CN114621205B - Derivative of oxygen-containing heterocyclic compound, light-emitting device, and display device - Google Patents

Derivative of oxygen-containing heterocyclic compound, light-emitting device, and display device Download PDF

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CN114621205B
CN114621205B CN202210241854.3A CN202210241854A CN114621205B CN 114621205 B CN114621205 B CN 114621205B CN 202210241854 A CN202210241854 A CN 202210241854A CN 114621205 B CN114621205 B CN 114621205B
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oxygen
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CN114621205A (en
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高荣荣
黎俊聪
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BOE Technology Group Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
    • C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

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Abstract

The embodiment of the disclosure provides a derivative of an oxygen-containing heterocyclic compound, a light-emitting device and a display device, wherein the derivative of the oxygen-containing heterocyclic compound has a structure shown in a general formula I:wherein R1-R4 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, C6-C60 mono-or di-arylphosphino, and C6-C60 arylamino.

Description

Derivative of oxygen-containing heterocyclic compound, light-emitting device, and display device
Technical Field
The disclosure relates to the technical field of display, in particular to a derivative of an oxygen-containing heterocyclic compound, a light-emitting device and a display device.
Background
An organic light emitting diode (Organic Light Emitting Diode, OLED) device is an electroluminescent device based on organic semiconductor materials, and with the rapid development of the OLED display industry, the requirement on the luminous efficiency of the OLED device is higher and higher.
Disclosure of Invention
The embodiment of the disclosure provides a derivative of an oxygen-containing heterocyclic compound, a light-emitting device and a display device.
In a first aspect, embodiments of the present disclosure provide a derivative of an oxygen-containing heterocyclic compound having a structure represented by formula I:
wherein R1-R4 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, C6-C60 mono-or di-arylphosphino, and C6-C60 arylamino;
at least two of the R1-R4 groups contain a first group; alternatively, one of the R1-R4 groups contains a second group;
wherein the first group has a structure represented by the general formula II:
x in the first group 1 -X 3 Each independently selected from C, N, and X 1 -X 3 Comprises at least two N;
Ar 1 and Ar is a group 2 Each independently selected from aryl and heteroaryl;
L 1 is directly bonded and is selected from one of aryl, heteroaryl, phenyl and heterocyclylene;
the second group has a structure shown in a general formula III:
ar in the second group 5 And Ar is a group 6 Each independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;
l is a direct bond, a substituted or unsubstituted phenylene, biphenylene, or naphthylene group;
y is selected from O or S.
In some embodiments, when at least two of R1-R4 contain a first group, the molecular formula of the derivative of the oxygen-containing heterocyclic compound is selected from the following formulas (1-1) through (1-8):
in some embodiments, when one of R1-R4 contains a second group, the derivative of the oxygen-containing heterocyclic compound has a structure represented by the general formula:
in some embodiments, any adjacent two groups of R1-R4 are capable of bonding to form a condensed ring.
In a second aspect, embodiments of the present disclosure provide a light emitting device, including:
a first electrode, a light emitting layer, and an electron transport layer between the first electrode and the light emitting layer;
the material of the electron transporting layer includes a derivative of the oxygen-containing heterocyclic compound according to any one of claims 1 to 5.
In some embodiments, the electron transport layer has a thickness of 20-100nm.
In some embodiments, the material of the electron transport layer further comprises Liq; the doping ratio of the derivative of the oxygen-containing heterocyclic compound to the Liq is between 0.9:1 and 1.1:1.
In some embodiments, the light emitting device further comprises: a second electrode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a hole blocking layer, and an electron injection layer;
the electron injection layer is positioned between the first electrode and the electron transport layer;
the hole blocking layer is positioned between the electron transport layer and the light emitting layer;
the light-emitting auxiliary layer, the hole transport layer, the hole injection layer and the second electrode are positioned on one side of the light-emitting layer away from the first electrode and are sequentially arranged along the direction away from the light-emitting layer.
In a third aspect, embodiments of the present disclosure provide a display substrate including the light emitting device of the second aspect.
