CN111740020A - Efficient and long-life blue light device - Google Patents
Efficient and long-life blue light device Download PDFInfo
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- CN111740020A CN111740020A CN202010509194.3A CN202010509194A CN111740020A CN 111740020 A CN111740020 A CN 111740020A CN 202010509194 A CN202010509194 A CN 202010509194A CN 111740020 A CN111740020 A CN 111740020A
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Abstract
The invention belongs to the technical field of organic electroluminescent device display, and particularly relates to a blue light device with high efficiency and long service life. The organic layer comprises more than one blue light emitting layer and more than one electron transmission layer; the light-emitting layer is used in combination with an electron transport layer; the blue light emitting layer is composed of a host material represented by formula 1 below and a guest material represented by formula 2; the electron transport layer is prepared by co-evaporating a compound represented by formula 3 and an organic alkali metal compound;
Description
the technical field is as follows:
the invention belongs to the technical field of organic electroluminescent device display, and particularly relates to a blue light device with high efficiency and long service life.
Background art:
organic electroluminescent devices (OLEDs), as a novel display technology, have the unique advantages of self-luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide applicable temperature range, low driving voltage, capability of manufacturing flexible, bendable and transparent display panels, environmental friendliness and the like, and can be applied to flat panel displays and new generation illumination and also can be used as a backlight source of LCDs.
The organic electroluminescent device is prepared by depositing a layer of organic material between two metal electrodes through spin coating or vacuum evaporation, and a classic three-layer organic electroluminescent device comprises a hole transport layer, a light emitting layer and an electron transport layer. Holes generated by the anode are combined with electrons generated by the cathode through the hole transport layer and the electron transport layer to form excitons in the light emitting layer, and then the excitons emit light. The organic electroluminescent device can be adjusted to emit various desired lights such as blue light, green light, red light, orange light, white light, and the like by changing the material of the light emitting layer as needed. The first fluorescent OLEDs relied on only 25% singlet excitons and 75% triplet excitons were wasted, and thus the internal quantum efficiency was only 25% and the corresponding external quantum efficiency was only between 5-7.5%, which can be classified into fluorescent and phosphorescent OLEDs based on the mechanism of light emission. The discovery of phosphorescent OLEDs is undoubtedly a major breakthrough since phosphorescent emitters can fully utilize all excitons, thus achieving nearly 100% IQE, with corresponding external quantum efficiencies of 20% to 30%.
Among the three primary colors (red, blue, green), red and green devices have been greatly developed due to the use of phosphorescent materials, and also meet the market demand of panels. However, because of the high energy gap of blue light, the stability and light purity of blue phosphorescent materials have great problems, and blue phosphorescent devices cannot meet practical application, so that the existing blue light devices are still based on blue fluorescent materials, which causes the blue light devices to need higher voltage and current density, reduces the efficiency and the service life of the blue light devices, and thus, the development of efficient and long-life blue light devices is needed.
In addition to the blue host combination luminescent layer with long luminous efficiency, the blue light device with high efficiency and long service life needs to be developed, and a proper electron transport material needs to be selected, so that electrons can be better injected into the luminescent layer, and the working voltage of the device is further reduced.
The invention content is as follows:
the present invention has been made in view of the above problems, and provides a blue light device having high efficiency and long lifetime, which comprises a specific combination of a host material, a guest material and an electron transport material.
