Luminescent layer guest materials, the luminescent layer comprising it and OLED display panel and electronicsEquipmentTechnical field
The invention belongs to Organic Light Emitting Diode preparation fields, and in particular to a kind of luminescent layer guest materials, comprising itsLuminescent layer and OLED display panel and electronic equipment.
Background technique
Organic Light Emitting Diode (OLED) originates from nineteen sixties, and Pope et al. will be passed to outside anthracene single crystal at that time100V DC voltage, thus the phenomenon that discovery is luminous, but because there is no extensive researchs for its lower practicability.Deng Qingyun in1987 are prepared for using vacuum deposition apparatus with 8-hydroxyquinoline aluminium (Alq3) OLED device as emitting layer material, really open upThe potential quality of its commercialization is shown.
In Organic Light Emitting Diodes, electrons and holes form exciton from the non-paired injection of cathode and anode respectively, togetherWhen generate triplet and the free parallel singlet state of spin pairing.And the exciton of usually only singlet state energy in nano-secondsIt enough generates radiation transistion and issues electroluminescent fluorescent, the radiation transistion of the triplet exciton of most of organic molecules is prohibited, to electricityThe contribution very little of photoluminescence, the energy overwhelming majority lost in the form of heat.The probability that triplet exciton generates is substanceThree times of state, so general OLED can only generate fluorescence using singlet excited, internal quantum efficiency is up to 25%, remaining75% corresponding energy is not utilized.
This field needs to develop a kind of luminescent layer of high-luminous-efficiency, and internal quantum efficiency can be substantially improved.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of luminescent layer, the luminescent layer includes firstKind material and second of the material mixed with the first described material；
The first described material and second of material meet:
EgT (1)-EgT (2) >=0.5eV formula 1；
EgS (2) > EgS (1) formula 2；
0≤2EgT (2)-EgS (2)≤0.2eV formula 3；
Wherein EgT (1) is the triplet of the first material, and EgT (2) is the triplet of second of material；EgSIt (2) is the singlet energy level of second of material, EgS (1) is the singlet energy level of the first material.
Present invention restriction EgT (1)-EgT (2) >=0.5eV, EgS (2) > EgS (1) and 0≤2EgT (2)-EgS (2)≤0.2eV can guarantee that the transition of triplet, with second of material three lines occur for the singlet energy level of the first materialState-triplet energy state transmitting；2 triplet states of second of material collide to obtain singlet, realize and shine after singlet transition.
Preferably, second of material has the structure of formula (I):
In formula (I), Ar1For any a kind in substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl；
R1、R2、R3、R4It is each independently selected from hydrogen atom, D-atom, halogen atom, substituted or unsubstituted alkyl baseGroup, the group of naphthene base of substituted or unsubstituted group of naphthene base, substituted or unsubstituted hydridization, substituted or unsubstituted heteroarylBase group.
The structure of formula (I) has the 2 phosphorus oxygen double bonds connected by phenyl ring, has high quantum efficiency, is not susceptible to gatherCollect quenching advantage.
Preferably, in formula (I), Ar1For the arlydene, substituted or unsubstituted of substituted or unsubstituted carbon atom number≤30Any a kind in the inferior heteroaryl of carbon atom number≤30, preferablyIn any a kind.
Preferably, R1、R2、R3、R4It is each independently selected from hydrogen atom, furan group, any a kind in thienyl group.
Preferably, second of material is any a kind or at least two kinds of of combination in following compound:
Preferably, the material of main part has the structure of formula (II):
In formula (II), M is metallic atom, Y1、Y2It is each independently selected from substituted or unsubstituted aromatic group or it spreads outBiological group, n+m are the oxidation state valence state of M.
Preferably, M is transition metal atoms, preferably pt atom or ruthenium atom.
Preferably, Y1、Y2It is each independently selected from the aromatic group of carbon atom number≤12 or derivatives thereof group, preferablyPhenyl, naphthalene, tolyl, any a kind in carboxyl phenyl.
Preferably, the first described material is Pt class material.
It selects Pt class material as the first material, there is longer triplet lifetime, be easy to happen triplet state-triplet stateBury in oblivion, i.e. TTA's is high-efficient；Luminous efficiency with higher, the low efficiency of nonradiative transition；More with the energy level of guest materialsMatching.
Preferably, in the luminescent layer, in the luminescent layer, the doping volume ratio of second material and the first material >=10:1, such as 11:1,12:1,13:1,14:1,15:1,16:1 etc..
The volume ratio of 10:1 can obtain higher triplet state-triplet state probability of happening and higher quantum efficiency, and firstThe excessive concentration of kind material, the energy transfer efficiency that will lead to triplet state reduce.
The second object of the present invention is to providing a kind of OLED display panel, including substrate, it is set in turn in the substrate sideFirst electrode, lamination and second electrode including organic luminous layer；
The organic luminous layer includes luminescent layer described in the first purpose.