In a fourth aspect, embodiments of the present disclosure provide a display device including the display substrate of the third aspect.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a schematic diagram of a synthesis process of a derivative of an oxygen-containing heterocyclic compound according to an embodiment of the present disclosure;
FIG. 2 is a schematic diagram of a synthesis process of a derivative of another oxygen-containing heterocyclic compound provided in an embodiment of the present disclosure;
FIG. 3 is a schematic diagram of a synthesis process of a derivative of another oxygen-containing heterocyclic compound provided in an embodiment of the present disclosure;
FIG. 4 is a perspective view of a derivative of an oxygen-containing heterocyclic compound according to an embodiment of the present disclosure;
FIG. 5 is a perspective view of a derivative of another oxygen-containing heterocyclic compound provided in an embodiment of the present disclosure;
FIG. 6 is an electron cloud distribution diagram of a derivative of an oxygen-containing heterocyclic compound according to an embodiment of the present disclosure;
fig. 7 is a schematic structural diagram of a light emitting device according to an embodiment of the present disclosure.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present disclosure. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present disclosure. All other embodiments, which can be made by one of ordinary skill in the art without the need for inventive faculty, are within the scope of the present disclosure, based on the described embodiments of the present disclosure.
Unless defined otherwise, technical or scientific terms used in embodiments of the present disclosure should be given the ordinary meaning as understood by one of ordinary skill in the art to which the present disclosure belongs. The terms "first," "second," and the like, as used in this disclosure, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Likewise, the word "comprising" or "comprises", and the like, means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof, but does not exclude other elements or items. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", etc. are used merely to indicate relative positional relationships, which may also be changed when the absolute position of the object to be described is changed.
With the advancement of information industry, conventional display devices have failed to meet the demands of people, for example: cathode ray tube displays are bulky and have high driving voltages; the liquid crystal display has low brightness, narrow viewing angle and small working temperature range; the plasma display is expensive, low in resolution and high in power consumption.
The organic electroluminescent device (Organic Light Emitting Diode, OLED) is an electroluminescent device based on organic semiconductor material, which is a completely new display technology, and has great advantages in various performances compared with the existing display devices, such as full solid state, self-luminescence, high brightness, high resolution, wide viewing angle, fast response speed, small volume, light weight, low power consumption, flexible substrate and low voltage dc drive. Based on the above characteristics, the OLED device has a very wide application market, such as lighting systems, communication systems, vehicle-mounted displays, portable electronic devices, high-definition displays, even military fields, and the like.
Although the OLED device has continuously achieved breakthrough in the display field, the conventional display device forms a powerful challenge, but there are still some problems to be solved in the research process of the luminescent materials in the OLED device.
The OLED device is a dual injection type light emitting device, electrons injected from a first electrode and holes injected from a second electrode are recombined in a light emitting layer under the driving of an external voltage to form electron-hole pairs at a bound energy level, that is, excitons are formed, and the excitons drop to a ground state to generate visible light. In order to enhance the injection and transport capabilities of electrons and holes in a light emitting device, an electron transport layer is generally added between a first electrode and a light emitting layer, and a hole transport layer is added between the light emitting layer and a second electrode, thereby improving light emitting performance. The electron transport material in the electron transport layer is in a system of electron deficiency in molecular structure, has strong electron accepting capability, and has a good reversible reduction process.
Common electron transport materials mainly include Tetracyanoquinodimethane (TCNQ), trinitrofluorenone (TNF), (8-hydroxyquinoline) aluminum (Alq 3), oxadiazole (Oxadiazole), triazole, naphthalene anhydride, flower anhydride, C60, derivatives thereof, and the like. The compound material has low three-dimensional property of a core structure and is easy to crystallize; secondly, effective separation of HOMO and LUMO cannot be achieved, and matching of material energy levels and adjacent functional layers cannot be flexibly adjusted; finally, the structure of the above compound materials is easily deformed, and the glass transition temperature is low, which cannot provide better thermal stability.
In summary, the electron transport materials disclosed in the prior art cannot simultaneously achieve both charge injection and transport characteristics, and have a certain effect on the light emitting efficiency and the device lifetime of the OLED device.
