H, 4.75; N, 10.18. HPLC-MS: The material had a molecular weight of 550.22 and a molecular weight of 550.47.

Hereinafter, the organic light-emitting device of the present invention will be described in detail by way of Examples 15-30 and Device Comparative Examples 1-11, and the performance test results of the devices obtained in the respective examples are shown in Table 2.

Example 15

The examples use ITO as the anode, Al as the cathode, compound DP-1 as the guest material, compound HI-1 as the hole injecting layer material, compound HT-14 as the hole transporting layer and electron blocking layer material, and compound ET-14 as Electron transport layer material, LiF as electron injection layer material. The specific production steps are as follows:

a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively, ultrasonically cleaning with deionized water, acetone, ethanol for 15 minutes, and then treating in a plasma cleaner for 2 minutes; b) passing through the ITO anode layer 2 The hole injection layer material HI-1 was deposited by vacuum evaporation to a thickness of 10 nm, and this layer was used as the hole injection layer 3; c) On the hole injection layer 3, the hole transport material HT was vapor-deposited by vacuum evaporation. -14, the thickness is 60 nm, the layer is hole transport 4; d) on the hole transport layer 4, the electron blocking layer material HT-14 is deposited by vacuum evaporation to a thickness of 20 nm, which is an electron blocking layer 5; e) evaporating the light-emitting layer 6 on the electron blocking layer 5, using the compound 3 and the compound 73 of the present invention as a host material, and DP-1 as a dopant material, and the mass ratio of the compound 3, 73 and DP-1 is 5:5:1, thickness: 30 nm; f) On the light-emitting layer 6, the electron transport material ET-14 is evaporated by vacuum evaporation to a thickness of 40 nm, and this organic material is used as a hole blocking/electron transport layer 7 Using g; on the hole blocking/electron transport layer 7, vacuum-evaporating the electron-injecting layer LiF to a thickness of 1 nm, the layer being Injection layer 8; H) on the electron injection layer 8, a cathode vacuum deposition Al (100nm), the reflective layer is a cathode electrode layer 9.

After completing the fabrication of the electroluminescent device according to the above steps, the IVL data, light decay lifetime and color coordinates (CIE) of the device were measured, and the results are shown in Table 2. The molecular organization of the relevant material is as follows:

Examples 16-30 and Comparative Examples 1-11

The fabrication processes of the devices of Examples 16-30 and Comparative Examples 1-11 and 15 were identical and the same was employed. The substrate material and the electrode material are also uniform in film thickness, except that the two bodies are different, and/or the mass ratios of the two bodies are different. See Table 1 for specific data.

Table 1

	First subject	Second subject	Guest material	Mass ratio
Example 16	Compound 3	Compound 73	Compound DP-1	7:3:1
Example 17	Compound 5	Compound 75	Compound DP-1	5:5:1
Example 18	Compound 5	Compound 75	Compound DP-1	7:3:1
Example 19	Compound 7	Compound 82	Compound DP-1	5:5:1
Example 20	Compound 7	Compound 82	Compound DP-1	7:3:1
Example 21	Compound 28	Compound 88	Compound DP-1	5:5:1
Example 22	Compound 28	Compound 88	Compound DP-1	7:3:1
Example 23	Compound 35	Compound 90	Compound DP-1	5:5:1
Example 24	Compound 35	Compound 90	Compound DP-1	7:3:1
Example 25	Compound 42	Compound 92	Compound DP-1	5:5:1
Example 26	Compound 42	Compound 92	Compound DP-1	7:3:1
Example 27	Compound 53	Compound 95	Compound DP-1	5:5:1
Example 28	Compound 53	Compound 95	Compound DP-1	7:3:1
Example 29	Compound 58	Compound 100	Compound DP-1	5:5:1
Example 30	Compound 58	Compound 100	Compound DP-1	7:3:1
Comparative example 1	Compound 3	-	Compound DP-1	10:0:1
Comparative example 2	-	Compound 73	Compound DP-1	0:10:1
Comparative example 3	Compound 7	-	Compound DP-1	10:0:1
Comparative example 4	-	Compound 75	Compound DP-1	0:10:1
Comparative Example 5	Compound 28	-	Compound DP-1	10:0:1
Comparative Example 6	-	Compound 88	Compound DP-1	0:10:1
Comparative Example 7	Compound 35	-	Compound DP-1	10:0:1
Comparative Example 8	-	Compound 92	Compound DP-1	0:10:1
Comparative Example 9	Compound 58	-	Compound DP-1	10:0:1
Comparative Example 10	Compound A	Compound B	Compound DP-1	5:5:1
Comparative Example 11	Compound A	Compound B	Compound DP-1	7:3:1

The structures of compounds A and B in the table are as follows:

The efficiency and lifetime data of the devices of the respective examples and comparative examples are shown in Table 2.

Table 2

It can be seen from the device data results of Table 2 that the dual-body organic light-emitting device of the present invention achieves a large improvement in both efficiency and lifetime relative to single-body devices and OLED devices of known materials.