Preferably, the OLED display panel successively includes first electrode, hole injection layer, hole transport from the bottom to topLayer, luminescent layer, electron transfer layer, electron injecting layer and second electrode；
The organic luminous layer includes luminescent layer described in the first purpose.
The three of the object of the invention are to provide a kind of electronic equipment, including OLED display surface described in the claim second purposePlate.
Compared with prior art, the present invention have it is following the utility model has the advantages that
The present invention meets the first material and second of material of formula 1, formula 2 and formula 3 by selecting, and can obtainLower starting voltage.Second of material of the invention uses the mechanism of up-conversion luminescence, by the first material of low energyEnergy is absorbed as sensitizer, is transferred to after second of material and second of material molecule is formed by triplet state-triplet state annihilationThe singlet of higher energy level realize that low energy absorbs later by the singlet radiation transistion of second of molecule, high-energy hairIt is penetrating as a result, being exactly that initial voltage is relatively low to the beneficial effect of device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the OLED device that the embodiment of the present invention 1 provides；
Wherein, 1 is anode, and 2 be hole injection layer, and 3 be hole transmission layer, and 4 be luminescent layer, and 5 be hole blocking layer, and 6 areElectron transfer layer, 7 be electron injecting layer, and 8 be cathode.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementationExample is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The preparation of compound B-11
In toluene and K2CO3Aqueous solution mixed solution (volume ratio be 4:1 toluene and water mixed solution) in, addEnter 6.5g compound 1 and 2.8g compound 2, adds 0.3g Pd (PPh3)4As catalyst, 80 DEG C are heated to, reaction 24 is smallWhen after be cooled to room temperature.Rear pillar chromatography is filtered, target compound B1,4.1g, yield 78% are obtained.
Characterize data:
The structure of gained complex of iridium pass through when laser desorption ionization m- flight mass spectrometer (MALDI-TOF-MASS) andNuclear magnetic resonance spectroscopy (1H NMR) is analyzed.
Molecular weight characterization MS 527.42
1H-NMR:(400MHz, CDCl3), δ (ppm): 7.33-7.38 (m, 20H), 6.38-6.44 (m, 4H)
Embodiment 2
The preparation of compound B2
In toluene and K2CO3Aqueous solution mixed solution (volume ratio be 4:1 toluene and water mixed solution) in, addEnter 3.3g compound 1 and 2.8g compound 2 and 4g compound 3, adds 0.3g Pd (PPh3)4As catalyst, it is heated to 80DEG C, reaction is cooled to room temperature after 24 hours.Rear pillar chromatography is filtered, target compound B2,1.3g, yield 22% are obtained.
Characterize data:
The structure of gained complex of iridium pass through when laser desorption ionization m- flight mass spectrometer (MALDI-TOF-MASS) andNuclear magnetic resonance spectroscopy (1H NMR) is analyzed.
Molecular weight characterization MS 593.92
1H-NMR:(400MHz, CDCl3), δ (ppm): 7.44-7.52 (m, 3H), 7.33-7.38 (m, 16H), 7.16 (d,1H) 6.38-6.44 (m, 4H), 6.22 (d, 2H)
Embodiment 3
The difference from example 2 is that 2 equimolar of compound is replaced with compound 4Obtain targetedClose object B3
Embodiment 4
The difference from embodiment 1 is that 1 equimolar of compound is replaced with compound 5By chemical combination2 equimolar of object replaces with compound 6Obtain target compound B4
Embodiment 5
The difference from example 2 is that 1 equimolar of compound is replaced with compound 5By chemical combination2 equimolar of object replaces with compound 63 equimolar of compound is replaced with into compound 7?To target compound B5
Application examples 1
A kind of OLED device, such as Fig. 1, the preparation method comprises the following steps:
(1) by the 25mm × 75mm × 1.1mm thick glass substrate with ito transparent electrode (100nm is thick) in isopropanolAfter carrying out supersound washing in 5 minutes, 30 minutes ozone washings are carried out.
(2) glass substrate with transparent electrode lines after washing is installed on the substrate holder of vacuum deposition apparatus, it is firstCompound HATCN is first deposited in the way of covering transparent electrode on the face for having transparent electrode lines sideThe compound HATCN film that film thickness is 10nm is formed, which is used as hole injection layer.And then it is depositedIt is 125nm as hole-injecting material that HIL2 forms film thickness on HATCN, and HIL2 has been depositedThe film thickness of 25nm and then is formed in vapor deposition HTM above afterwards, as hole mobile material.In HTMThe first material: A1 is deposited on film altogetherWith second of material B1Form filmThickness is the luminescent layer of 25nm, the first material concentration is about 7%, forms the luminescent layer that film thickness is 25nm, steams over the light-emitting layerPlating is as electron transport materialForm the electron transfer layer that film thickness is 20nm.In electron transfer layerUpper vapor deposition LiF forms the LiF layer that film thickness is 1nm.The evaporation metal Al on LiF forms the metallic cathode that film thickness is 80nm.