To solve at least one of the above technical problems, an embodiment of the present disclosure provides a derivative of an oxygen-containing heterocyclic compound having a structure represented by general formula i:
wherein R1-R4 are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, C6-C60 mono-or di-arylphosphino, and C6-C60 arylamino.
In some embodiments, at least two of R1-R4 contain a first group having a structure represented by formula II:
x in the first group 1 -X 3 Each independently selected from C, N, and X 1 -X 3 Comprises at least two N; ar (Ar) 1 And Ar is a group 2 Each independently selected from aryl and heteroaryl; l (L) 1 Is directly bonded and is selected from one of aryl, heteroaryl, phenyl and heterocyclylene.
Alternatively, when at least two of R1 to R4 contain a first group, the molecular formula of the derivative of the oxygen-containing heterocyclic compound is selected from the following formulas (1-1) to (1-8):
it should be noted that, the bonding between two to four first groups in the formula and the compound shown in the general formula i is performed through L1, but multiple L1 in the same formula may be the same or different, and each of them independently selects aryl, heteroaryl, phenyl, and heterocyclylene, which is not limited in the examples of the present disclosure.
The derivative of the oxygen-containing heterocyclic compound formed by combining the general formula I and the general formula II can provide higher mobility for transport carriers, namely, can improve the electron transport efficiency when being used as an electron transport material of an OLED device.
In some embodiments, one of R1-R4 contains a second group having a structure represented by formula III:
ar in the second group 5 And Ar is a group 6 Each independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; l is a direct bond, a substituted or unsubstituted phenylene, biphenylene, or naphthylene group; y is selected from O or S.
Alternatively, when one of R1-R4 contains a second group, it has a structure represented by the general formula:
when the derivative of the oxygen-containing heterocyclic compound shown in the general formula is used as an electron transport material of an OLED device, the electron injection efficiency can be improved.
The general formulae II and III are electron withdrawing groups. Because the oxygen-containing heterocyclic compound shown in the general formula I belongs to an electron donating group, the combination of the oxygen-containing heterocyclic compound and an electron withdrawing group can realize effective separation of HOMO and LUMO, and further can flexibly adjust the matching between the energy level of a compound material and an adjacent functional layer, thereby realizing better electron transmission capability.
In some embodiments, the electron withdrawing group comprises a first group;
the derivative of the oxygen-containing heterocyclic compound provided by the embodiment of the disclosure has an orthogonal space three-dimensional structure, so that crystallization of materials can be effectively prevented. As one of the spiro compounds, the spiro compound maintains a higher triplet energy level, prevents excitons generated in the light-emitting layer from diffusing into the electron transport layer, and further improves the light-emitting efficiency of the display device. In addition, the derivative of the oxygen-containing heterocyclic compound has a good rigid structure, and the structure is not easy to deform under the action of no external force, so that the material has a good glass transition temperature, and the stability of the material is improved.
In some embodiments, any two adjacent groups of R1-R4 are capable of bonding to form a condensed ring.
Some alternative examples of derivatives of oxygen-containing heterocyclic compounds are provided below:
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the compounds 1-50 in the examples of the derivative of the oxygen-containing heterocyclic compound have an orthogonal space three-dimensional structure and a good rigid structure, and can have higher luminous efficiency while ensuring high mobility of the material. Meanwhile, the electron withdrawing group contained in the polymer can realize effective separation of HOMO and LUMO, and is beneficial to realizing better electron injection and transmission performance.
Alternatively, compound 1 in the above-described examples of the derivative of the oxygen-containing heterocyclic compound may be synthesized by:
FIG. 1 is a schematic diagram showing a synthesis process of a derivative of an oxygen-containing heterocyclic compound according to an embodiment of the present disclosure, wherein, as shown in FIG. 1, after compound a1 (7.34 g) and compound a2 (15.54 g) are completely dissolved in 300ml of tetrahydrofuran in a 500ml round bottom flask under nitrogen atmosphere, 2M aqueous potassium carbonate solution (100 ml) is added, and bis (tri-t-butylphosphine) palladium (0.46 g) is added, followed by stirring under heating for 5 hours. The temperature was lowered to room temperature, the aqueous layer was removed, and after drying over anhydrous magnesium sulfate, concentration was performed under reduced pressure, and recrystallization was performed with 150ml of ethyl acetate, whereby compound 1 was obtained.
