CN110467630A - A kind of phosphorescent compound and the organic light emitting diode device using the compound - Google Patents

A kind of phosphorescent compound and the organic light emitting diode device using the compound Download PDF

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CN110467630A
CN110467630A CN201910682368.3A CN201910682368A CN110467630A CN 110467630 A CN110467630 A CN 110467630A CN 201910682368 A CN201910682368 A CN 201910682368A CN 110467630 A CN110467630 A CN 110467630A
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compound
phosphorescent compound
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light emitting
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郑贤哲
赵晓宇
华万鸣
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Zhejiang Hua Hui Photoelectric Technology Co Ltd
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Zhejiang Hua Hui Photoelectric Technology Co Ltd
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Abstract

The present invention relates to a kind of phosphorescent compound and use the organic light emitting diode device of the compound, more specifically, it is related to a kind of soluble phosphorescence host compound with excellent excitation purity and high brightness and luminous efficiency and the OLED device using the compound.A kind of phosphorescent compound, it is characterised in that: its structural formula as shown in formula 1 or formula 2,Ar1 and Ar2 is separately selected from C6~C60 aryl in above-mentioned formula 1 and formula 2, fluorenyl, including the heteroatomic C2~C60 heterocycle of O, N, S, Si and P wherein at least one, the alicyclic condensed ring radical with C6~C60 aromatic ring of C3~C60, C2~C20 alkenyl, one of C2~C20 alkynyl.L1 and L2 is separately selected from the group being made of singly-bound, C6~C60 arlydene, fluorenes alkenyl, the alicyclic condensed ring radical with C6~C60 aromatic ring of C3~C60, one of C2~C60 heterocycle.X1~X6 is independently selected from N atom or C atom, and wherein at least one of X1 to X6 is N.Wherein Y is selected from O, S and Se.Wherein Z is selected from O, S, Se and NAr3.The present invention uses luminescent layer of the phosphorescent compound as organic light emitting diode device shown in structural formula 1 and structural formula 2, has excellent excitation purity and brightness and extended durability effect.

Description

A kind of phosphorescent compound and the organic light emitting diode device using the compound
Technical field
The present invention relates to a kind of phosphorescent compound and using the organic light emitting diode device of the compound, it is more specific and Speech is related to a kind of soluble phosphorescence host compound with excellent excitation purity and high brightness and luminous efficiency and using should The OLED device of compound.
Background technique
Recently, the demand of flat-panel monitor (such as liquid crystal display and Plasmia indicating panel) is being increased.But These flat-panel monitors have lower response time and relatively narrow visual angle compared with cathode-ray tube (CRT).
Organic Light Emitting Diode (OLED) device is to be able to solve problem above and take up an area lesser next-generation FPD One of device.
The element of OLED device can be formed on flexible base board (such as plastic base).In addition, OLED device visual angle, There is advantage in terms of driving voltage, energy consumption and excitation purity.In addition, OLED device is enough to generate full-colour image.
In general, the light emitting diode of OLED device includes anode, hole injection layer (HIL), hole transporting layer (HTL), hair Optical material layer (EML), electron supplying layer (ETL), electron injecting layer (EIL) and cathode.
OLED device shines in the following manner: by the cathode as electron injection electrode and by as hole injecting electrode Anode respectively by electrons and holes inject light emitting compound layer in, to make electronics and hole-recombination to generate exciton, and make Exciton transits to ground state by excitation state.
Principle of luminosity can be divided into fluorescence radiation and phosphorescence shines.In fluorescence radiation, singlet excited state it is organic Thus molecular transition issues light to ground state.On the other hand, in phosphorescence shines, the organic molecule transition of triplet state excited state To ground state, light is thus issued.
When luminous material layer transmitting correspond to band gap light when, with 0 spin singlet exciton and with 1 spin Triplet excitons are generated with the ratio of 1:3.The ground state of organic material is singlet, this allows singlet exciton to transit to ground state And with luminous.But since triplet excitons cannot occur to use the OLED device of fluorescent material with luminous transition The internal quantum efficiency of part is limited within 25%.
On the other hand, if Quantum geometrical phase momentum is very high, singlet and triplet state mixing are so that in singlet Intersystem crossing is generated between triplet state, and triplet excitons can also transit to ground state and with luminous.Phosphor material can To use triplet excitons and singlet exciton, so that can have 100% interior amount using the OLED device of phosphor material Sub- efficiency.