In order to achieve the purpose, the invention adopts the following technical scheme that the LED comprises an anode, a cathode and an organic layer, wherein the organic layer comprises more than one blue light emitting layer and more than one electron transmission layer, and the light emitting layer and the electron transmission layer are matched for use;
the blue light emitting layer is composed of a host material represented by formula 1 below and a guest material represented by formula 2; the electron transport layer is prepared by co-evaporating a compound represented by formula 3 and an organic alkali metal compound;
wherein Ar is1、Ar2Is a substituted or unsubstituted aryl group of C6-C30, a substituted or unsubstituted heteroaryl group of C6-C30;
Ar3-Ar6is a substituted or unsubstituted aryl group of C6-C30, a substituted or unsubstituted heteroaryl group of C6-C30, R1、R2Is hydrogen, a substituted or unsubstituted alkyl group of C1 to C6;
R3is hydrogen, phenyl, biphenyl or naphthyl; ar (Ar)7、Ar8One is a pyridyl group or a benzonitrile group, and the other is a compound represented by the following formula 4,
wherein Ar is9、Ar10Is a substituted or unsubstituted aryl group of C6 to C30;
the total thickness of the organic layer is 1-1000nm, the thickness of the luminescent layer is 5-150nm, and the thickness of the electron transmission layer is 5-150 nm.
Preferably, Ar1、Ar2Is phenyl, naphthyl, biphenyl, phenylnaphthyl, naphthylphenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, phenyldibenzofuranyl or phenylbenzonaphthofuranyl.
Preferably, Ar3-Ar6Is phenyl, biphenyl, dibenzofuranyl or dibenzothienyl, R1、R2Is hydrogen, a substituted or unsubstituted alkyl group of C1 to C6.
Preferably, R3Is hydrogen or phenyl; ar (Ar)9And Ar10Independently represented as phenyl or biphenyl.
Formula 1 can be the following compound BH1-BH20,
formula 2 may be the following compounds BD1-BD24,
formula 3 can be the following compound ET1-ET24,
the organic layer is composed of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.
The organic layer is composed of a hole transport layer, a luminescent layer and an electron transport layer.
The host material of the blue light emitting layer is composed of more than one BH1-BH22 compound, the guest material is composed of more than one BD1-BD12 compound, and the electron transport layer is composed of more than one ET1-ET26 compound.
The proportion of the host material is 20-99.9% of the total weight of the luminescent layer, and the proportion of the guest material is 0.1-50%.
Preferably, the proportion of the host material is 80-99% of the total weight of the light-emitting layer, and the proportion of the guest material is 0.5-10%.
More preferably, the proportion of the host material is 90 to 99% by weight of the entire light-emitting layer.
The content ratio of the electron transport material to the alkali metal compound is 10: 90-90: 10.
Preferably, the content ratio of the electron transport material to the alkali metal compound is 30:70 to 70: 30.
More preferably, the content ratio of the electron transport material to the alkali metal compound is 40:60 to 60: 40.
The organic alkali metal compound in the electron transport layer is an organic ligand compound of more than one of lithium, sodium and potassium.
A more preferred alkali metal compound is lithium 8-hydroxyquinoline.
Preferably, the total thickness of the organic layer is 50 to 500nm, the thickness of the light emitting layer is 10 to 100nm, and the thickness of the electron transport layer is 10 to 100 nm.
More preferably, the thickness of the light-emitting layer is 15 to 80nm, and the thickness of the electron transport layer is 15 to 60 nm.
The hole transport layer and the hole injection layer are made of materials with good hole transport performance, holes can be effectively transported to the light-emitting layer from the anode, and other small molecule and high molecule organic compounds can be added into the hole transport layer and the hole injection layer, such as carbazole compounds, triarylamine compounds, biphenyldiamine compounds, fluorene compounds, phthalocyanine compounds, hexacyano hexa-triphenylene (hexanitrile hexaazatriphenylene), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanodimethyl-p-benzoquinone (F4-TCNQ), polyvinyl carbazole, polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer has good luminescent property, and the range of visible light can be adjusted according to requirements. Besides the structural formula 1 and the structural formula 2, the following compounds, naphthalene compounds, pyrene compounds, fluorene compounds and phenanthrene compounds can be added,
a fluoranthene compound, an anthracene compound, a pentacene compound, a perylene compound, a diarylethene compound, a triphenylamine ethene compound, an amine compound, a benzimidazole compound, a furan compound, or an organic metal chelate.
