CN107641129A - A kind of thermal activation delayed fluorescence material and its organic electroluminescence device - Google Patents
A kind of thermal activation delayed fluorescence material and its organic electroluminescence device Download PDFInfo
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- CN107641129A CN107641129A CN201710877987.9A CN201710877987A CN107641129A CN 107641129 A CN107641129 A CN 107641129A CN 201710877987 A CN201710877987 A CN 201710877987A CN 107641129 A CN107641129 A CN 107641129A
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- thermal activation
- delayed fluorescence
- activation delayed
- fluorescence material
- organic electroluminescence
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Abstract
The present invention provides a kind of thermal activation delayed fluorescence material and its organic electroluminescence device, belongs to technical field of organic electroluminescence.Thermal activation delayed fluorescence material category is single in the prior art for solution, can not meet the technical problem of OLED demand.The present invention, using arylamine or the thick and heteroaromatic for containing nitrogen-atoms as electron donor, obtains a kind of thermal activation delayed fluorescence material using imidazo Purinone derivatives as electron acceptor.The organic electroluminescence device prepared using thermal activation delayed fluorescence material provided by the invention, external quantum efficiency is high, and maximum current efficiency is up to 10.60cd/A, maximum power efficiency is up to 9.30lm/W, with higher luminous efficiency, and driving voltage is low, is a kind of excellent OLED material.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, and in particular to a kind of thermal activation delayed fluorescence material and its organic
Electroluminescent device.
Background technology
Organic electroluminescent LED (Organic Light-Emitting Diode, OLED) refers to luminous organic material
The diode to be lighted in the presence of electric current or electric field, electric energy can be converted into luminous energy by it.Kodak Company in 1987
Tang etc. has invented sandwich type organic bilayer film luminescent device, this breakthrough, allows it is seen that OLED technology
Move towards practical, move towards the great potential of commercial market, started the research boom of Organic Light Emitting Diode.Over 30 years, OLED
Technology achieves development with rapid changepl. never-ending changes and improvements, is moved towards the industrialization production from laboratory research.All solid state, the active of OLED technology
Luminous, high-contrast, it is ultra-thin, can Flexible Displays, low-power consumption, wide viewing angle, fast response time, operating temperature range is wide, it is real to be easy to
Many advantages, such as existing 3D display, " fantasy display " is referred to as by professional, will turn into following most potential new
Type Display Technique.
Certainly, the behind that OLED technology is advanced by leaps and bounds, luminous organic material play an important role.Luminous organic material root
It can be substantially divided into three classes according to luminescence mechanism:Conventional fluorescent material, phosphor material and thermal activation delayed fluorescence (Thermally
Activated Delayed Fluorescence, TADF) material.Wherein, conventional fluorescent material and phosphor material are in work
Industry metaplasia production in be applied, but they still have it is clearly disadvantageous.Traditional fluorescent material, in the condition of electroexcitation
Under, limited by spin quantum statistical theorem, singlet excitons and the triplet exciton ratio of number of formation are 1:3,75%
Triplet exciton can only be dissipated and can not be lighted by radiation transistion in the form of heat, only 25% singlet excitons can
Lighted by radiation transistion, i.e., traditional fluorescent material highest internal quantum efficiency (Internal Quantum Efficiency,
IQE it is only) 25%, if being 20% in view of optical coupling delivery efficiency, then the highest external quantum efficiency of its OLED
(External Quantum Efficiency, EQE) is only 5%.Although fluorescent material OLED has higher reliability
And stability, but relatively low external quantum efficiency still limits its application.And phosphor material generally comprises rare precious metals, cause
The problems such as expensive, and device stability can be poor, device efficiency decline is serious, all largely further limit
Its extensive commercial popularization.In recent years, thermal activation delayed fluorescence material has been increasingly becoming the new focus of this area research.The material
100% internal quantum efficiency can be realized under conditions of non precious metal, can not only avoid the use of the heavy metal of costliness, from
And cost is reduced to a certain extent, and it can be desirable to greatly improve device lifetime and spectrum stability, while there is luminous effect
Rate is high, the advantage such as environment-friendly, is referred to as third generation electroluminescent material.