Recently, by iridium complex, such as bis- (2- phenylchinoline) (acetylacetone,2,4-pentanedione) iridium (III) (Ir (2-phq) 2 (acac)), bis- (2- benzo [b] thiophene -2- yl pyridines) (acetylacetone,2,4-pentanedione) iridium (III) (Ir (btp) 2 (acac)) and three (2- phenyl Quinoline) introducing of iridium (III) Ir (2-phq) 3 dopant.
In order to obtain high current luminous efficiency (Cd/A) using phosphor material, excellent internal quantum, high is needed Excitation purity and long-life.In particular, referring to Fig.1, excitation purity is higher, that is, CIE (X) is higher, and colour sensitivity is poorer.As a result, In Under high internal quantum efficiency, very difficult acquisition luminous efficiency.Therefore, it is necessary to excellent excitation purity (CIE (X) >=0.65) and high-incidence The novel red phosphor compound of light efficiency.
On the other hand, other than above-mentioned iridium complex, for example, 4,4-N, N carbazole biphenyl (CBP) or other metal networks It closes object and is used as red phosphorescent compound.However, these compounds do not have ideal solubility in a solvent, thus cannot pass through Solution process forms luminescent layer.Luminescent layer should be formed by depositing operation, and therefore, manufacturing process is extremely complex, technique effect Rate is also extremely low.In addition, the waste material in depositing operation is very more, production cost is caused to increase.
Summary of the invention
The object of the present invention is to provide a kind of phosphorescent compound and using the compound organic light emitting diode device with Solve the deficiencies in the prior art place.
The present invention is the phosphorescent compound that technical solution is to provide formula 1 or formula 2 used by solving its technical problem,
Ar1 and Ar2 is separately selected from C6~C60 aryl, fluorenyl, including O in above-mentioned formula 1 and formula 2, N, S, Si and Heteroatomic C2~C60 the heterocycle of P wherein at least one, the alicyclic condensed ring radical with C6~C60 aromatic ring of C3~C60, C2 ~C20 alkenyl, one of C2~C20 alkynyl.L1 and L2 is separately selected from by singly-bound, C6~C60 arlydene, fluorenes alkenyl The group of composition, the alicyclic condensed ring radical with C6~C60 aromatic ring of C3~C60, one of C2~C60 heterocycle.X1~ X6 is independently selected from N atom or C atom, and wherein at least one of X1 to X6 is N.Wherein Y is selected from O, S and Se.Wherein Z is selected from O, S, Se and NAr3.
Further, it is miscellaneous to be selected from C6~C60 aryl, fluorenyl, including O, N, S, Si and P wherein at least one by the Ar3 C2~C60 heterocycle of atom, the alicyclic condensed ring radical with C6~C60 aromatic ring of C3~C60, C2~C20 alkenyl, C2~ One of C20 alkynyl.
Further, any structure of the formula 1 and formula 2 independently selected from 3~formula of formula 10:
Further, the phosphorescent compound is independently selected from following compounds:
Further, the organic electroluminescence device sequentially includes the anode of deposition, hole injection layer, hole transport Layer, luminescent layer, electron transfer layer, electron injecting layer and cathode, material of main part of the phosphorescent compound as luminescent layer.
The present invention has the advantages that the present invention uses phosphorescent compound shown in formula 1 or formula 2 as Organic Light Emitting Diode The luminescent layer of device has excellent excitation purity and brightness and extended durability effect.
Detailed description of the invention
Fig. 1 is organic electroluminescent LED lighting coloration and visibility relationship figure.
Fig. 2 is compound copper (II) phthalocyanine (CuPc) used in embodiments of the invention, NPB, (mxmq) 2Ir (acac), the structural formula of Alq3 and CBP.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below Diagram and specific embodiment are closed, the present invention is further explained.
Since the structural formula such as red phosphorescent compound of formula 1 and formula 2 all has excellent excitation purity, high brightness and excellent Luminous efficiency is now with RH-001, RH-014, RH-022, RH-145, RH-158 and RH-166 preparation method and test result Example, it was demonstrated that technical solution provided by the invention and the technical effect reached.
In following embodiments, NPB 4,4 '-bis- [N- (1- naphthalene)-N- phenylamino] biphenyl, CBP 4,4 '-N, N '- Two click biphenyl, CuPc are CuPc, and LiF lithium fluoride, ITO is tin indium oxide, and Alq3 is three (8-hydroxyquinoline) aluminium.
LC-MS: liquid chromatograph-mass spectrometer, M/Z: proton number/charge number ratio.