The organic electron transport material is required to have good electron transport performance, can effectively transport electrons from the cathode to the light-emitting layer, and has high electron mobility. In addition to using the compound having the structural formula 3 and an organic alkali metal, an oxaoxazole, a thiazole compound, a triazole compound, a triazine compound, a triazobenzene compound, an oxazoline compound, a diazoanthracene compound, a silicon-containing heterocyclic compound, a quinoline compound, a phenanthroline compound, a metal chelate (such as Alq3), a fluorine-substituted benzene compound, a benzimidazole compound, an alkali metal, an alkaline earth metal, a rare earth metal, an oxide or halide of an alkali metal, an oxide or halide of an alkaline earth metal, an oxide or halide of a rare earth metal, an organic complex of an alkali metal or an alkaline earth metal may be added; lithium, lithium fluoride, lithium oxide, lithium nitride, 8-hydroxyquinoline lithium, cesium carbonate, 8-hydroxyquinoline cesium, calcium fluoride, calcium oxide, magnesium fluoride, magnesium carbonate, magnesium oxide are preferable.
Each of the organic layers is prepared by a vacuum evaporation method, a molecular beam evaporation method, a dip coating method in a solvent, a spin coating method, a bar coating method, or an inkjet printing method. The metal electrode is prepared by an evaporation method or a sputtering method.
The invention has the beneficial effects that:
1. the blue light device of the invention has very high efficiency. The efficiency may be improved by injection of electrons from the electron transport layer into the light emitting layer to combine with holes to form excitons, which are efficiently converted into photons.
2. The blue light device has the advantage of long service life.
3. The blue light device of the invention has lower working voltage.
Description of the drawings:
FIG. 1 is a schematic structural diagram of the present invention.
110 is a glass substrate, 120 is an anode, 130 is a hole injection layer, 140 is a hole transport layer, 150 is a light emitting layer, 160 is an electron transport layer, 170 is an electron injection layer, and 180 is a cathode.
The specific implementation mode is as follows:
example 1
First, a transparent conductive ITO glass substrate 110 (with an anode 120 thereon) (south glass group, china ltd) was sequentially washed with deionized water, ethanol, acetone, and deionized water, and then treated with oxygen plasma for 30 seconds. Then, 5nm thick HIL was evaporated on the anode 120 as a hole injection layer 130; the evaporation of the compound HTL was continued to form a hole transport layer 140 having a thickness of 70 nm. Then, a light-emitting layer 150 having a thickness of 25nm was deposited on the hole-transporting layer, in which BH6 was a host light-emitting material and BD6 was 3% by weight as a guest material. Then, an electron transport layer 160 was evaporated onto the light-emitting layer to a thickness of 25nm, where the ratio of ET2 to LiQ was 50: 50. finally, 1nm LiF is evaporated to form the electron injection layer 170 and 100nm Al is evaporated to form the cathode 180 of the device.
The prepared device was analyzed by a Photo Research PR650 spectrometer at 10mA/cm2The test was performed at current density and the results are shown in table 1.
Example 2
The difference from example 1 is that BD8 is used as the guest material in the light-emitting layer instead of BD6, and ET6 is used as the electron transporting material instead of ET 2.
Example 3
The difference from example 1 is that the host material in the light-emitting layer was BH9 instead of BH6 and the electron transport material was ET6 instead of ET 2.
Example 4
The difference from example 1 is that the host material in the light-emitting layer was BH9 instead of BH6 and the electron transport material was ET22 instead of ET 2.
Comparative example 1
The difference from example 1 is that BD-a is used as the guest material in the light-emitting layer instead of BD 6.
Comparative example 2
The difference from mutexample 1 is that ET-a is used instead of ET2 for the electron transport material.
Comparative example 3
The difference from mutexample 1 is that BD6 was replaced with BD-a as a guest material of a light-emitting material, and ET2 was replaced with ET-a as an electron transporting material.
