CN111740020B - High-efficiency long-service-life blue light device - Google Patents
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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 light-emitting device 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 transport 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 the following formula 1 and a guest material represented by the formula 2; the electron transport layer is prepared from a compound represented by formula 3 and an organic alkali metal compound by co-evaporation;
Description
technical field:
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 background technology is as follows:
organic electroluminescent devices (OLEDs) are used as a novel display technology, have the unique advantages of self-luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, high response speed, wide applicable temperature range, low driving voltage, flexible, bendable and transparent display panel manufacturing, 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 an LCD.
The organic electroluminescent device is a device prepared by depositing a layer of organic material between two metal electrodes by spin coating or vacuum evaporation, and a classical three-layer organic electroluminescent device comprises a hole transport layer, a light emitting layer and an electron transport layer. Holes generated from the anode are combined with electrons generated from the cathode through the hole transport layer to form excitons in the light emitting layer through the electron transport layer, and then light is emitted. The organic electroluminescent device may adjust emission of 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 fluorescent OLED can be divided into a fluorescent OLED and a phosphorescent OLED according to a light emitting mechanism, the earliest fluorescent OLED only depends on 25% of singlet excitons, 75% of triplet excitons are wasted, then the internal quantum efficiency is only 25%, and the corresponding external quantum efficiency is only between 5 and 7.5%. The discovery of phosphorescent OLEDs is clearly a major breakthrough because phosphorescent emitters can fully utilize all excitons, thus achieving near 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, due to the high energy gap of blue light, the stability and the light purity of the blue phosphorescent material have great problems, so that the blue phosphorescent device cannot meet the practical application, and the current blue device is still based on the blue fluorescent material, thus the blue device needs higher voltage and current density, the efficiency and the service life of the blue device are reduced, and therefore, the development of the blue device with high efficiency and long service life is required.
In addition to selecting a blue light host combination light emitting layer with long light emitting efficiency, a suitable electron transport material is also required to be selected to enable electrons to be better injected into the light emitting layer and further reduce the operating voltage of the device, so that development of an applicable blue light device requires optimization of combining a light emitting material with thin film stability and good thermal stability and an electron transport material to obtain a device with carrier balance, high efficiency, low driving voltage and long lifetime.
The invention comprises the following steps:
the present invention addresses the above-described problems by providing a blue light device having a high efficiency and a long lifetime, which comprises a specific combination of a host material, a guest material, and an electron transport material.
In order to achieve the above purpose, the invention adopts the following technical scheme that the anode, the cathode and the organic layer are included, the organic layer comprises more than one blue light luminescent layer and more than one electron transport layer, and the luminescent layer and the electron transport layer are used in a matching way;
the blue light emitting layer is composed of a host material represented by the following formula 1 and a guest material represented by the formula 2; the electron transport layer is prepared from a compound represented by formula 3 and an organic alkali metal compound by co-evaporation;
wherein Ar is 1 、Ar 2 Substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C6-C30;
Ar 3 -Ar 6 is a C6-C30 substituted or unsubstituted aryl, a C6-C30 substituted or unsubstituted heteroaryl, R 1 、R 2 Substituted or unsubstituted alkyl of hydrogen, C1-C6;
R 3 hydrogen, phenyl, biphenyl or naphthyl; ar (Ar) 7 、Ar 8 One of them is a pyridyl group or a benzonitrile group, the other is a compound represented by the following formula 4,
wherein Ar is 9 、Ar 10 Substituted or unsubstituted aryl of C6-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 transport layer is 5-150nm.
Preferably Ar 1 、Ar 2 Is phenyl, naphthyl, biphenyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, phenyldibenzofuranyl or phenylbenzonaphthofuranyl.
Preferably Ar 3 -Ar 6 Is phenyl, biphenyl, dibenzofuranyl or dibenzothienyl, R 1 、R 2 Is hydrogen, C1-C6 substituted or unsubstituted alkyl.
Preferably, R 3 Is hydrogen or phenyl; ar (Ar) 9 And Ar is a group 10 Independently denoted phenyl or biphenyl.
Formula 1 may be the following compounds BH1-BH20,
formula 2 may be the following compounds BD1-BD24,
formula 3 may be the following compounds ET1-ET24,
the organic layer consists 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 light emitting 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 host material accounts for 20-99.9% of the total weight of the light-emitting layer, and the guest material accounts for 0.1-50%.