Form example
1. the synthesis of intermediate Sub-1:
1- hydroxyl -8- bromonaphthalene (150.0g, 672.4mmol) is added in 2000mL reaction flask, 2- nitrophenyl boronic acid (123.5g, 739.7mmol), tetrakis triphenylphosphine palladium (5mol%), potassium carbonate (278.8g, 2017.3mmol), tetrahydrofuran (8000mL) and water (800mL).Reaction system is warming up to 80 DEG C, reacts 12 hours under nitrogen protection.After the reaction was completed, it will react Liquid is cooled to room temperature, and is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, concentration, recrystallization gained crude product mistake Silicagel column obtains intermediate Sub-1 (114.2g, yield 64%) LC-MS:M/Z 266.3 (M+H)+。
2. the synthesis of intermediate Sub-2:
Intermediate Sub-1 (110.0g, 414.7mmol) and triethyl phosphite are added in 1000mL reaction flask (700mL).Reaction system is warming up to 80 DEG C, reacts 18 hours under nitrogen protection.After the reaction was completed, reaction solution is cooled to room Temperature is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, concentration, and recrystallization gained crude product is crossed silicagel column and obtained Intermediate Sub-2 (61.4g, yield 63%) LC-MS:M/Z 234.3 (M+H)+。
3. the synthesis of intermediate Sub-3:
Intermediate Sub-2 (60.0g, 257.2mmol) and methylene chloride (500mL) are added in 1000mL reaction flask, 0 The dichloromethane solution (200mL) of trifluoromethanesulfanhydride anhydride (108.8g, 385.8mmol) is added dropwise at DEG C.After being stirred overnight, with saturation Sodium bicarbonate quenching reaction.Organic phase is separated, with saturated common salt water washing and is dried over sodium sulfate.It is thick to produce after evaporating solvent Object is purified with column chromatography, and methylene chloride is used to obtain intermediate Sub-3 (70.5g, yield 75%) as eluant, eluent
LC-MS:M/Z 366.3(M+H)+。
4. the synthesis of intermediate Sub-4:
Intermediate Sub-3 (70.0g, 191.6mmol) is added in 2000mL reaction flask, 2- methylthio phenyl boric acid (35.4g, 210.8mmol), tetrakis triphenylphosphine palladium (5mol%), potassium carbonate (79.4g, 574.8mmol), tetrahydrofuran (600mL) and water (600mL).Reaction system is warming up to 80 DEG C, reacts 12 hours under nitrogen protection.After the reaction was completed, it will react Liquid is cooled to room temperature, and is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, concentration, recrystallization gained crude product mistake Silicagel column obtains intermediate Sub-4 (51.4g, yield 79%) LC-MS:M/Z 340.5 (M+H)+。
5. the synthesis of intermediate Sub-5:
Intermediate Sub-4 (50.0g, 147.3mmol) is added in 500mL reaction flask, hydrogen peroxide (32.6g, 368.2mmol), acetic acid (600mL) is added in round-bottomed flask and is stirred at room temperature.After the reaction was completed, acetic acid is removed, water is added Solid is precipitated, in methylene chloride by solid dissolution, column separation concentration obtains intermediate Sub-5 (42.9g, yield 82%) LC-MS:M/Z 356.5(M+H)+。
6. the synthesis of intermediate Sub-6:
Intermediate Sub-5 (40.0g, 112.5mmol) is added in 500mL reaction flask and is dissolved in excessive sulfuric acid (200mL) And it is stirred 3 days at 40 DEG C.When after the reaction was completed, solution being neutralized to pH8-9 with 0.2N- sodium hydrate aqueous solution.After filtering, Solution is extracted with dichloromethane and is concentrated, column separation simultaneously recrystallizes, and obtains intermediate Sub-6 (28.4g, yield 78%) LC-MS:M/Z 324.4(M+H)+。
7. the synthesis of intermediate Sub-7:
Intermediate Sub-6 (28.0g, 86.6mmol) is added in 2000mL reaction flask, nitromethane (150mL) is dissolved in two Chloromethanes (700mL), cools the temperature to 0 DEG C under nitrogen atmosphere.Ferric trichloride (70.2g, 432.9mmol) is added and stirs 1 afterwards Hour.After methanol (150mL) is added, organic layer is extracted with water (200mL).Organic layer is concentrated under reduced pressure, then passes through column chromatography point From obtaining intermediate Sub-7 (19.2g, yield 69%) LC-MS:M/Z 322.4 (M+H)+。
The synthesis of 8.RH-001:
Intermediate compound I -1 (3.0g, 10.7mmol) is added in 250mL three-necked flask, intermediate Sub-7 (3.8g, 11.8mmol), tris(dibenzylideneacetone) dipalladium (4mol%), tri-tert-butylphosphine (8mol%), potassium tert-butoxide (3.6g, 32.1mmol) and ortho-xylene (80mL).Reaction system is warming up to 120 DEG C, reacts 14 hours under nitrogen protection.Reaction is completed Afterwards, reaction solution is cooled to room temperature, is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, and concentration recrystallizes institute Crude product crosses silicagel column and obtains RH-001 (4.7g, yield 77%).LC-MS:M/Z 566.6(M+H)+。
The synthesis of 9.RH-014:
Intermediate compound I -2 (3.0g, 6.9mmol) is added in 250mL three-necked flask, intermediate Sub-7 (2.4g, 7.6mmol), tris(dibenzylideneacetone) dipalladium (4mol%), tri-tert-butylphosphine (8mol%), potassium tert-butoxide (2.3g, 20.6mmol) and ortho-xylene (80mL).Reaction system is warming up to 120 DEG C, reacts 14 hours under nitrogen protection.Reaction is completed Afterwards, reaction solution is cooled to room temperature, is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, and concentration recrystallizes institute Crude product crosses silicagel column and obtains RH-014 (3.5g, yield 71%).LC-MS:M/Z 721.8 (M+H)+。
The synthesis of 10.RH-022:
Intermediate compound I -3 (3.0g, 8.4mmol) is added in 250mL three-necked flask, intermediate Sub-7 (3.0g, 9.2mmol), tris(dibenzylideneacetone) dipalladium (4mol%), tri-tert-butylphosphine (8mol%), potassium tert-butoxide (2.8g, 25.2mmol) and ortho-xylene (80mL).Reaction system is warming up to 120 DEG C, reacts 14 hours under nitrogen protection.Reaction is completed Afterwards, reaction solution is cooled to room temperature, is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, and concentration recrystallizes institute Crude product crosses silicagel column and obtains RH-022 (3.9g, yield 73%).LC-MS:M/Z 642.7(M+H)+。
The synthesis of 11.RH-145:
Intermediate compound I -4 (3.0g, 10.7mmol) is added in 250mL three-necked flask, intermediate Sub-7 (3.8g, 11.8mmol), tris(dibenzylideneacetone) dipalladium (4mol%), tri-tert-butylphosphine (8mol%), potassium tert-butoxide (3.6g, 32.1mmol) and ortho-xylene (80mL).Reaction system is warming up to 120 DEG C, reacts 14 hours under nitrogen protection.Reaction is completed Afterwards, reaction solution is cooled to room temperature, is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, and concentration recrystallizes institute Crude product crosses silicagel column and obtains RH-145 (4.5g, yield 75%).LC-MS:M/Z 566.6(M+H)+。
The synthesis of 12.RH-158:
Intermediate compound I -5 (3.0g, 6.9mmol) is added in 250mL three-necked flask, intermediate Sub-7 (2.4g, 7.6mmol), tris(dibenzylideneacetone) dipalladium (4mol%), tri-tert-butylphosphine (8mol%), potassium tert-butoxide (2.3g, 20.6mmol) and ortho-xylene (80mL).Reaction system is warming up to 120 DEG C, reacts 14 hours under nitrogen protection.Reaction is completed Afterwards, reaction solution is cooled to room temperature, is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, and concentration recrystallizes institute Crude product crosses silicagel column and obtains RH-158 (3.5g, yield 70%).LC-MS:M/Z 721.8(M+H)+。
The synthesis of 13.RH-166:
Intermediate compound I -6 (3.0g, 8.4mmol) is added in 250mL three-necked flask, intermediate Sub-7 (3.0g, 9.2mmol), tris(dibenzylideneacetone) dipalladium (4mol%), tri-tert-butylphosphine (8mol%), potassium tert-butoxide (2.8g, 25.2mmol) and ortho-xylene (80mL).Reaction system is warming up to 120 DEG C, reacts 14 hours under nitrogen protection.Reaction is completed Afterwards, reaction solution is cooled to room temperature, is extracted with o-dichlorohenzene and water.Organic layer is dry with anhydrous magnesium sulfate, and concentration recrystallizes institute Crude product crosses silicagel column and obtains RH-166 (3.9g, yield 72%).LC-MS:M/Z 642.7(M+H)+。
Embodiment
1. first embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, wash patterned ito glass Substrate.
The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBRH-001+(mxmq)2Ir (acac) ((5%)Alq3 LiF And AlThe layer for sequentially forming organic substance.
At 0.9 ma, brightness is equal to 1869cd/m2(5.2V).At this time, CIEx=0.657, y=0.341.