TABLE 1
As can be seen from Table 1, the combination of the blue host material and guest material, and electron transport material using the present invention was found to be at 10mA/cm2The operating voltage at current density of 3.Between 62 and 3.70V, the current efficiency is between 6.29 and 7.46cd/A, the power efficiency is between 5.69 and 6.84m/W, and the brightness is between 628 and 735cd/m2When the light-emitting material is replaced by BD-A, these values are 4.14V, 5.06cd/A, 4.10lm/W, 483.67cd/m, respectively2. When the electron transport layer is changed to ET-A or the emissive guest material is changed to BD-A and the electron transport material is changed to ET-A, the efficiency of the device is lower than that of mut mutexamples 1-4. In addition, another important parameter of the blue light device is the lifetime, the lifetimes of examples 1-4 using the material combination of the present invention are between 24-31 hours, while the lifetimes of comparative examples 1-3, prepared by varying the different electron transport materials and guest emitting materials, show a large difference between 15-20 hours.
When comparing comparative examples 1-3 with examples 1-4 of devices made using the material combinations of the present invention, the device efficiencies and lifetimes of examples 1-4 are significantly better than those of comparative examples 1-3 which do not use the combination. As described above, the organic electroluminescent device according to the present invention, which uses the compound of formula 1 as a light emitting host material, the compound of formula 2 as a light emitting guest material, and the compound of formula 3 as an electron transporting material, has high efficiency and long lifetime.
The structural formula of the compound in the device is as follows, all commercially available:
Claims (8)
1. the blue light device is characterized by comprising an anode, a cathode and an organic layer, wherein the organic layer comprises more than one blue light emitting layer and more than one electron transmission layer;
the blue light emitting layer is composed of a host material represented by formula 1 below and a guest material represented by formula 2; the electron transport layer is prepared by co-evaporating a compound represented by formula 3 and an organic alkali metal compound;
wherein Ar is1、Ar2Is a substituted or unsubstituted aryl group of C6-C30, a substituted or unsubstituted heteroaryl group of C6-C30;
Ar3-Ar6is a substituted or unsubstituted aryl group of C6-C30, a substituted or unsubstituted heteroaryl group of C6-C30, R1、R2Is hydrogen, a substituted or unsubstituted alkyl group of C1 to C6;
R3is hydrogen, phenyl, biphenyl or naphthyl; ar (Ar)7、Ar8One is a pyridyl group or a benzonitrile group, and the other is a compound represented by the following formula 4,
wherein Ar is9、Ar10Is a substituted or unsubstituted aryl group of C6 to C30; the total thickness of the organic layer is 1-1000nm, the thickness of the luminescent layer is 5-150nm, and the thickness of the electron transmission layer is 5-150 nm.
2. A high efficiency long lived blue light device as recited in claim 1, wherein Ar is1、Ar2Is phenyl, naphthyl, biphenyl, phenylnaphthyl, naphthylphenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, phenyldibenzofuranyl or phenylbenzonaphthofuranyl.
3. A high efficiency long lived blue light device as recited in claim 1, wherein Ar is3-Ar6Is phenyl, biphenyl, dibenzofuranyl or dibenzothienyl, R1、R2Is hydrogen, a substituted or unsubstituted alkyl group of C1 to C6.
4. A high efficiency long lifetime blue light device as claimed in claim 1, wherein R is3Is hydrogen or phenyl; ar (Ar)9And Ar10Independently of each otherRepresented as phenyl or biphenyl.
5. A high efficiency long life blue light device as claimed in claim 1, wherein said organic layer is composed of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.
6. A high efficiency long lived blue light device as claimed in claim 1 wherein the organic layer is comprised of a hole transport layer, a light emitting layer, an electron transport layer.
7. A high-efficiency long-life blue light device as claimed in claim 1, wherein the organic alkali metal compound in the electron transport layer is one or more organic ligand compounds of lithium, sodium and potassium.
8. A high efficiency long lifetime blue light device as claimed in claim 1, wherein the total thickness of the organic layers is 50-500nm, the thickness of the light emitting layer is 10-100nm, and the thickness of the electron transport layer is 10-100 nm.
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