Alternatively, the compound 39 in the above-described derivative example of the oxygen-containing heterocyclic compound may be synthesized by:
FIG. 2 is a schematic diagram showing a synthesis process of a derivative of another oxygen-containing heterocyclic compound provided in the example of the present disclosure, as shown in FIG. 2, after completely dissolving compound b1 (9.17 g) and compound b2 (6.09 g) in 200ml of tetrahydrofuran in a 500ml round bottom flask under nitrogen atmosphere, 2M aqueous potassium carbonate solution (100 ml) was added, and bis (tri-t-butylphosphine) palladium (0.50 g) was added, followed by stirring with heating for 12 hours. The temperature was lowered to room temperature, the aqueous layer was removed, and after drying over anhydrous magnesium sulfate, concentration was performed under reduced pressure, and recrystallization was performed with 150ml of ethanol, whereby compound b3 was obtained.
After compound b3 (13.52 g) and compound b4 (8.07 g) were completely dissolved in 200ml of tetrahydrofuran in a 500ml round-bottomed flask under a nitrogen atmosphere, 2M aqueous potassium carbonate solution (100 ml) was added, and bis (tri-t-butylphosphine) palladium (0.40 g) was added, followed by stirring with heating for 12 hours. The temperature was lowered to room temperature, the aqueous layer was removed, and after drying over anhydrous magnesium sulfate, concentration was performed under reduced pressure, and recrystallization was performed with 150ml of ethanol, whereby compound 39 was obtained.
Alternatively, the compound 45 in the above-described derivative example of the oxygen-containing heterocyclic compound may be synthesized by:
fig. 3 is a schematic diagram of a synthesis process of a derivative of another oxygen-containing heterocyclic compound provided in an embodiment of the present disclosure, as shown in fig. 3, compound c1 (15.0 g), compound c2 (13.6 g), and potassium carbonate (13.9 g) are added to dioxane (135 mL) and water (51 mL) under a nitrogen atmosphere, and the resulting mixture is degassed with nitrogen. Tetrakis (triphenylphosphine) palladium (0) (0.519 g) was then added. Stirred at 90℃overnight. The reaction mixture was cooled and the solvent was removed under vacuum. The crude residue was dissolved in dichloromethane and washed with deionized water (3X 100 ml). The organic phase was dried over MgSO 4 Drying, concentration under reduced pressure, and recrystallization from toluene gave compound 45.
Fig. 4 is a perspective view of a derivative of an oxygen-containing heterocyclic compound according to an embodiment of the present disclosure, and fig. 5 is a perspective view of a derivative of another oxygen-containing heterocyclic compound according to an embodiment of the present disclosure.
In addition, the derivative of the oxygen-containing heterocyclic compound shown in the above general formula I has a structure of a three-dimensional configuration shown in FIG. 4 or FIG. 5 when the material properties thereof are simulated using molecular simulation software. Because the structure of the oxygen-containing heterocyclic compound belongs to an orthogonal space three-dimensional configuration, the structure can enable the derivative of the oxygen-containing heterocyclic compound to effectively prevent crystallization of materials due to the existence of the spiro compound.
Fig. 6 is an electron cloud distribution diagram of a derivative of an oxygen-containing heterocyclic compound according to an embodiment of the present disclosure, where HOMO of the derivative of the oxygen-containing heterocyclic compound is better separated from LUMO as shown in fig. 6, so that the energy level of the material can be adjusted to achieve optimal matching with an adjacent functional layer. Meanwhile, because a plurality of fragments with larger dipole moment are introduced into the oxygen-containing heterocyclic compound, the dipole moment of the material can be improved, the electron injection characteristic of the organic electroluminescent material can be improved, the transmission characteristic of the material can be improved, the driving voltage of the light-emitting device can be reduced, and the light-emitting efficiency of the light-emitting device can be improved.