Preferably, the host material is 80-99% by weight of the entire light emitting layer, and the guest material is 0.5% -10%.
More preferably, the host material is present in an amount of 90-99% 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 and the alkali metal compound is 40:60 to 60:40.
The organic alkali metal compound in the electron transport layer is more than one organic ligand compound of lithium, sodium and potassium.
A more preferred alkali metal compound is lithium 8-hydroxyquinoline.
Preferably, the total thickness of the organic layer is 50-500nm, the thickness of the light emitting layer is 10-100nm, and the thickness of the electron transporting layer is 10-100nm.
More preferably, the light emitting layer has a thickness of 15 to 80nm and the electron transporting layer has a thickness of 15 to 60nm.
The hole transport layer and the hole injection layer have good hole transport performance, and can effectively transport holes from the anode to the light-emitting layer, and other small molecules and high molecular organic compounds such as carbazole compounds, triarylamine compounds, biphenyldiamine compounds, fluorene compounds, phthalocyanine compounds, hexacyanohexa-triphenyl (hexa-tril-hexa-triphenyl), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl p-benzoquinone (F4-TCNQ), polyvinylcarbazole, polythiophene, polyethylene or polystyrene sulfonic acid can be added into the hole transport layer and the hole injection layer.
The luminous layer has good luminous characteristics and can adjust the range of visible light according to the requirement. In addition to the structural formulas 1 and 2, the following compounds, naphthalene compounds, pyrene compounds, fluorene compounds, phenanthrene compounds,
a class of compounds, fluoranthene compounds, anthracene compounds, pentacene compounds, perylene compounds, diarylethenes compounds, triphenylamine vinyl compounds, amines compounds, benzimidazoles compounds, furans compounds, or organometallic chelates.
The organic electron transport material is required to have good electron transport properties, to be able to efficiently transport electrons from the cathode into the light emitting layer, and to have a large electron mobility. In addition to the compounds of formula 3 and organic alkali metals, oxaoxazoles, thiazoles, triazoles, triazabenzenes, oxines, diazines, silaheterocycles, quinolines, phenanthrines, metal chelates (e.g., alq 3), fluorine-substituted benzenes, benzimidazoles, alkali metals, alkaline earth metals, rare earth metals, oxides or halides of alkali metals, oxides or halides of alkaline earth metals, oxides or halides of rare earth metals, organic complexes of alkali metals or alkaline earth metals can be added; preferred are lithium, lithium fluoride, lithium oxide, lithium nitride, lithium 8-hydroxyquinoline, cesium carbonate, cesium 8-hydroxyquinoline, calcium fluoride, calcium oxide, magnesium fluoride, magnesium carbonate, and magnesium oxide.
Each of the organic layers is prepared by a vacuum evaporation method, a molecular beam evaporation method, a solvent-soluble dip coating method, 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 present invention has very high efficiency. The improvement in efficiency may be due to the injection of electrons from the electron transport layer to the light emitting layer to combine with holes sufficiently 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 has lower working voltage.
Description of the drawings:
fig. 1 is a schematic structural view 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 embodiment is as follows:
example 1
First, a transparent conductive ITO glass substrate 110 (with an anode 120 thereon) (south glass group limited of china) was washed with deionized water, ethanol, acetone, deionized water in this order, and then treated with oxygen plasma for 30 seconds. Next, HIL having a thickness of 5nm was vapor-deposited as a hole injection layer 130 on the anode 120; the evaporation of the compound HTL was continued to form a 70nm thick hole transport layer 140. Then, a light-emitting layer 150 having a thickness of 25nm was deposited on the hole transport layer, wherein BH6 was used as a host light-emitting material and BD6 having a weight ratio of 3% was used as a guest material. Then, an electron transport layer 160 of 25nm thickness was evaporated on the light emitting layer, wherein the ratio of ET2 to LiQ was 50:50. finally, 1nm LiF was evaporated as the electron injection layer 170 and 100nm Al as the device cathode 180.
The prepared device was measured at 10mA/cm using a Photo Research PR650 spectrometer 2 The test was conducted at current density and the results are shown in table 1.