But the correlative study at present on thermal activation delayed fluorescence material is also fewer, material category is still single, nothing
Method meets the exploitation demand of OLED, and novel high-performance thermal activation delayed fluorescence material is urgently developed.
The content of the invention
In view of this, thermal activation delayed fluorescence material category is single in order to solve in the prior art, can not meet OLED devices
The technical problem of part demand, the present invention provide a kind of thermal activation delayed fluorescence material and its organic electroluminescence device.
Present invention firstly provides a kind of thermal activation delayed fluorescence material, has the structural formula as shown in formula (I):
Wherein, in arylamine of the Ar selected from substituted or unsubstituted C6-C60, substituted or unsubstituted C4-C60 heteroaromatic
Any one.
Preferably, the Ar is selected from substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C4-C30 virtue
Any one in heterocycle.
Preferably, any one of the Ar in following structure:
Wherein, R1、R2Alkyl independently selected from C1-C10, one kind in substituted or unsubstituted C6-C30 aryl;
R3、R4Alkyl independently selected from H, C1-C10, one kind in substituted or unsubstituted C6-C30 aryl, or R3Or R4With
The group at place forms condensed ring.
Preferably, the thermal activation delayed fluorescence material, shown in any one in following compound:
The present invention also provides a kind of organic electroluminescence device, including anode, negative electrode and positioned at the anode and negative electrode
Between several organic function layers, the organic function layer includes any one of described thermal activation delayed fluorescence material
Or at least two combination.
Preferably, the organic function layer includes luminescent layer, and the luminescent layer includes described thermal activation delayed fluorescence material
Material any one or at least two combination.
Preferably, the thermal activation delayed fluorescence material is used as dopant material, co-doped material or master in luminescent layer
Body material.
Beneficial effects of the present invention:
Thermal activation delayed fluorescence material category is single in order to solve in the prior art, can not meet the skill of OLED demand
Art problem, the present invention provide a kind of thermal activation delayed fluorescence material and its organic electroluminescence device.The present invention is with the thiophene of benzo two
Fen diketone, using arylamine or the thick and heteroaromatic for containing nitrogen-atoms as electron donor, makes to have suction in molecule concurrently as electron acceptor
Electronics and electron donating group, HOMO and LUMO electron cloud separation is realized, effectively induction produces Intramolecular electron transfer, favorably
Transmitted in the devices in carrier, and then improve the characteristics of luminescence of organic electroluminescence device.
Test result indicates that the organic electroluminescence prepared using thermal activation delayed fluorescence material provided by the invention
Part, external quantum efficiency are high, maximum current efficiency up to 10.60cd/A, maximum power efficiency up to 9.30lm/W, have higher
Luminous efficiency, and driving voltage is low, is a kind of excellent OLED material.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
It should be noted that unless otherwise prescribed, the implication of scientific and technical terminology used in the present invention and people in the art
The implication that member is generally understood is identical.
Alkyl of the present invention refers to minus the alkyl that a hydrogen atom forms in alkane molecule, and it can be straight chain alkane
Base, branched alkyl or cycloalkyl, example may include methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl group, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Arylamine of the present invention can be monocyclic diaryl-amine, polycyclic diaryl-amine or monocyclic and polycyclic diaryl-amine.
Aryl of the present invention refers to after removing a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule, is left the total of univalent perssad
Claiming, it can be monocyclic aryl or fused ring aryl, and example may include phenyl, xenyl, naphthyl, anthryl, phenanthryl or pyrenyl etc., but
Not limited to this.
Heteroaromatic of the present invention refers to the total of the group that one or more aromatic core carbon substitute to obtain by hetero atom in aromatic ring
Claim, the hetero atom includes but is not limited to oxygen, sulphur, nitrogen or silicon atom, and the heteroaromatic can be monocyclic or condensed ring, and example can wrap
Include pyridine radicals, phenothiazinyl, phenoxazine base, pyrimidine radicals, benzo pyrimidine radicals, carbazyl, triazine radical, benzothiazolyl, benzo miaow
Oxazolyl, acridinyl etc., but not limited to this.