Fig. 7 is a schematic structural diagram of a light emitting device according to an embodiment of the present disclosure, and as shown in fig. 7, the light emitting device includes a substrate 10 disposed thereon: a first electrode 1, an electron transport layer 2 and a light emitting layer 3, wherein the electron transport layer 2 is located between the first electrode 1 and the light emitting layer 3, and the material of the electron transport layer 2 comprises the above oxygen-containing heterocyclic compound. Based on the oxygen-containing heterocyclic compound, the oxygen-containing heterocyclic compound has an orthogonal space three-dimensional structure and a good rigid structure, can prevent crystallization of materials, and improves the luminous efficiency of the luminous device. Meanwhile, the glass fiber reinforced plastic composite material has a good rigid structure, and the structure is not easy to deform under the action of no external force, so that the material has a good glass transition temperature, and the stability of electron transmission is improved.
In some embodiments, the electron transport layer 2 has a thickness of 20-100nm. Preferably, the thickness of the electron transport layer 2 is 30nm.
In some embodiments, the material of the electron transport layer further comprises Liq; the doping ratio of the derivative of the oxygen-containing heterocyclic compound to Liq is between 0.9:1 and 1.1:1. For example, the doping ratio of the derivative of the oxygen-containing heterocyclic compound to Liq is 1:1.
In some embodiments, as shown in fig. 7, the light emitting device further includes a light emitting element disposed on the substrate base plate 10: a second electrode 4, a hole injection layer 5, a hole transport layer 6, a light emitting auxiliary layer 7, a hole blocking layer 8, and an electron injection layer 9. Wherein the electron injection layer 9 is located between the first electrode 1 and the electron transport layer 2; a hole blocking layer 8 is located between the electron transport layer 2 and the light emitting layer 3; the light-emitting auxiliary layer 7, the hole transport layer 6, the hole injection layer 5 and the second electrode 4 are positioned on the side of the light-emitting layer 3 away from the first electrode 1 and are sequentially arranged along the direction away from the light-emitting layer 3.
It should be further noted that, the light emitting device provided in the embodiment of the present disclosure may be a front-mounted light emitting device, or may be an inverted light emitting device, that is, the second electrode 4, the hole injection layer 5, the hole transport layer 6, the light emitting auxiliary layer 7, the light emitting layer 3, the hole blocking layer 8, the electron transport layer 2, the electron injection layer 9, and the second electrode 1 may be sequentially disposed in a direction away from the substrate 10, or the second electrode 4, the hole injection layer 5, the hole transport layer 6, the light emitting auxiliary layer 7, the light emitting layer 3, the hole blocking layer 8, the electron transport layer 2, the electron injection layer 9, and the second electrode 1 may be sequentially disposed in a direction close to the substrate 10. In addition, the light emitting device provided by the embodiment of the present disclosure may be a top emission type light emitting device or a bottom emission type light emitting device; that is, the first electrode 1 may be provided as a transparent electrode and the second electrode 4 as a reflective electrode; the first electrode 1 may be provided as a reflective electrode and the second electrode 4 as a transparent electrode. In addition, the sequential lamination described in the embodiments of the present disclosure does not mean sequential contact, and other film layers may be provided therein, for example, an electron blocking layer or the like may be further provided between the hole transport layer 6 and the light emitting layer 3. In view of the above, the present disclosure is not limited in this regard.
The steps for manufacturing the light emitting device will be described in detail with reference to specific embodiments. Meanwhile, it can be seen that the lifetime of the light emitting device provided in the various embodiments of the present disclosure is significantly improved by comparing the data between the various embodiments and the comparative example.
Example 1
The light emitting device provided by the embodiment of the disclosure can be manufactured through the following steps:
s1, a substrate base 10 is provided, which employs a rigid or flexible transparent substrate, such as a glass substrate, a polyimide substrate, or the like.