2. the second embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, wash patterned ito glass Substrate.
The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBRH-014+(mxmq)2Ir (acac) (5%)Alq3 LiFWith AlThe layer for sequentially forming organic substance.
At 0.9 ma, brightness is equal to 1831cd/m2(5.4V).At this time, CIEx=0.658y=0.340.
3. third embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, wash patterned ito glass Substrate.
The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBRH-022+(mxmq)2Ir (acac) (5%)Alq3 LiFWith AlThe layer for sequentially forming organic substance.
At 0.9 ma, brightness is equal to 1850cd/m2(5.3V).At this time, CIEx=0.657, y=0.341.
4. the 4th embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, wash patterned ito glass Substrate.
The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBRH-145+(mxmq)2Ir (acac) (5%)Alq3 LiF And AlThe layer for sequentially forming organic substance.
At 0.9 ma, brightness is equal to 1861cd/m2(5.3V).At this time, CIEx=0.657, y=0.340.
5. the 5th embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, wash patterned ito glass Substrate.
The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBRH-158+(mxmq)2Ir (acac) (5%)Alq3 LiF And AlThe layer for sequentially forming organic substance.
At 0.9 ma, brightness is equal to 1822cd/m2(5.4V).At this time, CIEx=0.658, y=0.340
6. the 6th embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, wash patterned ito glass Substrate.
The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBRH-166+(mxmq)2Ir (acac) (5%)Alq3 LiF And AlThe layer for sequentially forming organic substance.
At 0.9 ma, brightness is equal to 1839cd/m2(5.3V).At this time, CIEx=0.657, y=0.340.
7. comparative example
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, wash patterned ito glass Substrate.
The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.On an ito substrate with CuPcNPBCPB+(mxmq)2Ir (acac) (5%)Alq3 LiFAnd AlThe layer for sequentially forming organic substance.
At 0.9 ma, brightness is equal to 1409cd/m2(5.7V).At this time, CIEx=0.657, y=0.341.
The excitation purity of display organic electroluminescence light emitting device as shown in Figure 1 increases (becoming much larger with the X value of chromaticity coordinate) Visibility reduces.
According to the embodiment above and comparative example, efficiency, chromaticity coordinate, and the characteristic of brightness are shown in table 1 below.
Table 1
As shown in table 1, or even when excitation purity is high, which also expeditiously runs at low voltage.Further, with comparison Example is compared, and the second embodiment current efficiency increases by 30% or more.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent defines.

Claims (5)

1. a kind of phosphorescent compound, it is characterised in that: its structural formula as shown in formula 1 or formula 2,
In above-mentioned formula 1 and formula 2 Ar1 and Ar2 be separately selected from C6~C60 aryl, fluorenyl, including O, N, S, Si and P its At least one of heteroatomic C2~C60 heterocycle, C3~C60 is alicyclic and the condensed ring radical of C6~C60 aromatic ring, C2~ C20 alkenyl, one of C2~C20 alkynyl；L1 and L2 is separately selected from by singly-bound, C6~C60 arlydene, fluorenes alkenyl group At group, C3~C60 is alicyclic and the condensed ring radical of C6~C60 aromatic ring, one of C2~C60 heterocycle；X1~X6 Independently selected from N atom or C atom, wherein at least one of X1~X6 is N；Wherein Y is selected from O, S and Se；Wherein Z is selected from O, S, Se and NAr3.
2. phosphorescent compound as described in claim 1, it is characterised in that: wherein Ar3 be selected from C6~C60 aryl, fluorenyl, including O, N, the heteroatomic C2~C60 heterocycle of S, Si and P wherein at least one, C3~C60 are alicyclic thick with C6~C60 aromatic ring Ring group, C2~C20 alkenyl, one of C2~C20 alkynyl.
3. the phosphorescent compound as described in any one of claim 1, which is characterized in that the formula 1 and formula 2 independently selected from Any structure of 3~formula of formula 10:
4. the phosphorescent compound as described in any one of claim 1-3, it is characterised in that: the phosphorescent compound is independent Ground is selected from following compounds:
。
5. a kind of organic electroluminescent diode apparatus using phosphorescent compound described in any one of claim 1-4, It is characterized by: the organic electroluminescence device sequentially includes the anode of deposition, hole injection layer, hole transmission layer, hair Photosphere, electron transfer layer, electron injecting layer and cathode, material of main part of the phosphorescent compound as luminescent layer.
CN201910682368.3A 2019-07-26 2019-07-26 A kind of phosphorescent compound and the organic light emitting diode device using the compound Pending CN110467630A (en)

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