Present invention firstly provides a kind of thermal activation delayed fluorescence material, has the structural formula as shown in formula (I):
Wherein, in arylamine of the Ar selected from substituted or unsubstituted C6-C60, substituted or unsubstituted C4-C60 heteroaromatic
Any one.
According to the present invention, preferably Ar is selected from substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C4-C30
Heteroaromatic in any one.Hetero atom in the heteroaromatic is preferably one or both of N, O, S and Si;Further
, the heteroaromatic is preferably thick and heteroaromatic.
According to the present invention, any one of further preferably described Ar in following structure:
Wherein, R1、R2Alkyl independently selected from C1-C10, one kind in substituted or unsubstituted C6-C30 aryl;
R3、R4Alkyl independently selected from H, C1-C10, one kind in substituted or unsubstituted C6-C30 aryl, or R3Or R4With
The group at place forms condensed ring.Preferably, R1、R2Independently selected from methyl, ethyl, propyl group, butyl, phenyl, xenyl or three
Phenyl, more preferably methyl, ethyl or phenyl;Preferably, R3、R4Independently selected from H, methyl, ethyl, propyl group, butyl, phenyl
Or xenyl, or R3Or R4Form condensed ring with the group at place, more preferably H, methyl, ethyl or phenyl, or for phenyl with
The group at place forms naphthalene nucleus.
As an example, it is not particularly limited, thermal activation delayed fluorescence material of the present invention is as follows:
It is enumerated above some specific structure types of thermal activation delayed fluorescence material of the present invention, but the present invention
Be not limited to these listed chemical constitutions, it is every based on structure shown in formula (I), Ar be group as defined above all
It should be included.
The present invention using benzene thiophene diketone as electron acceptor, using arylamine or contain the thick and heteroaromatic of nitrogen-atoms as
Electron donor, make to have electrophilic and electron donating group in molecule concurrently, realize HOMO and LUMO electron cloud separation, effectively induce
Intramolecular electron transfer is produced, is advantageous to carrier and transmits in the devices, and then improves the luminous spy of organic electroluminescence device
Property.
The preparation method of the thermal activation delayed fluorescence material of the present invention, can be by by the thiophene of dibromo benzo two shown in formula (II)
Fen dione compounds obtain the thermal activation delayed fluorescence material shown in formula (I) with the compound containing Ar groups through ullmann reaction
Material.
The present invention does not have particular/special requirement to the reaction condition of above-mentioned reaction, with such reaction well known to those skilled in the art
Normal condition.The present invention has no particular limits to the source of the raw material employed in above-mentioned all kinds of reactions, Ke Yiwei
Commercially available prod is prepared using preparation method well-known to those skilled in the art.Wherein, the selection of the Ar is same as above institute
State, will not be repeated here.
The present invention also provides a kind of organic electroluminescence device, and the organic electroluminescence device is those skilled in the art
Known organic electroluminescence device, organic electroluminescence device of the present invention include anode, negative electrode and are located at
Several organic function layers between the anode and negative electrode, the organic function layer include described thermal activation delayed fluorescence
Material any one or at least two combination.The organic function layer can include hole injection layer, hole transmission layer, electricity
At least one layer in sub- barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer, preferably described organic work(
Ergosphere includes luminescent layer, the luminescent layer include described thermal activation delayed fluorescence material any one or at least two group
Close.More preferably described thermal activation delayed fluorescence material is used as dopant material, co-doped material or main body material in luminescent layer
Material.
The substrate in traditional organic electroluminescence device, example can be used in substrate in organic electroluminescence device of the present invention
Such as glass or plastics, it is preferred that use glass substrate in the present invention.
The electrode material with big work function can be used in anode material, can be such as indium oxide, zinc oxide, tin indium oxide
(ITO), metal oxide of indium zinc oxide (IZO) or its mixture etc..Preferably, tin indium oxide is used in the present invention
(ITO) it is used as anode material.