S2, the second electrode 4 is formed on the base substrate 10, and the second electrode 4 is formed on the base substrate by, for example, a vacuum deposition method to have a thickness of 5 to 30nm. Wherein the thickness of the second electrode 4 is 10nm. Then, the substrate with the second electrode 4 formed thereon is subjected to ultrasonic treatment in a cleaning agent, rinsed in deionized water, subjected to ultrasonic degreasing in an acetone-ethanol mixed solvent, and baked in a clean environment until the water is completely removed.
Wherein the second electrode 4 can be a single-layer transparent electrode made of high work function electrode material, such as transparent oxide ITO, IZO; the composite electrode may be formed of ITO/Ag/ITO, ag/IZO, CNT/ITO, CNT/IZO, GO/ITO, GO/IZO, etc.
And S3, forming a hole injection layer 5. Optionally, the substrate with the second electrode 4 is placed in a vacuum chamber, and vacuumized to 1×10 -5 ～1×10 -6 Pa, a hole injection material is vacuum deposited on the second electrode 4 to form a hole injection layer 5 having a thickness of 5 to 30nm. For example, the thickness of the hole injection layer 5 is 10nm.
The material of the hole injection layer 5 may be specifically an inorganic oxide such as molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, or the like; dopants of a strong electron withdrawing system such as F4TCNQ, HATCN (the molecular formula of which is shown below) and the like are also possible. The hole injection layer 5 can also be formed by co-evaporation by P-type doping in the hole transport material with a doping thickness of 5-20 nm.
S4, a hole transport layer 6 is formed on the hole injection layer 4. Alternatively, the hole transport layer 6 is formed to have a thickness of 100 to 200nm by vapor deposition. For example, the thickness of the hole transport layer 6 is 100nm.
The material of the hole transport layer 6 may be specifically an arylamine or carbazole compound material, such as NPB (the molecular formula of which is shown below), TPD, BAFLP, DFLDPBi, and the like, which have good hole transport properties.
S5, a light-emitting auxiliary layer 7 is formed on the hole transport layer 6, and may be formed by vacuum evaporation. The light-emitting auxiliary layer 7 may be a red light-emitting auxiliary layer, a green light-emitting auxiliary layer, or a blue light-emitting auxiliary layer. The light-emitting auxiliary layer 7, such as CBP (whose molecular formula is shown below), PCzPA, and the like.
S6, forming an electron blocking layer on the light emitting auxiliary layer 7. Optionally, an electron blocking layer with a thickness of 5-100 nm is formed by vacuum evaporation. For example, the electron blocking layer has a thickness of 35nm.
S7, forming a light emitting layer 3 on the electron blocking layer, optionally forming the light emitting layer 3 with a thickness of 20-100nm by vacuum evaporation. For example, the thickness of the light emitting layer 3 is 20nm.
The light emitting layer 3 may include a host material and a guest material, and be formed by a multi-source co-evaporation method, wherein the weight ratio of the host material to the guest material is 9:1.
In one example, the light emitting layer 3 includes a host material BH and a guest material BD doped in BH, and the doping ratio of the guest material BD in the host material BH is 3wt%.
The light emitting material included in the light emitting layer 3 may be one of a red light emitting material, a green light emitting material, and a blue light emitting material. The luminescent material corresponding to each color can only comprise one material, and can also comprise two or more mixed materials. The luminescent materials of the three colors are respectively as follows:
the host material in the blue luminescent material can be selected from anthracene derivatives ADN, MADN, and the like; the guest material may be a pyrene derivative, a fluorene derivative, a perylene derivative, a styrylamine derivative, a metal complex, or the like, such as TBPe, BDAVBi, DPAVBi, FIrpic, or the like.
The host material in the green luminescent material can be selected from coumarin dye, quinacridone derivatives, polycyclic aromatic hydrocarbon, diamine anthracene derivatives, carbazole derivatives, such as DMQA, BA-NPB, alq 3 Etc. ObjectThe material may be a metal complex, such as Ir (ppy) 3 、Ir(ppy) 2 (acac), and the like.
The host material in the red luminescent material can be selected from DCM series materials such as DCM, DCJTB, DCJTI, etc., and the guest material can be metal complex such as Ir (piq) 2 (acac)、PtOEP、Ir(btp) 2 (acac), and the like.