In order to compare the efficiency degradation of different devices at high current densities, define the efficiency attenuation coefficient.

Representation, which represents the ratio between the difference between the maximum efficiency μ100 of the device and the maximum efficiency μm of the device at a driving current of 100 mA/cm ² and the maximum efficiency. The larger the value, the more severe the device's efficiency roll-off, and conversely, the problem that the device decays rapidly at high current densities is controlled. Efficiency decay coefficients were performed on Examples 15-30 and Comparative Examples 1-11, respectively.

The measurement results are shown in Table 3:

table 3

From the data of Table 3, it can be seen from the comparison of the efficiency attenuation coefficients of the examples and the comparative examples that the organic light-emitting device of the present invention can effectively reduce the efficiency roll-off.

The OLED devices prepared in Examples 15 to 30 and Comparative Examples 1 to 11 were tested at a high temperature driving life of 120 ° C. The results are shown in Table 4.

Table 4

As can be seen from the data in Table 4, the OLED device provided by the present invention has a very good high temperature driving life, while the life of a single body device and a known material device is significantly reduced at high temperatures.

It is understood that the specific examples described above are merely illustrative of the invention and are not intended to limit the invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (21)

1. An organic light-emitting device comprising a hole transporting region, an electron transporting region, and a light-emitting layer, wherein the light-emitting layer comprises a first host material represented by the general formula (1) and a general formula (2) Second body material:

   

   In the formula (1), R ₁ , R ₂ and R ₃ are each independently represented by a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a phenanolyl group, a benzimidazolyl group, a benzoxazolyl, pyridoindoleyl, quinoxalinyl or naphthyridyl group;

   Ar _{1 is} represented by one of a phenyl group, a biphenyl group, a naphthyl group or a pyridyl group;

   

   Expressed as a nitrogen-containing six-membered heterocyclic ring, n=1, 2 or 3;

   In the formula (2), A ₁ , A ₂ , A ₃ and A ₄ are each independently represented by a phenyl group, a naphthyl group, a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group or a 2,6-naphthyridine group. 1,1,8-naphthyridinyl, 1,5-naphthyridinyl, 1,6-naphthyridinyl, 1,7-naphthyridinyl, 2,7-naphthyridinyl, quinoxalinyl, pyridazinyl Or one of a quinoxalinyl group or a porphyrin group;

   X ₁ represents an oxygen atom, a sulfur atom, C(R ₉ )(R ₁₀ ), Si(R ₉ )(R ₁₀ ), P(R ₉ ), B(R ₉ ), P(=O)(R ₉ ) Or N-[(L ₃ )a ₃ -(R ₁₁ )b ₁₁ ];

   a ₁ , a ₂ and a ₃ are independently represented as ₁ , ₂ , ₃ , 4 or 5; b ₄ , b ₅ , b ₆ , b ₇ , b ₈ and b ₁₁ are independently represented as 1, 2, 3 Or 4;

   L ₁ , L ₂ and L ₃ are each independently represented by a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C6 group. -C60 aryl, substituted or unsubstituted C1-C60 heteroaryl, substituted or unsubstituted divalent non-aromatic fused polycyclic, substituted or unsubstituted divalent non-aromatic fused Any of a heteropolycyclic group;

   R ₄ and R ₁₁ are each independently represented by a substituted or unsubstituted C3-C10 cycloalkyl, a substituted or unsubstituted C1-C10 heterocycloalkyl, a substituted or unsubstituted C6-C60. Aromatic, substituted or unsubstituted C1-C60 heteroaryl, substituted or unsubstituted divalent non-aromatic fused polycyclic, substituted or unsubstituted valent non-aromatic fused heteropolycyclic Any one of -N(Q ₁ )(Q ₂ ), -Si(Q ₃ )(Q ₄ )(Q ₅ ) or -B(Q ₆ )(Q ₇ );

   Wherein Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ and Q ₇ are each independently represented by a hydrogen atom, a C1-C60 alkyl group, a C1-C60 alkoxy group, or a C6-C60 aryl group. a C1-C60 heteroaryl group, a monovalent non-aromatic fused polycyclic group or a monovalent non-aromatic fused heterocyclic group;

   R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently represented by a hydrogen atom, a halogen atom, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amino group, Mercapto, fluorenyl, fluorenyl, carboxy or carboxylate, sulfonate or sulfonate, phosphate or phosphate, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2- Alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted Substituted C1-C10 heterocycloalkyl, substituted or unsubstituted C3-C60 cycloalkenyl, substituted or unsubstituted C1-C60 heterocycloalkenyl, substituted or unsubstituted C6-C60 aromatic a substituted, unsubstituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted one Any one of a non-aromatically fused polycyclic group, a substituted or unsubstituted monovalent non-aromatic fused heterocyclic group.
2. The organic light-emitting device according to claim 1, wherein in the formula (1)