Hole transmission layer can use various tri-arylamine group materials.Preferably, NPB is used in the present invention.
Cathode material can be used with low work function electrode material, metal or its mixture structure can be used, as Mg,
Ag, Ca or electron injecting layer/metal-layer structure, such as LiF/Al, Li2The common cathode structure such as O/Al.Preferably, originally
The electron injection material used in invention is LiF, and negative electrode is Al.
The present invention has no particular limits to the source of the raw material employed in following examples, can be commercially available prod or
It is prepared using preparation method well-known to those skilled in the art.
Embodiment 1:The synthesis of compound 1
First, by dibromo benzene thiophene diketone (0.013mol, 5g), 9,9- dimethyl acridiniums (0.026mol, 5.56g)
It is placed in round-bottomed flask, addition 50mL toluene, iodate Asia ketone, potassium phosphate, trans 1,2 cyclohexanediamine, is passed through nitrogen protection, reaction
Overnight, reaction is stopped afterwards.Product after drying, is purified with column chromatography by extraction, obtains 10.2g products.Yield:
60.4%.
Mass spectrum m/z:634.30 (calculated values:634.17).Theoretical elemental content (%) C40H30N2O2S2:C, 75.68;H,
4.76;N, 4.41;O, 5.04;S, 10.10 actual measurement constituent contents (%):C, 75.80;H, 4.80;N, 4.42;O, 5.06;S,
10.10。
Embodiment 2:The synthesis of compound 3
The step of synthesis step is with embodiment 1, a kind of raw material 9 therein, 9- dimethyl acridiniums are simply changed into Fen Evil
Piperazine.
Mass spectrum m/z:582.19 (calculated values:582.07).Theoretical elemental content (%) C34H18N2O4S2:C, 70.09;H,
3.11;N, 4.81;O, 10.98;S, 11.00 actual measurement constituent contents (%):C, 70.21;H, 3.12;N, 4.82;O, 10.96;S,
11.01。
Embodiment 3:The synthesis of compound 4
The step of synthesis step is with embodiment 1, a kind of raw material 9 therein, 9- dimethyl acridiniums are simply changed into fen thiophene
Piperazine.
Mass spectrum m/z:614.15 (calculated values:614.03).Theoretical elemental content (%) C34H18N2O2S4:C, 66.43;H,
2.95;N, 4.56;O, 5.20;S, 20.86 actual measurement constituent contents (%):C, 66.51;H, 2.97;N, 4.61;O, 5.23;S,
20.90。
Embodiment 4:The synthesis of compound 5
The step of synthesis step is with embodiment 1, a kind of raw material 9 therein, 9- dimethyl acridiniums are simply changed into hexichol
Amine.
Mass spectrum m/z:554.19 (calculated values:554.11).Theoretical elemental content (%) C34H22N2O2S2:C, 73.62;H,
4.00;N, 5.05;O, 5.77;S, 11.56 actual measurement constituent contents (%):C, 73.71;H, 4.00;N, 5.02;O, 5.76;S,
11.60。
Embodiment 5:The synthesis of compound 11
The step of synthesis step is with embodiment 1, a kind of raw material 9 therein, 9- dimethyl acridiniums are simply changed into carbazole.
Mass spectrum m/z:550.19 (calculated values:550.08).Theoretical elemental content (%) C34H18N2O2S2:C, 74.16;H,
3.30;N, 5.09;O, 5.81;S, 11.64 actual measurement constituent contents (%):C, 74.21;H, 3.30;N, 5.12;O, 5.80;S,
11.70。
Embodiment 6:The preparation of organic electroluminescence device
The glass substrate for being coated with ito transparent electrode is ultrasonically treated in commercial detergent, rinsed in deionized water,
In acetone:Ultrasonic oil removing in alcohol mixed solvent, it is baked in clean environment and removes moisture completely, it is clear with ultraviolet light and ozone
Wash.