S8, a hole blocking layer 8 is formed on the light emitting layer 3. Alternatively, the hole blocking layer 8 is formed by vacuum evaporation to a thickness of 5 to 100nm. For example, the hole blocking layer 8 has a thickness of 5nm.
The material of the hole blocking layer 8 may be an aromatic heterocyclic compound such as a pyrimidine derivative, a triazine derivative, or a oxazine derivative; examples of the compounds include compounds having a nitrogen-containing six-membered ring structure (including compounds having a phosphine oxide substituent on the heterocycle), such as quinoline derivatives, isoquinoline derivatives and phenanthroline derivatives, and examples include OXD-7, TAZ, p-EtTAZ, BPhen and BCP.
S9, the electron transport layer 2 is formed on the hole blocking layer 8. Alternatively, the electron transport layer 2 is formed to a thickness of 20 to 100nm by vacuum evaporation. For example, the thickness of the electron transport layer 2 is 30nm.
The material of the electron transport layer 2 described above adopts the above compound 1 provided in the examples of the present disclosure.
In addition, the material of the electron transport layer 2 may further include Liq, where the doping ratio of the above compound 1 to Liq in the electron transport layer is 1:1.
S10, an electron injection layer 9 is formed on the electron transport layer 2. Alternatively, the electron injection layer 9 is formed to have a thickness of 1 to 10nm by vacuum evaporation. Preferably, the thickness of the electron injection layer 9 is 1nm.
The material of the electron injection layer 9 may be an alkali metal or a metal, for example LiF, yb, mg, ca or a compound formed by combining the above metals, or the like.
S11, the first electrode 1 is formed on the electron injection layer 9. Alternatively, the thickness of the first electrode 1 is between 50 and 200nm, for example 100nm, and the material of the first electrode 1 may be Al.
Example two
The difference from the first embodiment is that: the electron transport layer 2 in S9 uses the above-described compound 39 instead of the compound 1 in the embodiment. The other steps are the same as in the first embodiment.
Example III
The difference from the first embodiment is that: the electron transport layer 2 in S9 uses the above-described compound 41 instead of the compound 1 in the embodiment. The other steps are the same as in the first embodiment.
Example IV
The difference from the first embodiment is that: the electron transport layer 2 in S9 uses the above-described compound 45 instead of the compound 1 in the example. The other steps are the same as in the first embodiment.
Comparative example
The difference from the first embodiment is that: the electron transport layer 2 in S9 uses the following compound Ref1 instead of the compound 1 in the example, and the other steps are the same as in the first example.
Table 1 shows the comparison results of the evaluation indexes of the examples and comparative examples. The plurality of evaluation indexes include a driving voltage of the light emitting device, a light emission peak (nm), an external quantum efficiency (external quantum efficiency, EQE), and a lifetime. In table 1, the results of the evaluation indexes of the first to fourth embodiments were obtained with reference to the evaluation indexes of the comparative examples. The external quantum efficiency EQE refers to the ratio of the number of photons finally emitted by the light emitting device to the number of injected carriers, reflecting the overall light emitting efficiency of the light emitting device.
As can be seen from the data comparison results in table 1, the light emitting device provided in the embodiment of the present disclosure, that is, the light emitting device using the derivative of the above-mentioned oxygen-containing heterocyclic compound in the electron transport layer, has no significant change in the emission peak value, but has significantly improved EQE and lifetime, compared with the comparative example, because the oxygen-containing heterocyclic compound material itself has higher mobility, better transport property and material stability. In addition, in the table 1, because the oxygen-containing heterocyclic compound has a deeper HOMO energy level, the driving voltage of the light-emitting device is reduced to different degrees, and the driving power consumption is saved.