Example 2
The difference from example 1 is that the guest material in the light-emitting layer is BD8 instead of BD6 and the electron transport material is ET6 instead of ET2.
Example 3
The difference from example 1 is that BH9 is used instead of BH6 as the host material in the light-emitting layer, and ET6 is used instead of ET2 as the electron-transporting material.
Example 4
The difference from example 1 is that the host material in the light-emitting layer is BH9 instead of BH6 and the electron transport material is ET22 instead of ET2.
Comparative example 1
The difference from example 1 is that BD-a is used instead of BD6 as the guest material in the light emitting layer.
Comparative example 2
The difference from example 1 is that the electron transport material replaces ET2 with ET-a.
Comparative example 3
The difference from example 1 is that the guest material of the light emitting material was BD-A instead of BD6 and the electron transporting material was ET-A instead of ET2.
TABLE 1
As can be seen from Table 1, the combination of the blue host material and the guest material, and the electron transporting material, to which the present invention was applied, was measured at 10mA/cm 2 The working voltage under the current density is 3.62-3.70V, the current efficiency is 6.29-7.46cd/A, the power efficiency is 5.69-6.84m/W, and the brightness is 628-735cd/m 2 When the light-emitting material is replaced with BD-A, the values are 4.14V,5.06cd/A,4.10lm/W,483.67cd/m, respectively 2 . When the electron transport layer is changed to ET-A or the light emitting guest material is changed to BD-A, the electron transport material is changed to ETAt-a, the efficiency of the device was lower than in examples 1-4. In addition, another important parameter of the blue light device was lifetime, and the lifetime of examples 1 to 4 using the material combination of the present invention was 24 to 31 hours, whereas the lifetime of comparative examples 1 to 3 prepared by changing different electron transporting materials and guest light emitting materials was 15 to 20 hours, showing a large difference.
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 such combinations. As described above, the organic electroluminescent device of 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, is prepared with high efficiency and long lifetime.
The structural formula of the compounds in the device is as follows, and the compounds are obtained from the market:
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 transport layer, and the light emitting layer and the electron transport layer are matched for use;
the blue light emitting layer is composed of a host material represented by the following formula 1 and a guest material represented by the formula 2; the electron transport layer is prepared from a compound represented by formula 3 and an organic alkali metal compound by co-evaporation;
wherein Ar is 1 、Ar 2 Substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C6-C30;
Ar 3 -Ar 6 is a C6-C30 substituted or unsubstituted aryl, a C6-C30 substituted or unsubstituted heteroaryl, R 1 、R 2 Substituted or unsubstituted alkyl of hydrogen, C1-C6;
R 3 hydrogen, phenyl, biphenyl or naphthyl; ar (Ar) 7 、Ar 8 One of them is a pyridyl group or a benzonitrile group, the other is a compound represented by the following formula 4,
wherein Ar is 9 、Ar 10 Substituted or unsubstituted aryl of C6-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 transport layer is 5-150nm.
2. The high efficiency long life blue light device according to claim 1, wherein Ar 1 、Ar 2 Is phenyl, naphthyl, biphenyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, phenyldibenzofuranyl or phenylbenzonaphthofuranyl.
3. The high efficiency long life blue light device according to claim 1, wherein Ar 3 -Ar 6 Is phenyl, biphenyl, dibenzofuranyl or dibenzothienyl, R 1 、R 2 Is hydrogen, C1-C6 substituted or unsubstituted alkyl.
4. The high efficiency long life blue light device of claim 1, wherein R 3 Is hydrogen or phenyl; ar (Ar) 9 And Ar is a group 10 Independently denoted phenyl or biphenyl.
5. The blue light component according to claim 1, wherein said organic layer comprises 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. The high efficiency long life blue light device according to claim 1, wherein the organic layer is comprised of a hole transporting layer, a light emitting layer, an electron transporting layer.
7. The blue light component of claim 1, wherein said organic alkali metal compound in said electron transport layer is one or more organic ligand compounds of lithium, sodium and potassium.
8. The blue light component of claim 1, wherein the total thickness of the organic layer is 50-500nm, the thickness of the light-emitting layer is 10-100nm, and the thickness of the electron transport layer is 10-100nm.
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