The above-mentioned glass substrate for being coated with ito transparent electrode is placed in vacuum chamber, is evacuated to 10-5–10-3Pa, evaporation
Hole transmission layer NPB, evaporation rate 0.1nm/s, thickness 20nm.On hole transmission layer be deposited the present invention in based on fast
The hot activation delayed fluorescence material of purine derivative is as luminescent layer, evaporation rate 0.1nm/s, thickness 30nm.In luminescent layer
Upper one layer of AlQ of vacuum evaporation3As electron transfer layer, evaporation rate 0.1nm/s, thickness 20nm.On the electron transport layer
Electron injecting layers and negative electrode of the LiF and Al as device, thickness difference 1nm and 100nm is deposited.The luminescent properties of measurement device,
It the results are shown in Table 1.
The characteristics of luminescence of luminescent device prepared by the embodiment of the present invention of table 1
As can be seen that the organic electroluminescence device prepared using thermal activation delayed fluorescence material provided by the invention, outside
Quantum efficiency is high, and maximum current efficiency has higher light up to 10.60cd/A, maximum power efficiency up to 9.30lm/W
Efficiency, and driving voltage is low, is a kind of excellent OLED material.
Obviously, the explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should refer to
Go out, under the premise without departing from the principles of the invention, can also be to this hair for the those of ordinary skill of the technical field
Bright to carry out some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (7)
1. a kind of thermal activation delayed fluorescence material, there is the structural formula as shown in formula (I):
Wherein, appointing in arylamine of the Ar selected from substituted or unsubstituted C6-C60, substituted or unsubstituted C4-C60 heteroaromatic
Meaning is a kind of.
2. a kind of thermal activation delayed fluorescence material according to claim 1, it is characterised in that Ar is selected from substitution or unsubstituted
C6-C30 arylamine, any one in substituted or unsubstituted C4-C30 heteroaromatic.
3. a kind of thermal activation delayed fluorescence material according to claim 1, it is characterised in that Ar is in following structure
Any one:
Wherein, R1、R2Alkyl independently selected from C1-C10, one kind in substituted or unsubstituted C6-C30 aryl;R3、R4Solely
On the spot one kind in the alkyl selected from H, C1-C10, substituted or unsubstituted C6-C30 aryl, or R3Or R4With the base at place
Group forms condensed ring.
4. a kind of thermal activation delayed fluorescence material according to claim 1, it is characterised in that compound is any one as follows
Shown in kind:
5. a kind of organic electroluminescence device, including anode, negative electrode and several between the anode and negative electrode have
Machine functional layer, it is characterised in that the thermal activation delay that the organic function layer is included described in any one of Claims 1 to 4 is glimmering
Luminescent material any one or at least two combination.
6. a kind of organic electroluminescence device according to claim 5, it is characterised in that the organic function layer includes hair
Photosphere, the luminescent layer include any one of Claims 1 to 4 described in thermal activation delayed fluorescence material any one or at least
Two kinds of combination.
A kind of 7. organic electroluminescence device according to claim 6, it is characterised in that the thermal activation delayed fluorescence material
Material is used as dopant material, co-doped material or material of main part in luminescent layer.
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CN112225747A (en) * | 2019-11-27 | 2021-01-15 | 杭州师范大学 | Organic luminescent material with thermal induced delayed fluorescence property and preparation method and application thereof |
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CN106414447A (en) * | 2014-05-19 | 2017-02-15 | Udc 爱尔兰有限责任公司 | Fluorescent organic light emitting elements having high efficiency |
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CN106414447A (en) * | 2014-05-19 | 2017-02-15 | Udc 爱尔兰有限责任公司 | Fluorescent organic light emitting elements having high efficiency |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112225747A (en) * | 2019-11-27 | 2021-01-15 | 杭州师范大学 | Organic luminescent material with thermal induced delayed fluorescence property and preparation method and application thereof |
CN112225747B (en) * | 2019-11-27 | 2021-09-21 | 杭州师范大学 | Organic luminescent material with thermal induced delayed fluorescence property and preparation method and application thereof |
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