   

   The structure represented by the general formula (3), the general formula (4), the general formula (5), the general formula (6) or the general formula (7):

   

   Wherein R ₁₂ and R ₁₃ are each independently represented by phenyl, biphenyl, naphthyl, pyridyl, quinolyl, isoquinolinyl, phenanolyl, benzimidazolyl, benzoxazolyl, pyridine. One of a mercapto group, a quinoxalinyl group or a naphthyridinyl group.
3. The organic light-emitting device according to claim 1, wherein in the formula (1)

   

   Expressed as:

   

   

   

   

   

   

   

   Any of them.
4. The organic light emitting device according to claim 1, wherein said second host material is represented by the general formula (8):

   

   Wherein A ₁ to A ₄ , X ₁ , L ₁ , a ₁ , R ₄ and b ₄ in the formula (8) are as defined in the formula (2).
5. The organic light emitting device according to claim 1, wherein said second host material is represented by the general formula (9):

   

   Among them, A ₁ , A ₄ , X ₁ , L ₁ , a ₁ , R ₄ and b _{4 in the} formula (9) are as defined in the formula (2).
6. The organic light-emitting device according to claim 1, wherein the specific structural formula of the compound represented by the general formula (1) is:

   

   

   

   

   

   Any of them.
7. The organic light-emitting device according to claim 1, wherein the specific structural formula of the compound represented by the general formula (2) is:

   

   

   

   

   Any of them.
8. The organic light emitting device according to claim 1, wherein said light emitting layer further comprises a guest dopant.
9. The organic light emitting device according to claim 8, wherein said guest dopant is represented by the general formula (10):

   

   Wherein M is one of metal platinum, that is, Pt, yttrium, Ir, yttrium, or copper, or Cu; and X ₂ , X ₃ , X ₄ , and X ₅ are independently represented by oxygen, carbon, or nitrogen atoms. One; A ₅ and A ₆ are each independently represented as an aromatic group, A ₇ is an organic ligand; n ₁ = 0, 1, 2 or 3; n ₂ = 1, 2 or 3.
10. The organic light emitting device according to claim 1, wherein the hole transporting region comprises one or more of a hole injecting layer, a hole transporting layer, a buffer layer, and an electron blocking layer.
11. The organic light-emitting device according to claim 10, wherein the hole injecting layer material is one of the following structural formulas (11), (12) or (13):

    

    Wherein, in the formula (11), Er ₁ -Er ₃ are independently represented as one of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C1-C60 heteroaryl group; Er ₁ -Er ₃ can be the same or different;

    In the general formula (12) and the general formula (13), Fr ₁ -Fr ₆ are each independently represented by a hydrogen atom, a nitrile group, a halogen, an amide group, an alkoxy group, an ester group, a nitro group, and a C1-C60 straight. One of a chain or branched alkyl substituted carbon atom, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C1-C60 heteroaryl group.
12. The organic light-emitting device according to claim 10, wherein the hole transport layer material is a compound of a triarylamine group, and the structural formula is as shown in the formula (14):

    

    Wherein, in the general formula (14), Ar ₂ , Ar ₃ and Ar ₄ are each independently represented by a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C1-C60 heteroaryl group; .
13. The organic light emitting device according to claim 1, wherein the electron transporting region comprises one or more of an electron injecting layer, an electron transporting layer, and a hole blocking layer.
14. The organic light-emitting device according to claim 13, wherein the material of the electron injecting layer is one of lithium, a lithium salt or a phosphonium salt.
15. The organic light-emitting device according to claim 13, wherein the material of the electron-transporting layer is any of the compounds represented by the following formula (15), (16), (17, (18) or (19); One kind:

    

    

    Wherein the general formula (15), (16), (17), (18) and (19) Dr ₁ -Dr ₁₀ each independently represent a hydrogen atom, a substituted or unsubstituted C6-C60 aryl group, a substituted Or any of the unsubstituted C1-C60 heteroaryl groups.
16. The organic light-emitting device according to claim 1, wherein the organic light-emitting device comprises a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, and a light-emitting layer, The luminescent layer includes a first body, a second body, and a guest dopant.
17. The organic light-emitting device according to any one of claims 1 to 16, wherein a mass ratio of the first body to the second body is between (1:99) and (99:1).
18. The organic light-emitting device according to any one of claims 8, 9 or 16, wherein a ratio of the mass of the guest dopant to the total mass of the first and second bodies is between (0.5 and 20):100. .
19. The organic light-emitting device according to any one of claims 1 to 16, wherein the first body and the second body have a mass ratio of 1:5 to 5:1.
20. The organic light-emitting device according to any one of claims 8, 9 or 16, wherein the ratio of the mass of the guest dopant to the total mass of the first and second bodies is from 0.1 to 1:1.
21. An organic light-emitting device according to claim 1, wherein said light-emitting layer comprises a first host material represented by the general formula (1) and a second host material represented by the formula (71):

    

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