Above-mentioned OLED device is indicated with skeleton symbol are as follows:
ITO (100nm)/HATCN (10nm)/HIL2 (125nm)/HTM (25nm)/EML (B1:A1=13:1,25nm)/ETL(20nm)/LiF(1nm)/Al(80nm)。
Application examples 2
The difference from embodiment 1 is that second material selection compound B2.
Above-mentioned OLED device is indicated with skeleton symbol are as follows:
ITO (100nm)/HATCN (10nm)/HIL2 (125nm)/HTM (25nm)/EML (B2:A1=13:1,25nm)/ETL(20nm)/LiF(1nm)/Al(80nm)。
The first materials A 1With second of material B2
Application examples 3
The difference from embodiment 1 is that second material selection compound B3.
Above-mentioned OLED device is indicated with skeleton symbol are as follows:
ITO (100nm)/HATCN (10nm)/HIL2 (125nm)/HTM (25nm)/EML (B2:A1=13:1,25nm)/ETL(20nm)/LiF(1nm)/Al(80nm)。
The first materials A 1With second of material B3
Application examples 4
The difference from embodiment 1 is that second material selection compound B4.
Above-mentioned OLED device is indicated with skeleton symbol are as follows:
ITO (100nm)/HATCN (10nm)/HIL2 (125nm)/HTM (25nm)/EML (B2:A1=13:1,25nm)/ETL(20nm)/LiF(1nm)/Al(80nm)。
The first materials A 1With second of material B4
Application examples 5
The difference from embodiment 1 is that second material selection compound B5.
Above-mentioned OLED device is indicated with skeleton symbol are as follows:
ITO (100nm)/HATCN (10nm)/HIL2 (125nm)/HTM (25nm)/EML (B2:A1=13:1,25nm)/ETL(20nm)/LiF(1nm)/Al(80nm)。
The first materials A 1With second of material B5
Comparative example 1
The difference from embodiment 1 is that the first material selection compound A2.
Above-mentioned OLED device is indicated with skeleton symbol are as follows:
ITO (100nm)/HATCN (10nm)/HIL2 (125nm)/HTM (25nm)/EML (B1:A2=13:1,25nm)/ETL(20nm)/LiF(1nm)/Al(80nm)。
The first materials A 2With second of material B1
Table 1 gives the EgT (2) and EgS (2) of the EgT (1) and EgS (1) and B1-B5 of compound A1 and A2.
Table 1
| Material | EgT(1) | EgS(1) | Material | EgT(2) | EgS(2) |
| A1 | 2.25 | 2.58 | B1 | 1.42 | 2.64 |
| A2 | 2.52 | 2.76 | B2 | 1.44 | 2.70 |
| | | B3 | 1.45 | 2.70 |
| | | B4 | 1.42 | 2.72 |
| | | B5 | 1.41 | 2.73 |
As can be seen that the first material and second of material of application examples 1~5 are all satisfied:
EgT (1)-EgT (2) >=0.5eV formula 1；
EgS (2) > EgS (1) formula 2；
0≤2EgT (2)-EgS (2)≤0.2eV formula 3；
And the first material and second of material of comparative example 1 are unsatisfactory for formula 2.
Performance test:
The OLED device that embodiment and comparative example will be obtained, at 1000nit test test current efficiency, chromaticity coordinates,Service life the results are shown in Table 2.
Table 2
| Project | Voltage/V | Current efficiency Cd/A | Chromaticity coordinates CIEx | Chromaticity coordinates CIEy | Service life LT97/h |
| Application examples 1 | 3.8 | 11 | 0.129 | 0.147 | 37 |
| Application examples 2 | 4.1 | 10.5 | 0.127 | 0.147 | 37.5 |
| Application examples 3 | 3.7 | 10.2 | 0.127 | 0.147 | 36.3 |
| Application examples 4 | 3.8 | 11.4 | 0.128 | 0.146 | 36.6 |
| Application examples 5 | 3.7 | 10.8 | 0.129 | 0.147 | 36.2 |
| Comparative example 1 | 5.7 | 3.1 | 0.127 | 0.146 | 21 |
From test result as can be seen that when the first material and second of material meet formula 1, formula 2, formula 3 simultaneously,Low starting voltage 4.1V can be obtained hereinafter, high current efficiency 10.2Cd/A or more, longer service life LT97 36h withOn, thus it is speculated that it is transition of the singlet energy level due to meeting the first material of formula 1, formula 2, formula 3 to triplet,Triplet state-triplet state energy transmission occurs with second of material；2 triplet states of second of material collide to obtain singlet, singleIt realizes and shines after line state transition.When being unable to satisfy formula 2 for the material that comparative example 1 provides, just compared to the starting of embodimentVoltage is high, and current efficiency is low.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely onProcess equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the inventionWithin protection scope and the open scope.