TABLE 1
As can be seen from the data comparison results in table 1, the light emitting device provided in the embodiment of the present disclosure, that is, the light emitting device using the derivative of the above-mentioned oxygen-containing heterocyclic compound in the electron transport layer, has no significant change in the emission peak value, but has significantly improved EQE and lifetime, compared with the comparative example, because the oxygen-containing heterocyclic compound material itself has higher mobility, better transport property and material stability. In addition, in the table 1, because the oxygen-containing heterocyclic compound has a deeper HOMO energy level, the driving voltage of the light-emitting device is reduced to different degrees, and the driving power consumption is saved.
It should be further noted that, the derivative of the oxygen-containing heterocyclic compound provided in the embodiments of the present disclosure has a higher glass transition temperature Tg due to its stronger structural rigidity. The high Tg determines the thermal stability of the material in vapor deposition, and the higher Tg is, the better the thermal stability of the material is.
Table 2 shows the glass transition temperature test results of a plurality of compounds among the above examples of the derivatives of the oxygen-containing heterocyclic compounds and comparative examples provided in the examples of the present disclosure. This comparative example is the same as the comparative example in table 1 above. As shown in table 2, the glass transition temperatures of the above-mentioned compound 1, compound 39, compound 41, compound 45 and comparative example were measured by a DSC differential scanning calorimeter under a test atmosphere of nitrogen gas at a temperature rise rate of 10 ℃/min and in a test environment at a temperature range of 50 to 300 ℃.
TABLE 2
Tg(℃)
Comparative example 122
Compound 1 137
Compound 39 132
Compound 41 139
Compound 45 135
As shown in table 2, the Tg of the derivatives of the oxygen-containing heterocyclic compounds provided in the examples of the present disclosure were higher than that of the comparative examples. The higher Tg is beneficial to improving the thermodynamic stability of the material, and the material is not easy to crack and change when the light-emitting device is subjected to an evaporation process, so that the light-emitting device is beneficial to maintaining a higher service life.
The embodiment of the disclosure also provides a display substrate, which comprises the light-emitting device.
In some embodiments, the display substrate includes a plurality of pixel regions, each of which has the light emitting device described above disposed therein. Wherein the plurality of pixel regions include a red pixel region, a blue pixel region, and a green pixel region. The material of the light emitting device in the red pixel region is a red light emitting material, the material of the light emitting device in the blue pixel region is a blue light emitting material, the material of the light emitting device in the green pixel region is a green light emitting material, and specific material components of the light emitting materials of the three colors are described in detail in the above embodiments, which is not repeated here.
The embodiment of the disclosure also provides a display device, which comprises the display substrate.
The display device may be: any product or component with a display function, such as electronic paper, mobile phone, tablet computer, television, display, notebook computer, digital photo frame, navigator, etc., which is not limited in this disclosure.
It is to be understood that the above embodiments are merely exemplary embodiments employed to illustrate the principles of the present disclosure, however, the present disclosure is not limited thereto. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the disclosure, and are also considered to be within the scope of the disclosure.

Claims (7)

1. A derivative of an oxygen-containing heterocyclic compound, wherein the derivative of an oxygen-containing heterocyclic compound has the following structure:
2. a light emitting device, comprising:
a first electrode, a light emitting layer, and an electron transport layer between the first electrode and the light emitting layer;
the material of the electron transport layer includes a derivative of the oxygen-containing heterocyclic compound according to claim 1.
3. The light-emitting device according to claim 2, wherein the thickness of the electron transport layer is 20 to 100nm.
4. The light-emitting device according to claim 2, wherein the material of the electron transport layer further comprises Liq;
the doping ratio of the derivative of the oxygen-containing heterocyclic compound to the Liq is between 0.9:1 and 1.1:1.
5. The light-emitting device according to claim 2, further comprising: a second electrode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a hole blocking layer, and an electron injection layer;
the electron injection layer is positioned between the first electrode and the electron transport layer;
the hole blocking layer is positioned between the electron transport layer and the light emitting layer;
the light-emitting auxiliary layer, the hole transport layer, the hole injection layer and the second electrode are positioned on one side of the light-emitting layer away from the first electrode and are sequentially arranged along the direction away from the light-emitting layer.
6. A display substrate, characterized in that the display substrate comprises the light emitting device according to any one of claims 2-5.
7. A display device comprising the display substrate of claim 6.
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